Scientific UNITED Group

2nd International Conference on Catalysis and Chemical Engineering February 19-21, 2018

Venue Paris Marriott Charles de Gaulle Airport Hotel 5 Allee du Verger, Zone Hoteliere Roissy en France, 95700 France

Exhibitors

Supporting Sponsor Publishing Partner Supporter

Index

Keynote Presentations ...... 06 - 13

Speaker Presentations ...... 14 - 100

Poster Presentations ...... 102 - 123

About Organizer ...... 124 - 125 Key Concepts

→ Catalytic Materials & Mechanisms → Catalysis for Chemical Synthesis → Catalysis and Energy → Nanocatalysis → Material Sciences → Electrocatalysis → Environmental Catalysis → Chemical Kinetics → Reaction Engineering → Surface and Colloidal Phenomena → Enzymes and Biocatalysts → Photocatalysis → Nanochemistry → Polymer Engineering → Fluid Dynamics & its Phenomena → Simulation & Modeling → Catalysis for Renewable Sources → Organometallics Chemistry → Catalysis and Zeolites → Catalysis in Industry → Catalysis and Pyrolysis February 19 1Monday Keynote Presentations

The Development of Phosphorus- and Carbon-Based Photocatalysts

Jimmy C Yu The Chinese University of Hong Kong, Hong Kong

Abstract

This presentation describes the recent progress in the design and fabrication of phosphorus- and carbon-based photocatalysts. Phosphorus is one of the most abundant elements on earth. My research group discovered in 2012 that elemental red phosphorus could be used for the generation of hydrogen from photocatalytic water splitting. Subsequent studies show that the activity of red-P can be greatly improved by structural modification. Among the phosphorus compounds, the most stable form is phosphate. Its photocatalytic property was reported decades ago. Phosphides have also attracted attention as they can replace platinum as an effective co-catalyst. In terms of environmental friendliness, carbon is even more attractive than phosphorus. In 2017, we found that carbohydrates in biomass can be converted to semi conductive hydrothermal carbonation carbon (HTCC). Under solar light illumination, HTCC generates photoexcited electrons, holes and hydroxyl radicals. These species can be used for photocatalytic treatment such as water disinfection and degradation of organic pollutants. We have prepared recently HTCC nanosheets from carbohydrates under hydrothermal conditions. The nanosheets are extremely active for photocatalytic disinfection compared to its bulk counterpart. As we can use agricultural waste as a raw material, our conversion of carbohydrates to HTCC may be considered as a “trash to treasure” approach.

Biography

Jimmy Yu is Choh-Ming Li Professor of Chemistry and Head of United College at The Chinese University of Hong Kong. He has graduated from St. Martin’s College in 1980, and received a PhD from the University of Idaho in 1985. He taught at University of Puget Sound and University of Central Missouri before joining the Department of Chemistry at CUHK in 1995. Professor Yu is a prolific writer who also holds several patents on photocatalytic nanomaterials. He appears on the list of Thomson Reuters’ Highly Cited Researchers 2016 in both Chemistry and Materials Science.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 6 Versatile Transition Metal-Phosphate Catalysts and Applications

Ange Nzihou*, Nathalie Lyczko, Rajesh Munirathinam, Bruna Rego de Vasconcelos and Doan Pham Minh Université de Toulouse, France

Abstract

Support effect in catalysis is an important field of investigation to optimize catalyst properties. Catalyst supports such as alumina, silica, titania, niobia, zirconia, zeolite, ceria, carbon-based materials, silicon carbide, metal-organic frameworks, and metal foams as used in various catalytic applications. The properties such as metal-support interaction, support size, morphology, acid-base nature, surface area, porosity of the support, and change in electronic properties of the metal clusters are crucial to the activity of the catalyst. Hydroxyapatite (CaP, Ca10(PO4)6(OH)2), is a double salt of tricalcium phosphate and calcium hydroxide- based material that contains both acid and base functionalities . Further, it exhibits high thermal stability, extremely low water solubility, and tunable surface area with or without porosity. The molar ratio of Ca/P in the stoichiometric form of CaP is 1.67. The ionic radius of CaP’s component elements (Ca and P) permits to certain extent the transfer or loss of ions within its crystal structure, consequently leading to non-stoichiometric CaP (Ca10-Z(HPO4)Z(PO4)6-Z(OH)2-Z ; 0 < Z ≤ 1) with a Ca/P molar ratio in the range of 1.50 ≤ 1.67 ≤ 1.80. This possibility helps in tuning the density of acid and base sites, which is not possible in the case of conventional catalyst carriers. Further, the calcium ions in HAP can be easily exchanged with most divalent cations, for example, Pb2+, Zn2+, Cd2+, Co2+, etc. without affecting the stability of the phosphate. These characteristics of CaP make it a unique support in heterogeneous catalysts. The functions and properties together with some applications will be discussed.

Biography

Ange Nzihou is Director RAPSODEE Research Center -CNRS, IMT Mines Albi – France. He is Editor-in-Chief of a Springer Journal “Waste and Biomass Valorization”. He has published more than 120 papers in peer reviewed journal and has been cited about 970 times. He is Guest Professor in number leading universities in USA, China and Europe. He has developed outstanding research in Thermochemical conversion Processes of Biomass and Waste to Energy and Added Value Materials. The second main field is the characterization, mechanisms, elaboration, functionalization of composite / hybrid materials (sorbents, catalysts, energy carriers, sensors) for energy and depollution.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 7 Characterization of Ce-Fe Oxides: Influence of the Dopant on the Structure

Martin Schmal1*, Rodrigo Brackmann1, Fabio S. Toniolo1 and Sergio Gustavo Marchetti2 1NUCAT/COPPE/UFRJ, Brasil 2CINDECA-UNLP, Argentina

Abstract

+3 We studied the influence of Fe incorporation into CeO2 oxide on its physicochemical properties aiming application for

NOx abatement by CO-SCR. Ce1-xFexO2-δ mixed oxides (x = 0; 0.05; 0.1; 0.15 and 0.2) were prepared by Pechini method.The + image of the mixed oxide Ce0,8Fe0,2O2-δ calcained and reduced of the mixed oxides. The EPR spectra revealed a presence of Ce 3 +3 in the non-doped CeO2, indicating the existence of intrinsic vacancies. In iron-doped samples are present isolated Fe sites + 3 with orthorhombic distortion, as well as Fe species in clusters. The Ce1-xFexO2-δ (x = 0,15 and 0,2) samples were investigated by Mossbauer before and after reduction. Results showed that there are 53% isolated Fe3+ and 47% of iron Fe3+clusters. The magnetization measurements and the presence of a pure Cerium have a diamagnetic component (typical of the CeO2 insulating structure) and a ferromagnetic component. This option is related to the oxygen vacancies through the structure Ce+3- δ - Ce+3, which characterizes a quasi-particle, where δ symbolizes an anion vacancy, which compromises the presence of this type of + 3 defeat in CeO2. All samples doped with Fe showed paramagnetic and ferromagnetic components. The doped component increases with the increasing Fe+3 content up to 10% and then decreases. This behavior is related to a competition between two mechanisms: a formation of polarized (Ce+3-δ-Ce+3 and Ce+3-δ-Fe+3) that increases ferromagnetism and the formation of super interactions exchange Fe+3-δ-Fe+3 anti- ferromagnetic.

Biography

Martin Schmal is a Professor Emeritus at Federal University of Rio de Janeiro. He has about 285 publications and 5 Books and has above 6000 citations (IH 43, 44).

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 8 Streamlined Nanocomposites for Heterogeneous Catalysis

Hua Chun Zeng National University of Singapore, Singapore

Abstract

Systems of heterogeneous catalysis can be viewed as dispersed solid-liquid or solid-gas flows. Therefore, the geometric shape of particulate catalysts is fundamentally important, because an optimal shape configuration of catalysts can promote the transport processes and thus enhance catalytic activity in fluid-related reactions or environments. For example, a streamline body represents a superior geometry since it experiences minimum fluid resistance. However, utilization of streamline-shaped catalysts has remained an unexplored area due to the lack of easy-to-use techniques to produce such shaped catalysts, especially in the small length scale of submicron to micron regime. In this presentation, we will report our recent development of a class of prototype nanocatalysts with streamline shapes and complex chemical compositions. Advantages related to the streamline morphology of catalysts will be demonstrated with a number of solid-solution systems such as alcohol oxidation, olefin hydrogenation, and Suzuki-Miyaura coupling. Significantly, such streamline-shaped nanocatalysts indeed can reduce fluid resistance and provide structural benefits in catalytic applications compared to other commonly used counterparts. We envision that future development of streamline-based composite materials, in combination with various functional nanostructured materials, will play a greater role in design and synthesis of new generation catalysts or sorbents for multiphase processes.

Biography

Hua Chun Zeng obtained his B.Sc. in Chemistry from Xiamen University in 1982 and Ph.D. in Physical Chemistry (with Professor Keith A. R. Mitchell) from University of British Columbia in 1989. Following postdoctoral work (with Professor John C. Polanyi, Nobel Laureate in Chemistry, 1986) at University of Toronto, he joined the faculty at National University of Singapore in 1991. His research interests are, at present, focused on the exploratory design and synthesis of inorganic nanostructures, with an emphasis on heterogeneous catalysis.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 9 Nanoscopic Aluminium Fluoride - The Strongest Solid Lewis Acid Ever

Erhard Kemnitz* and Thoralf Krahl 1Humboldt-University of Berlin, Germany 2Nanofluor GmbH Berlin, Germany

Abstract

High surface aluminium fluoride,HS -AlF3, and aluminium chlorofluoride, ACF, (AlClxF3–x, x = 0.05…0.3) are amorphous solids with an extraordinary high Lewis acidity, which play an increasingly important role in heterogeneous catalysis. They are excitingly good heterogeneous catalysts for C–H and C–F activation reactions which perform already at room temperature at ambient pressure, and thus, outperform in several cases even precious metal based homogenous catalysts. Although the catalytic performances of both phases are often very similar, differences can be found that originate from the differences in their porosity.

This is, ACF is dominantly microporous whereasHS -AlF3 is rather mesoporous. That means larger molecules show better reaction performances at HS-AlF3 as catalysts whereas smaller molecules as a rule perform better at ACF. There is another distinct difference between both AlF3 phases: ACF is extremely moisture-sensitive and undergoes irreversible hydrolysis reaction that turns the existing Al–Cl bonds into Al–OH bonds. As a result, ACF completely loses its high Lewis acidity, and thus, its superior catalytic properties. This is different withHS AlF3, which expectedly adsorbs water easily but without undergoing a hydrolysis reaction. Consequently, adsorbed water can be desorbed from the solid followed by CFC activiation, and the full Lewis potential is recovered this way.

Biography

Erhard Kemnitz studied chemistry at the Humboldt-Universität zu Berlin (Germany). In 1977 he received his doctoral, in 1986, he finished his Habilitation. In 1988 he became an assistant professor and received a full-time tenure track in 1994, both at the Humboldt-Universität zu Berlin. He was head of the Chemistry Department of Humboldt-University from 2001 until 2004. His main research interests cover the synthesis and characterisation of nanoscopic metal fluorides for applications in the field of heterogeneous catalysis, optics, ceramics, surface coating etc. He published about 450 papers, 11 review articles,12 books and/or book chapters, and filed several patents.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 10 Chemically Modified Carbon Nanotubes & Graphene for Energy & Catalytic Applications

Sang Ouk Kim Korea Advanced Institute of Science and Technology, South Korea

Abstract

Carbon nanotubes and graphene attract enormous research attention for their outstanding material properties along with molecular scale dimension. Optimized utilization of the graphene based materials in various application fields inevitably requires the subtle controllability of their structures and properties. In this presentation, our recent research works associated to nanoscale assembly and chemical modification of the graphene based nanomaterials will be presented. Carbon nanotubes and graphene can be efficiently assembled into various three-dimensional structures via self-assembly principles. The resultant carbon assembled structures with extremely large surface and high electro-conductivity are potentially useful for catalysis, energy storage and so on. Aqueous dispersion of graphene oxide shows liquid crystalline phase, whose spontaneous molecular ordering is useful for display, fiber spinning, membrane and so on. In addition, the substitutional doping of graphitic carbon with B- or N- was achieved via pre- or post-synthetic treatment. The resultant chemically modified graphene based nanostructures with tunable workfunction and remarkably enhanced surface activity/catalytic activity could be employed for organic solar cells, nanocomposites, catalysts and dopant specific unzipping process for innovative functionalities and device performances.

Biography

Sang Ouk Kim is the Professor in the Department of Materials Science and Engineering at KAIST, Korea and the director of National Creative Research Initiative Center for Multi-Dimensional Directed Nanoscale Assembly. He obtained his Ph.D at KAIST in 2000 and experienced postdoctoral research at University of Wisconsin-Madison, USA. Prof. Kim has published more than 200 SCI journal papers and delivered more than 300 invited presentations thus far. He is the recipient of numerous prestigious awards including Presidential Young Scientist Award and KAIST Academic Grand Prize. Prof. Kim is serving as editorial board member for more than 10 scientific journals publisehd by RSC, ACS, Wiley, Elevier, Springer, etc.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 11 Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

Jean-Marie Basset*, Manoja Samantaray, Anissa Bendjeriou-Sedjerari, Eva Pump and Jérémie D. A. Pelletier King Abdullah University of Science and Technology, Saudi Arabia

Abstract

Heterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render it more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their “acid strengths” or “redox properties” are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure–activity relationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure–activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure–activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).

Biography

Basset received his PhD in 1969 from the University of Lyon, France. After a postdoctoral position in Toronto he moved to the Institute of Catalysis in Lyon where he became vice-director. He is Chevalier dans l’Ordre National du Mérite. He came to CNRS in 1971 and has occupied several positions, including vice-director of the Institute of Catalysis. He is the author of over 500 publications and 50 patents. His main research interests are the relations between homogeneous and heterogeneous catalysis, the metathesis of olefins and alkanes as well as Ziegler–Natta depolymerization. He has discovered thanks to the discipline of Surface organometallic Chemistry.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 12 Development of Ni-Based Catalysts Coupled with Membrane Reactor for H2 Production

Sibudjing Kawi National University of Singapore, Singapore

Abstract

H2 has been regarded as a renewable and green energy source which is promising to replace the conventional fossil fuel.

One way to get H2 is via catalytic reforming, such as steam/dry reforming of methane, steam reforming of biomass etc. The main challenge to be address is to develop economic, effective and stable catalysts. Nickel, as a cheap and common transient metal, shows excellent catalytic performance has been studied a lot and our group has been working on development of Ni- based catalysts for H2 production for decades. We have developed several strategies to enhance the catalytic activity and stability, including strong-metal support interaction, confinement effect, and synergistic effect of alloy and so on. Those catalysts show superb activity, selectivity and stability for steam/dry reforming of methane, steam reforming of toluene and water-gas shift reaction. Meantime, we are trying to combine catalysts with H2 and O2 permeable membrane to further increase the activity.

Membrane reactors combining catalysts with Pd membranes and perovskite membranes are developed and modified for 2H and O2 involving reactions respectively.

Biography

Sibudjing Kawi (PI) is a productive researcher and has published more than 220 international peer-reviewed journal articles. He obtained his Ph.D. in Delaware and has been attached to the Department of Chemical and Bio-molecular Engineering at the National University of Singapore since 1994. In the past decade, his research has focused on the design and synthesis of nano-catalysts for green and sustainable development, such as CO2 reforming with methane to bio-syngas and hydrogen, CO2 methanation, biogas reforming, biomass gasification, and the water gas shift reactions. His expertise also includes the synthesis of novel inorganic membranes, as well as catalytic membrane reactors with in-situ oxygen and hydrogen separation and reaction.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 13 Speaker Presentations

Scientific Session 1: Catalysis for Chemical Synthesis

Translating Organometallic Properties into High-Performance Catalysts for Organic Synthesis

Michael G. Organ University of Ottawa, Canada

Abstract

Considerable effort for almost half a century has been devoted to understanding how ligand steric and electronic properties modulate the reactivity of a metal centre in a large number of catalytic processes. This is confounded by the fact that many of these transformations have two or more steps in their catalytic cycles, which may mean that a favorable attribute in one step may act to disfavor another step. Many groups have worked diligently to develop methods to probe and grade ligand properties such that they can be used in, ideally, a predictive fashion to guide the development of new catalysts. In this presentation our approach to rational ligand design in cross-coupling applications will be discussed and how this approach has been used to improve catalyst performance. In particular, time will be dedicated to the discussion of 1) the incorporation of secondary alkyl centers without isomerization and 2) in the introduction of primary amines without over arylation.

Biography

Michael G. Organ received his PhD in 1992 at the University of Guelph under the tutelage of Professor Gordon L. Lange. He then was an NSERC Postdoctoral Scholar in the laboratory of Professor Barry M. Trost at Stanford (1994). Effective January 2016, he is the new Director of the Centre for Catalysis Research and Innovation (CCRI) at the University of Ottawa. His group’s effort in catalysis has led to the creation of a broadening series of N-heterocyclic carbene (NHC)-based organometallic complexes (coined PEPPSI for pyridine-enhanced pre-catalyst preparation, stabilization, and initiation) that have shown unsurpassed reactivity and selectivity in a wide number of cross-coupling applications.

Chiral Bifunctional Phase-Transfer Catalysis – Catalyst Design and Applications

Mario Waser Johannes Kepler University Linz, Austria

Abstract

Chiral Phase-Transfer-Catalysis is one of the outstanding catalytic principles for asymmetric reactions and has attracted the interest of academic and industrial chemists. Over the course of the last years our group has been systematically addressing the design and use of novel chiral bifunctional phase-transfer catalysts for a variety of challenging transformations. In this talk I will give a detailed overview about this topic, highlighting the advantages and also the limitations of this powerful catalysis methodology.

Biography

Mario Waser was born in Austria and studied chemistry at the University Linz, Austria was he obtained his Ph.D. in 2005 in the group of Prof. Heinz Falk, working on hypericin-based photosensitizers. After a postdoctoral stay in the group of Prof. Alois Fürstner at the MPI für Kohlenforschung (Mülheim, Germany), contributing to the first total syntheses of iejimalide B and iejimalide A, he spent two years as an R&D chemist at DSM. In 2009 he started his independent career as an Assistant Professor in Linz. In 2014 he obtained his habilitation (venia docendi) and became Associate Professor. His main research interests are on the design and application of asymmetric organocatalysts and on the development of catalytic synthesis methods.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 14 The Manipulation of Electron-Electron Interactions in Graphene on SrTiO3 via Temperature

Choongyu Hwang Pusan National University, South Korea

Abstract

Near the charge neutral point, graphene exhibits interesting many-body interactions beyond what Fermi liquid theory can predict. We investigate such many-body effects in charge neutral graphene using angle-resolved photoemission spectroscopy. The electron band structure shows strong deviation from the characteristic linearity at low temperatures. Our finding suggests a possible realization of strong correlations between Dirac fermions in graphene via temperature.

Biography

Choongyu Hwang worked as an Assistant Pprofessor of Physics department in Pusan National University, South Korea from 2013-2017. Since 2017, he is working as an Associate Professor of Physics department in Pusan National University, South Korea. His research interests are realization and manipulation of strong electronic correlations in two-dimensional systems.

Catalytic Activity of Bimetallic AuPd Alloys Supported MgO and MnO2 Nanostructures and their Role in Selective Aerobic Oxidation of Alcohols

Hamed Alshammari1*, MosaedAlhumaimess2, Mohammad HayalAlotaibi3 and Abdullah S Alshammari1 1Ha’il University, Saudi Arabia 2Aljouf University, Saudi Arabia 3King Abdulaziz City for Science and Technology, Saudi Arabia

Abstract

The use of metal oxides as supports for gold and palladium (Au-Pd) nanoalloys constitutes new horizons to improve new active catalysts in very important reactions1. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance2, 3. In this study, nanostructures of Magnesium oxide (MgO) and nano Manganese dioxide (MnO₂) were synthesized and utilized as supports for Au-Pd nanoparticles catalysts. Gold and palladium were deposited on these supports using sol-immobilization method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol, aliphatic, aromatic alcohols and 1-octanol, respectively. This catalyst was found to be selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

Figure 1: Graphical Abstract.

References: 1. Bartley, J. K., Xu, C., Lloyd, R., Enache, D. I., Knight, D. W. & Hutchings, G. J. 2012.. Applied Catalysis B: Environmental, 128, 31-38. 2. Y., Luan, Y., Yu, J., Peng, X. & Wang, G. 2015. Chemistry–A European Journal, 21, 1589-1597. 3. Yu, J., Luan, Y., QI, Y., Hou, J., Dong, W., Yang, M. & Wang, G. 2014. RSC Advances, 4, 55028-55035.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 15 Heterogeneous Catalysts for Lower Alkane Activation: Structure and Activity

Shiju Raveendran University of Amsterdam, The Netherlands

Abstract

Heterogeneous catalysts enable many chemical transformations of fossil as well as renewable resources into useful products. Several of the industrial catalysts are nanostructured metal oxides or contain an active component in the form of nanoparticles that are dispersed onto high surface area supports. Their catalytic performance often depends on their nanostructure. Understanding these nanostructure-activity relations is crucial in designing novel efficient catalysts. In this talk, I will present our recent results on the influence of structural features on catalytic activity in the activation of lower alkanes.

One example is the effect of basal planes of Mo- and V- based mixed oxide catalysts on the selectivity of partial oxidation products of propane. By selectively passivating the external surface, we enhanced the selectivity for partial oxidation. Another example is the partial oxidation of butane to produce butenes and butadienes, which are important raw materials for the synthesis of polymers and other chemical products. Traditionally they are obtained mainly from steam cracking and catalytic cracking units. Recently we discovered that Ti3AlC2, a MAX phase, which hitherto had not used in catalysis, efficiently catalyses the ODH of n-butane to butenes and butadiene. The catalyst, which combines both metallic and ceramic properties, is stable for at least 30 h on stream, even at low O2: butane ratios without suffering from coking. This material has neither lattice oxygens nor noble metals, yet a unique combination of numerous defects and a thin surface mixed oxide layer that is rich in oxygen vacancies makes it an active catalyst.

Biography

Shiju Raveendran is an Associate Professor at the University of Amsterdam and is interested in developing catalytic processes for commercially important chemical transformations. In 2010, he won the Amsterdam Science Park Ideas Prize for the discovery of a new catalyst. He has obtained grants for CO2 conversion to chemicals in a plasma-catalytic hybrid reactor and in an electrocatalytic reactor, for Design of Heterogeneous Catalysts for Chemo-selective Synthesis of Cyclohexylamines, for developing an economic process for converting biomass derived levulinic acid to value-added products and for developing graphene-metal oxide composite coatings.

Possibility of Technological Development by Vanadium Complexes based Polymer Supported Catalysts

Mannar R Maurya Indian Institute of Technology Roorkee, India

Abstract Solid supported catalysts can go a long way in developing catalyst-based technology because of their high efficiency with recyclability and easy separation from the reaction mixture. Immobilisations of homogeneous catalysts through covalent bond with chloromethylated polystyrene cross-linked with divinylbenzene and develop them as environmentally safe heterogeneous catalysts for oxidation reaction have attracted attention in recent years. This method has now become a very specialized method because polymer-anchored catalysts inherit the advantages of both homogenous as well as heterogeneous catalysts as they are thermally more stable, selective and recyclable, and allow their easy recovery from the reaction products at the end of the reaction. Recently, effort from our research laboratory was to synthesize new recyclable polymer-supported vanadium complexes based heterogeneous catalysts. Thus, chloromethylated polystyrene cross linked with 5% divinylbenzene was used as support to prepare variety of polymer supported vanadium catalysts. These catalysts have been characterized with the help of various physico-chemical techniques such as elemental, spectral (FT-IR, electronic, 1H- and 51V NMR, and EPR), field emission scanning electron microscope coupled with an energy dispersive X-ray analyses (EDAX), atomic force microscopy imaging and thermal analysis patterns. The formulations of the polymer-anchored complexes are based on the respective neat complexes and conclusions drawn from the various characterization studies. These catalysts have successfully been used for the oxidation and oxidative bromination of various organic substrates. The catalytic oxidative desulfurization of organosulfur compounds (model of fuel diesel) has been carried out using supported vanadium complexes. The percent conversion of substrate, analysis of reaction products and their selectivity were calculated

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 16 from gas chromatography data. The identity of the products was confirmed using a GC-MS by comparing the fragments of each product with the library available.

Keeping in mind the industrial usage of the heterogeneous catalysts, the leaching and recycle ability of all polymer- supported catalysts has also been tested. All these catalysts are stable and do not leach during the catalytic reactions.

References: 1. M.R. Maurya, A. Kumar and J. Costa Pessoa, Coord. Chem. Rev., 255, 2315-2344 (2011) 2. M.R. Maurya and J. Costa Pessoa, J. Organometal. Chem., 696, 244–254 (2011) 3. J. Costa Pessoa and M.R. Maurya, Inorg. Chim. Acta, 455, 415–428 (2017).

Formation and Dissociation of Methane, Oxygen evolution Reaction and Hydrogenation of Carbonyl Compounds: First Principles Studies

Swapan K Pati1*, Shubhajit Das1, Pallavi Bothra2 and Swastika Banerjee1 1Jawaharlal Nehru Centre for Advanced Scientific Research, India 2Stanford University, CA, USA

Abstract

It includes discussion of four catalytic processes, namely, (a) formation mechanism of methane [1], (b) dissociation of Methane gas and steam methane reforming reaction [2] (c) oxygen evolution reaction [3] and hydrogenation of carbonyl compounds [4]. For (a), we have considered the complete hydrogenation mechanisms of CO2 on Ni (110) surface. For (b), we have studied the complete dehydrogenation of methane and then steam methane reforming reaction (SMR) on pure Ni (110) and single Rh layer deposited Ni (110) surface. For (c), a comparative study of the electrochemical behavior of pure and metal doped cobalt oxides, Co3O4 and MxCo3−xO4, (M = Fe, Ni, Cu) have been performed to understand their structure, mechanism, and activity behavior towards the oxygen evolution reaction (OER). Finally, by using metal free frustrated Lewis pair catalysis, we have derived a detail mechanism behind hydrogenation of carbonyl compounds to the corresponding secondary alcohols [4]. In the case of rechargeable battery, we have looked at the potential of using Boron-sheet, BCN layer and Black Phosphorous as anode materials for Li, Na and Mg ion rechargeable battery [5-7].

References: Co-authors and S. K Pati: 1. Phys. Chem. Chem. Phys. 15, 5701 (2013) 2. Nanoscale 6, 6738 (2014) 3. ACS Energy Lett. 1, 858 (2016) 4. Chem: A Euro J. 23, 1078 (2017) 5. J. Mater. Chem. A 2, 3856 (2014) 6. J. Mater. Chem. A 4, 5517 (2016) 7. Chem. Commun. 52, 8381 (2016)

Biography

Swapan K Pati is a full professor and currently chairman of Theoretical Sciences Unit, JNCASR, Bangalore. He has been a visiting faculty member to a number of Universities and Institutes in USA, Europe and also Universities in China and Japan. He has a vibrant group of young researchers who develop and use a large number of theoretical tools. His work encompasses the interdisciplinary areas of Physics, Chemistry, Materials Science and Engineering. Because of his versatility in calculations over many time, energy and length scales, he is sought after by experimentalists across science and engineering disciplines for providing insights.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 17 Catalysis in Peroxide Synthesis from Carbonyl Compounds and H2O2

Alexander Terent’ev1, 2*, Peter S. Radulov1, Anatoly E. Velikotsky1 and Yuliya Yu. Belyakova1 1N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Russia 2D. I. Mendeleev University of Chemical Technology of Russia, Russia

Abstract

In the last decades, organic peroxides have received considerable attention from chemists and drug design experts, which is associated with a need in the search for drugs for the treatment of parasitic diseases, such as malaria and helminth infections. Peroxides having antitumor or growth-regulatory activity were also documented. Traditionally organic peroxides are applied in industry as initiators of free radical polymerization and oxidants. In our work we developed new and green methods for synthesis of various types of peroxides using hydrogen peroxide and carbonyl compounds. Nature of a catalyst plays the decisive role on the selectivity of peroxide preparation.

R1 R2 O R1 O O O R O O 2 O O R R3 H2O2 O 4 2 R1 O R R O 3 R2 9 O O R O O 1 4 O 2 R O O R R1 R

References: 1. A.O. Terent’ev, I.A. Yaremenko, V.V. Chernyshev, V.M. Dembitsky, G.I. Nikishin, J.Org.Chem. 2012, 77, 1833 2. K. Ingram, I.A. Yaremenko, I.B. Krylov, L. Hofer, A.O. Terent’ev, J. Keiser, J.Med.Chem. 2012, 55, 8700 3. I.A. Yaremenko, A.O. Terent’ev, V.A. Vil’, R.A. Novikov, V.V. Chernyshev, V.A. Tafeenko, D.O. Levitsky, F. Fleury, G.I. Nikishin, Chem.Eur.J. 2014, 20, 10160 4. dos Passos Gomes, G., I.A. Yaremenko, P.S. Radulov, R.A. Novikov, V.V. Chernyshev, A.A. Korlyukov, G.I. Nikishin, I.V. Alabugin, A.O. Terent’ev, Angew.Chem.Int.Ed. 2017, 56, 495

Biography

Alexander O. Terent’ev was born in Moscow, in 1973. He has obtained PhD degree in 2000 and D.Sc. degree in 2009. Since 2011, he is working as a Professor at D. Mendeleev University of Chemical Technology of Russia. He is the Head of laboratory in N.D. Zelinsky Institute of Organic Chemistry RAS, Head of laboratory in All-Russian Research Institute of Phytopathology. His interests are organic chemistry, medical and agricultural chemistry, chemical technology. He published 3 chapters in books, 100 research papers, and 30 patents.

First Principles Analysis of Catalytic Activity of Alloys and Compounds

Seung-Cheol Lee* and Kapil Gupta Indo Korea Science and Technology Center, India

Abstract

There has been a constant effort to find a replacement to the precious metal Pt as a catalyst in Hydrogen Evolution Reaction (HER). Non-precious Metal phosphides are found to show remarkable catalytic activity as compared to platinum. In this work from our first principle density functional calculations we discuss, how Ni2P surface evolve during electrolysis and assist in Hydrogen evolution. From our calculations we show the most stable termination of Ni2P (0001) surface. We show that Ni2P (0001) surface gets modified under excess phosphorous available. Using our first principle results we show how this modified surface further assists H adsorption on these surfaces. We use ab-initio thermodynamics to approximate and compare the catalytic activity with Pt and other precious metals. Our calculation results successfully explained surface behavior observed in experiments and also provided further guidelines.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 18 In addition to phosphide surfaces, we will present our recent works on developing alloy catalysts for HER, OER and ORR.

Biography

Seung-Cheol Lee has received his PhD in Materials Science from Seoul National University in 1999. He has worked for materials design through density functional theory calculation and molecular dynamics simulation. His research interests are modeling atomic structures and atomistic behavior to understand catalytic reactions and mechanical properties of materials.

The Role of Magnetism in the Chemical Reactivity of the Transition Metal Surfaces

Satadeep Bhattacharjee1*, Umesh V. Waghmare2 and Seung-Cheol Lee1 1Indo Korea Science and Technology Center, India 2Jawaharlal Nehru Centre for Advanced Scientific Research, India

Abstract

This presentation overviews our recent works which relate the magnetism to the chemical reactivity of the transition metals and their alloys. For the prediction of the trend of the catalytic behaviour in transition and noble metals, the most widely used model known to be the so called d-band center model, which correlates the adsorption energy to the average energy of the d electrons (d band center) of the metal surface, and has been proved successful in understanding the chemical bonding in heterogeneous interfaces various solid-gas and solid-liquid phases. We demonstrated that this model, which was initially proposed for studying the adsorption of small molecules on the so-called platinum group of metals, is inadequate in capturing the complete catalytic activity of the magnetically polarized transition metal (TM) surfaces and propose its generalization by invoking two distinct band centers for spin majority and spin minority d-electrons. Also, we studied the role of spin orientation in the oxygen based electrochemical reactions such as oxygen reduction reaction (ORR) using PdFe (001) surface as a model ferromagnetic electrode. We demonstrated that the strength of the bindings of the reaction intermediates can be related to their relative spin orientations with respect to the direction of the electrode’s magnetization. We discuss about the possibility of controlling such chemical reactions through magnetic field by introducing a new quantity: spin orientation dependent overpotential.

Biography

Satadeep Bhattacharjee obtained his PhD in physics from the University of Madras in 2005. After his PhD, he worked in different places such as University of Bonn, Germany, University of Liege, Belgium, Uppsala University, Sweden, and University of Arkansas, USA. His research interest is in materials theory with an orientation towards magnetism. Prior joining to Indo Korea Science and Technology Center his research activities mainly involved the study of multiferroic oxides under strain, electric field etc using density functional theory based methods and magnetization dynamics, study of spin switching in metallic multilayers, electronic structure of the magnetic molecules etc.

Kinetic Modeling of the Direct Amination of n-Octanol with Ammonia over a Ag- Co/Al2O3 catalyst

Javier Ibáñez1,2, Sébastien Paul1, Marcia Araque-Marin1 and Marc Pera-Titus2 1Unite de Catalyse et de Chimie du Solide (UCCS), France 2Eco-Efficient Products and Process Laboratory (E2P2L), China

Abstract

Despite the scientific interest dedicated to the discovery of catalytic formulations for amination reactions, only very few comprehensive kinetic studies have been reported in the literature. More specifically, the effect of2 H pressure has been generally omitted. To fill the existing gap in the current understanding of amination catalysts, herein we conducted a rigorous and comprehensive kinetic study surveying the effect of the different operation variables on a homemade 5 wt% Ag3-Co97/Al2O3 catalyst for the gas-phase amination of n-octanol with NH3.

By implementing a full factorial design of experiments, 126 gas-phase catalytic tests were carried out in a high-throughput Flowrence unit (Avantium®, REALCAT platform). For the most part, the observed kinetic trends matched traditional kinetic models reported for amination, considering alcohol dehydrogenation as rate determining step. On the contrary, the effect of hydrogen pressure was unexpected: hydrogen increased the n˗octanol conversion and boosted the formation of the secondary

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 19 amine. A kinetic model was developed, proposing a plausible coking-regeneration mechanism explaining the a priori non- intuitive effects of the 2H pressure. The intermediaten -octylimine was identified as the most likely coke sourcevia statistic model discrimination. The fitted kinetic model was able to faithfully describe the complex reaction network over a broad range of experimental conditions and could correctly extrapolate to higher conversions. Furthermore, the model provides an optimal explanation of the unexpected effect of the 2H pressure on the catalytic activity and selectivity.

Highly Efficient Decomposition of Rhodamine B under Visible-Light with Nanotubular Ag@AgCl@ AgI Photocatalysts

Kuen-Song Lin1*, Jun-Qi Xiao1,2 and Chao-Lung Chiang1 1Yuan Ze University, Taiwan 2Fuzhou University, China

Abstract

In recent decades, AgX (X = Cl, Br, I) have been regarded as the novel and efficient visible-light photocatalysts for the decomposition of different organic compounds, especially for dyes. In this study, heterostructured Ag@AgCl@AgI nanotubes were prepared with an anion-exchange method, using Ag@AgCl nanotubes and I− anions. Their photocatalytic activities towards the decomposition of organic pollutants were also investigated. These as-prepared photocatalysts were respectively characterized with X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy combined with energy-dispersive X-ray spectroscopy (HR-TEM/EDS), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. Moreover, the structure characterization results clarified that the photocatalyst sowed unique nanotubular morphology. In comparison of polyhedral Ag@AgI nanoparticles, the incorporation of Br− ions into the Ag@AgCl framework obviously improved the photocatalytic activities. Because of their high stability, these as-prepared Ag@AgCl@AgI nanotubes can be reused for many times. Notably, more than 91.8% of Rhodamine B (RhB) was decomposed within 45 min using the catalyst AI-2 (Cl-/I- = 1:1) under visible light irradiation. The surface area-enhanced AI-2 catalyst shows its outstanding photocatalytic activity and photoelectron transfer, which is ascribed to its unique nanotubular heterostructure.

Biography

Kuen-Song Lin, a senior professor in the Department of Chemical Engineering and Materials Science, Yuan Ze University in Taiwan. He is also the director of Environmental Technology Research Center (ETRC) and dean of Research and Development (R&D office) in Yuan Ze University. His research topics includes the waste recycling/reutilization, on-site soil/ water pollution remediation, environmental/photocatalytic catalyst preparation technologies, hydrogen storage, carbon capture, and sustainable energy generation.

Modeling Residence Time Distribution of Lab-Scale Packed Bed Reactor

Jaipat Seripanu1*, Atittahn Wongkia2, Arthit Vongachariya2, Wipada Lertpukpon2, Kongkiat Suriye2, Piyasan Praserthdam1 and Suttichai Assabumrungrat1 1Chulalongkorn University, Thailand 2SCG Chemicals, CO., Ltd., Thailand

Abstract

A plug flow model has been widely used to simulate a packed bed reactor, a main reactor commonly used in both laboratory and industry, but researchers have still observed unexpected flow behavior in a real reactor. Therefore, reactor analysis by investigating residence time distribution is essential to predict and to understand real behavior which deviates from the ideal reactor model. In this study, the residence time distribution of lab-scale packed bed reactor was modeled using RTD 3.14 which allowed users to compute output signal for the flow model by Laplace transform method. The tracer experiments were conducted at T = 573 K by feeding ethylene downward from the top of a reactor (I.D. = 157.5 mm) at a flowrate of 100 cm3/ min and the distribution curve was determined after a transient step input of helium as a tracer. The experiments were studied both in the empty reactor and the reactor packed with catalyst (5.04 g). The operating pressure was varied up to 30 bar, while 3 types of packing were varied to study effect of void fraction.The result curves show fraction of material leaving reactor (F) and the model can predict experimental data well. Increasing operating pressure leads to lower Peclet number and longer mean

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 20 residence time which mean more deviation from ideal case. Shorter residence time is expected when decreasing void fraction. Additionally, Computational Fluid Dynamics was also employed to simulate flow inside reactor.

Biography

Jaipat Seripanu was born on March 27th, 1994 in Bangkok, Thailand. She graduated with a bachelor’s degree in chemical engineering from the Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand, in June 2016. She continued her study in master degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2016 under the SCG Chemical Co.,Ltd., (Thailand) scholarship.

Characterization of Acidity and Basicity on Aluminium Magnesium Oxide (AMO) and Hydrotalcite Catalysts

Narut Asawawetmongkon1*, Kongkiat Suriye2, Piyasan Praserthdam1 and Joongjai Panpranot1 1Chulalongkorn University, Thailand 2SCG Chemicals, CO., Ltd., Thailand

Abstract

Aluminium magnesium oxide (AMO) and hydrotalcite catalyst are two different types of magnesium aluminium catalysts that have been using in industry. The acidity and basicity of different catalysts were studied to obtain the effects for catalyst activity by using temperature program desorption of ammonia(NH3-TPD) and carbon dioxide temperature-programmed desorption (CO2-TPD).The results showed that AMO catalyst has higher amount of acid sites and strong basic sites than hydrotalcite catalyst. Furthermore, the study of thermal stability of catalyst was investigated via vary calcined temperatures. The collapsed structure was characterized by X-ray diffraction (XRD) technique. Other physical properties of catalysts were characterized by N2 physisorption and Fourier-transformed infrared spectroscopy (FT-IR).

Biography

Narut Asawawetmongkon was born on December7th, 1993 in Bangkok, Thailand. He graduated with a bachelor’s degree (first class honors) in chemical engineering from the Faculty of Engineering, Kasetsart University, Bangkok, Thailand, in May 2016. He continued his study in master’s degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2016 under the SCG Chemical Co., Ltd., (Thailand) scholarship.

New Defect Structure Controlling of Silicalite by Alkoxide and Precipitation Route

Noppasak Viputvipaporn1*, Kongkiat Suriye2, Joongjai Panpranot1 and Piyasan Praserthdam1 1Chulalongkorn University, Thailand 2SCG Chemicals, CO., Ltd., Thailand

Abstract

The physical properties of silicalite were studied by using tetraethyl orthosilicate (TEOS) and colloidal silica (LUDOX) as precursors of SiO2. The structural and morphology of catalyst were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), N2 physisorption, X-ray photoelectron spectroscopy (XPS) and using temperature program desorption of ammonia (NH3-TPD) to observe acidity of catalysts. The results showed similar MFI structure over XRD while SEM showed different morphology. The results were studied further by using XPS, it is found that TEOS tended to formulate SiO2 according to oxidation estimating, while LUDOX formulated as SiOx. Therefore, synthesis using LUDOX as a precursor gives more defect structure of Si in order to form SiO2.

Biography

Noppasak Viputvipaporn was born on January 3rd, 1994 in Bangkok, Thailand. He graduated with a bachelor’s degree in chemical engineering from the Faculty of Engineering, King Mongkut’s University of Technology Thonburi, Bangkok, Thailand, in May 2016. He continued his study in master degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2016 under the SCG Chemical Co.,Ltd., (Thailand) scholarship.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 21 Scientific Session-2: Reaction Engineering | Simulation & Modeling

Global Kinetics and Reaction Heat for Catalytic Hydrogen Combustion in a Monolith Reactor

Van Nhu Nguyen*, Robert Deja, Roland Peters, Ludger Blum and Detlef Stolten Forschungszentrum Jülich GmbH, Germany

Abstract

The catalytic combustion of hydrogen is highly suitable for avoiding flames. If hydrogen is utilized as an energy carrier on a large scale, the issue of safety must be taken into account. Any hydrogen in the exhaust gas of a hydrogen-using device must remain within a particular limit. The catalytic combustion of hydrogen provides a safe way of removing 2H from exhaust gas in fuel cell technologies. An experimental study of catalytic hydrogen combustion in the presence of excess oxygen was conducted in a monolith plug-flow reactor, with emphasis on the determination of global kinetics. Commercial catalysts containing Pt were used. By varying the initial composition of hydrogen and the total volumetric feed rate, measurements of the temperature and composition of the product in steady state condition were performed. The conversion of hydrogen was determined in two ways: measurements of the composition of the reaction product and also by means of the thermodynamic approach using material and energy balances. The kinetic expression of Arrhenius type (second order in the mole fraction of hydrogen and zero order in oxygen) was proposed. The estimated activation energy is in very good agreement with the desorption activation energy for O2 from graphene-covered Pt(111) surfaces using temperature-programmed desorption. The obtained result indicates that the desorption of O2 from the Pt surface is the rate-limiting step of the overall oxidation process in lean hydrogen-air mixtures.

Biography

Van Nhu Nguyen (also known as Nguyen Van Nhu) graduated from Martin-Luther University Halle 1975 and completed his PhD and postdoctoral studies at Ruhr University in Bochum, Germany. He has worked at the University of Hanoi, Vietnam, Ruhr University Bochum, University of Cologne, Technical University of Munich and RWTH Aachen University, Germany. Since 2010, he has been a researcher at the ForschungszentrumJülich, Germany. His major interests are in chemical and electrochemical engineering, applied chemical engineering thermodynamics, electrolysis and fuel cells.

Catalytic Propylene Production from Hydrocarbons Over Zeolite-based Composites at Low Energy Consumption

Shinya Hodoshima*, Azusa Motomiya, Shuhei Wakamatsu, Ryuichi Kanai and Fuyuki Yagi Chiyoda Corporation, Japan

Abstract

Propylene, a basic chemical in petrochemical industry, has becomesignificant because of its increasing demand. Conventional thermal cracking of naphtha can no longer meet the increasing demand due to its low propylene yield. Additionally, thermal crackingprocesses are unfavorable in terms of energy consumption. It is thus necessary to establish any alternative method for producing propylene efficiently from widely available feedstocks (e.g., naphtha) from these viewpoints. Though catalytic cracking of various hydrocarbons over zeolites in fixed-bed operation have been actively investigated as a promising choice for on-purpose propylene production, this method hasn’t been commercialized because stable catalysts, being applicable to fixed- bed reactor, are still undeveloped. In the research by our group, unique composite catalysts, consisting of MFI-type zeolites and silicon oxide, have been developed to demonstrate efficient propylene production from naphtha at moderate temperatures in fixed-bed operation. Excellent properties of the presentcatalysts are summarized below. (1) MFI-type zeolites containing Fe, Ga and Alspecies at optimized ratios, giving both high propylene selectivity and low aromatics selectivity due to their unique acidity, were synthesized as main component. The Fe-Ga-Al-MFI zeolites combined with silicon oxide were employed as composite catalysts for cracking. These catalysts exhibited the following excellent o performance in cracking of C5-C8 hydrocarbons: (A) High overall propylene yields at around 600 C (25-35 wt%); (B) Long lifetime in fixed-bed operation (1,000-1,500 h).

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 22 o (2) Energy consumption in reactor over the Fe-Ga-Al-MFI/SiO2 catalyst at 595-620 C was estimated to be reduced by 50-60% compared to thermal cracking, because no thermal energy for heating diluent such as steam was needed as well as its moderate temperature. It was suggested on these experimental basis that catalytic cracking of hydrocarbons over the present composites in fixed- bed mode is feasible as an efficient method for on-purpose propylene production.

Biography

Shinya Hodoshima obtained a PhD in catalytic chemistry from the Tokyo University of Science in 2002. After he spent four years as a postdoctoral research fellow at the Tokyo University of Science, he joined research & development center of Chiyoda Corporation in 2006. He has investigated zeolite synthesis and catalytic cracking of hydrocarbons using zeolites as a group leader. His research interests include applied catalysis and chemical reaction engineering. He received the outstanding presentation award at the 79th Spring Meeting of the Chemical Society of Japan (2001) and the best paper award in the Fuels & Petrochemicals division at the AIChE Spring Meeting (2014).

Oscillations in Stability of Consecutive Chemical Bonds at the Molecule-Metal Interface

Piotr Cyganik1*, Jakub Ossowski1, M. Krawiec2, Z. Postawa1, Jakub Rysz1 and A. Terfort3 1Jagiellonian University, Poland 2Marie Curie Sklodowska University, Poland 3Goethe University, Germany

Abstract

The interface between organic molecule and metal electrode is of fundamental importance for many applications including molecular electronics and catalysis. Unfortunately, it remains extremely difficult in experimental analysis limiting thus our efforts in purposeful design of related devices. Therefore, new experimental approaches in exploring molecule-substrate interface stability are urgently needed to provide systematic and general observations which could in turn push forward theoretical models. In this presentation we demonstrate that static S-SIMS can play such a role to reveal stability mechanisms which could not be analyzed so far by any other technique. The experiments have been conducted using self-assembled monolayers (SAMs) which are considered as a model systems of thin organic films [1,2].Our data exhibit clear positional oscillations in the stability of consecutive chemical bonds along the adsorbed molecule, with the amplitudes diminishing with increasing distance from the molecule-metal interface. To explain these observations, we have performed molecular dynamics (MD) simulations and density functional theory (DFT) calculations. Our calculations show that the observed oscillations in chemical bond stability have a very general character in chemistry related to breaking the translational symmetry in molecules.

References: 1. Ossowski et al. Angew. Chem. Int. Ed.2015, 54, 1336-1340. 2. Ossowski et al. J. Phys. Chem. C, 2017, 121, 459-470.

Biography

Piotr Cyganik received his PhD in 2002 from the Jagiellonian University. After 3 years of postdoctoral research in UK as a Leverhulm Trust fellow and in Germany as an Alexander von Humboldt fellow he returned to his Alma Mater and works currently as an associate professor at the Department of Physics of Nanostructures and Nanotechnology. The scientific interest of his group is focused on experimental analysis (STM, AFM, XPS, IRRAS, SIMS, SNMS, SPR) of structure, stability and conductivity of self-assembled monolayers (SAMs) to investigate properties of molecule-metal interface. He has published 47

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 23 papers which are over 1400 times cited.

Nanoscale Modeling, Prediction and Validation of Transport Phenomena at Catalyst Layer/Gas Diffusion Medium Interface and Catalyst Utilization by the Lattice Boltzmann Method

Seungho Shin*, Sukkee Um and Ah-Reum Kim Hanyang University, South Korea

Abstract

In the present study, a three-dimensional lattice Boltzmann model based on the quasi-random nanostructural model is proposed to simulate the reactant transport phenomena at the fuel cell catalyst layer and gas diffusion medium (GDM) interface in pursuance of catalyst utilization improvement. A series of catalyst layers / GDM complex is randomly generated based on the experimental mass-based properties with the 95% confidence level to reflect the heterogeneity of both catalyst layers and GDM nanostructures. The nanoscale gas transport phenomena inside the catalyst layers / GDM complex are simulated by the D3Q19 lattice Boltzmann method, and the corresponding mass transport characteristics are mathematically modeled in terms of structural properties. Considering the nanoscale reactant transport phenomena, a transport-based effective catalyst utilization factor is defined and statistically analyzed to determine the structure-transport influence at catalyst layers / GDM interface. The effective mass diffusion coefficient is calculated by applying the pre-determined tortuosity factors to the Knudsen diffusion coefficient in the catalyst layers, and it shows good agreement with published experimental data. These results indicate that Knudsen diffusion is the dominant mass transfer mechanism and that the pre-estimated tortuosity accurately reflects the mass transfer phenomena in the fuel cell systems. Furthermore, catalyst utilization at catalyst layers can be limited by the substantive reactant mass transport path inside the GDM and catalyst layers of fuel cell systems.

Biography

Sukkee Um has completed his PhD and postdoctoral studies from the Electrochemical Engine Center at the Pennsylvania State University, USA. He worked for Hyundai motor company as a senior research engineer and performed various researches at Korea Institute of Energy Research in South Korea. Currently, he is the director of Multi Transport Energy Laboratory (METLAB) at Hanyang University, Seoul, S. Korea. His expertise is in the field of computational engineering optimization and design of electrochemical energy systems.

Strong Metal-Support Interaction and Catalytic Edge-Effects for Controlling Electrical Transport in Nanocontacts to Nanowires

Alex M Lord Swansea University, UK

Abstract

Semiconductor nanowires grown by techniques catalyzed with metal nanoparticles present a bottom-up solution for new technological devices. Here, we discuss a strong metal-support interaction (SMSI) that encapsulates the Au growth particle adding material to the edge-region of the interface between the catalyst and the ZnO nanowire [1]. The electron microscopy analysis shows the process occurs at room temperature over a long time period and in ambient benign conditions which is unusual for a SMSI that is normally studied at elevated temperatures and in reactive atmospheres. It is shown by directly correlating atomic-resolution electron microscopy to electrical transport measurements of individual nanowires that the nature of the SMSI-diffused ZnO material at the interface edge creates a channel that affects the quantum-mechanical tunnelling electron transport. The results are confirmed by using the enhanced catalytic activity of the Au-ZnO interface edge to etch away a few atomic layers of the ZnO at the edge-region undercutting the metal nanoparticle. The microscopy analysis and transport measurements show the etch process removes the material from the edge-region and eliminates the quantum-mechanical tunnelling path providing a route to determine the nature of the electrical contacts as Schottky or Ohmic without changing the metal-semiconductor interface or Au-ZnO scheme [2]. This work correlates catalytic edge-effects with electrical transport edge-effects found in metal-semiconductor electrical contacts and progresses to show that the nanometric effects displayed can have profound implications for technological devices.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 24 References: 1. Lord, A. M.; Ramasse, Q. M.; Kepaptsoglou, D. M.; Evans, J. E.; Davies, P. R.; Ward, M. B.; Wilks, S. P. Nano Lett.2017, 17, 687–694. 2. Lord, A. M.; Maffeis, T. G.; Kryvchenkova, O.; Cobley, R. J.; Kalna, K.; Kepaptsoglou, D. M. D.; Ramasse, Q. M.; Walton, A. S.; Ward, M. B.; Koeble, J.; Wilks, S. P. Nano Lett.2015, 15, 4248–4254.

Biography

Alex M Lord is a research scientist at the Centre for NanoHealth, Swansea University, UK where research concentrates on the interface between fundamental nanotechnology research and the eventual integration in to Health applications. Dr. Lord is embarking on a Sêr Cymru II Fellowship which is part-funded by the European Regional Development Fund through the Welsh Government that will develop a new and unique effect in nanotechnology to create an ultra-sensitive electronic sensing device platform by combining the fields of nanoscience and catalysis. Key collaborative partners include world-leading institutions such as Harvard University, IBM, Eindhoven University of Technology and SuperSTEM: The EPSRC National Facility for Aberration-Corrected STEM. Dr. Lord specialises in combining multi-probe scanning microscopy techniques with atomic-resolution electron microscopy.

Direct Measurements of Surface Free Energy of Solid Solutions: Phase Transitions and Complexions

Sergei Zhevnenko National University of Science and Technology “MISIS” , Russia

Abstract

The surfaces are key elements of nanomaterials and catalysts. The main thermodynamic properties of surfaces are their chemical composition and energy. To determine the composition of the surface there are a number of effective methods such as AES, XPS, TEM. Direct measurements of the interfacial free energy of “solid - gas” interface is practically not carried out. This is related with experimental difficulties. We have developed a method for in situ measurements of surface energy of solid metals and alloys. We conducted the experiments on two-component Cu-based systems in an inert or reducing gas atmosphere. Measurements on solid solutions Cu [Ag] and Cu [Co] show the presence of phase transitions on the surfaces [1, 2]. Isotherms of the surface energy have singularities (a minimum in the case of copper solid solutions with silver and the maximum in the case of solid solutions with cobalt). In both cases, the surface phase transitions lead to the surface miscibility gap: a monolayer (multilayer) formation (Cu-Ag), or formation of nanoscale particles (Cu-Co). In accordance with the volume phase diagrams, concentration and temperature of the surface phase transitions correspond to the solid solution in volume. Experiments on similar systems (Cu-Fe, Cu-Pb) lead to the conclusion that in all peritectic systems it should be expected an increase in the surface energy by adding component with a higher melting point and surface phase transitions “surface solid solution – two phase surface with particles” . In eutectic systems, component with a lower melting point reduces the surface energy and forms continuous layers.

References: 1. S.N. Zhevnenko, Interfacial Free Energy of Cu – Co solid solutions // Metall. Mater.Trans. A, 44, 2533 (2013) 2. S. Zhevnenko,A. K. Khayrullin, Interfacial Free Energy and Viscosity of Cu(Ag) Solid Solutions // J. Phys. Chem. C, Volume 120 (2016) pp.14082−14087 3. S.N. Zhevnenko, S.V. Chernyshikhin, Surface phase transitions in Cu-based solid solutions // Appl. Surf. Sci., Volume 421, Part A, (2017) pp. 77-81

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 25 Single-Shell Carbon Nanotubes Covered by Iron Nanoparticle for Ion-Lithium Batteries: Thermodynamic Stability and Charge Transfer

Olga E Glukhova Saratov State University, Russia

Abstract

At present, a perspective field of nanoindustry is the development of lithium-ion batteries based on carbon nanotubes (CNTs), including the tubes decorated by metal oxides like MnO2/SnO2/ Al2O3. A novel and extremely promising directioninthisfield is the battery class, which uses a nanomaterial based on iron (Fe2O3) nanoparticles as a negative electrode. Developed technology for a synthesis of the CNTs with Fe2O3 nanoparticles inside and on the surface of tubes allows us to obtain this material in a macro-scale. This work is devoted to a study of new composite nanomaterial – the single-shell CNTscovered by Fe2O3 nanoparticles and to estimate of its perspectives as an electrode for ion-lithium batteries. Atomistic models of the considered composites are constructed according to the data of natural experiments. A thermodynamic stability of the constructed models is studied by calculation results of the enthalpy of formation. The processes and physical phenomena in this material are studied by the quantum methods - the self-consistent charge density functional tight-binding (SCCDFT) method and the nonequilibrium Green‘s functions (NEGF)method usingDFTB+ and Mizar computer software. For the first time, the regularities in charge transfer from an iron nanoparticle to CNT are studied depending on the type of nanoparticle and its dimensions. It has been established that the CNT + iron nanoparticle complex has a much higher electrical conductivity than the ideal nanoparticle. Such complexes are very promising and will soon be used as an electrode material for ion-lithium batteries. Biography

O.E. Glukhova, Doctor of science in physics and mathematics, now is a head of Department of Radiotechnique and electrodynamics at Saratov State University and leads the Division of Mathematical modeling in Educational and scientific institution of nanostructures and biosystems at Saratov State University. She received her DSc degree in solid state electronics and nanoelectronics from Saratov State University in 2009. Her main fields of investigation are: nanoelectronics, computational modeling of biomaterials and nanostructures, mechanics of nanostructures, quantum transport, photovoltaics and optoelectronics, carbon nanostructures (fullerenes, nanotubes, graphene), material science. She has published about 170 peer-reviewed journal papers and four monographs.

How to Properly Use Keggin Heteropolyacids in the Methanol-to-DME Reaction

Eric M. Gaigneaux* and Josefine Schnee Université catholique de Louvain (UCL), Belgium Abstract

Being a promising renewable fuel, the production of dimethylether (DME) via the gas phase dehydration of methanol nowadays attracts growing interest. Because of their exceptionally high Brönsted super-acidity, heteropolyacids (HPAs) deserve to be exploredin this context.

The Keggin 3H PW12O40 HPA indeed allows reaching high methanol conversions at much lower temperatures than conventional acid catalysts and leads to much better selectivity to DME. However, bulk H3PW12O40 displays low surface area which might limit its overall performance.

A first option to cope with this is to exploit the capability of HPAs to catalyze reactions in the pseudo-liquid way, precisely to perform the dehydration of methanol not only at the surface of HPA crystals but also within their bulk, so exploiting the protons located therein. This behavior has already been evoked in the past but yet not really exploited. Thanks to a Ramanoperando approach, we will show how to succeed this. Precisely, we will enlighten the pretreatment conditions allowing H3PW12O40 to have its bulksimultaneously accessible for methanol and catalytically active.

A second option is to disperse HPAs on supports. TiO2 is often claimed as an excellent choice. but this is actually a mistake

! We will demonstrate that if indeed HPAs disperse well on it, their strong interaction with TiO2 markedly lowers their acid strength, with correspondingly a lowered efficiency to convert methanol. In this context, we will point hexagonal boron nitride as a much better support.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 26 Biography

Being bioengineer (UCL, 1993) EMG got his PhD (UCL, 1997, supervisor B. Delmon), and was fellow of the belgian FNRS (1993-2004). After stays in UK (ICI-Katalco, 1995), USA (University of Notre-Dame, supervisor E. Wolf, 1995), Germany (Fritz Haber Institute,supervisor R. Schlögl, 1998) and Japan (University of Tokyo, supervisor Y. Iwasawa, 1998-1999), he became professor (UCL, 2004). He is full professor since 2014, and guest professor at EPN (Quito, Ecuador, 2014-). EMG got the ExxonMobil Award (2003), and the belgian Royal Chemical Society award (2013). He mainly works on heterogeneous catalystspreparation, situ/operando characterization,biofuelproduction, depollution, valorization of hydrocarbons/alcohols/ biomass.

References: 1. Catalysis Science & Technology, 2017, 7, 817-830 2. ACS Catalysis, 2017, 7, 4011-4017

A Novel Two-stage CO2 Conversion Process in Dual Fixed-bed Catalytic Reactor with Ni-Ga and Cu-based Catalysts for Methanol and Dimethyl Ether Productions

Chao-Lung Chiang* and Kuen-Song Lin Yuan Ze University/Environmental Technology Research Centre, Taiwan

Abstract

Experimentally, Ni-Ga (Ni5Ga3/SiO2) and Cu-based (CuO-ZnO-Al2O3/HYZ; HYZ: protonated Y-type zeolite) catalysts were prepared using co-precipitation method with subsequent calcination in a flowing airstream. Afterwards, methanol (MeOH) and dimethyl ether (DME) were continuously synthesized in a dual fixed-bed catalytic reactor which respectively filled with Ni-Ga and Cu-based catalysts, with a (CO2 + H2) mixed gaseous feeding stream. High reaction temperatures (150, 250, 350 ˚C) and pressure (50 bar) were applied for the syntheses of MeOH and DME to investigate the related kinetics and thermodynamic parameters. Particularity, the oxidation states and fine structural parameters of metal atoms in catalysts were analyzed by XANES and EXAFS, respectively. In the period of MeOH production, the oxidation state of Ga over Ni-Ga catalyst was transformed from Ga (0) to Ga (III) with the obvious coordination number and bond length shifts. Contrarily, the oxidations of Cu and Zn on Cu-based catalyst surface remained as Cu (II) during DME production. In-situ FTIR and GC spectra have shown the existences of high-purity MeOH and DME in following product gas streams. At 50 bar and 250 ˚ C, the optimal CO2 (99.7%) and MeOH (91.7%) conversions at fixed-bed columns of Ni-Ga and Cu-based catalysts were obtained. In addition, the highest MeOH (72.2%) and DME (82.7%) yields were also gained. Reaction mechanisms of MeOH and DME formations over Ni-Ga and Cu-based catalysts were proposed. A profitable pilot-scale plant with high MeOH (5.67 ton/day) and DME (3.98 ton/day) productions for CO2-mixed syngas (CO + H2 and CO2+CO+H2) conversion were designed.

Biography

Chao-Lung Chiang, a PhD student from the Department of Chemical Engineering and Materials Science, Yuan Ze University in Taiwan. His research topics in master and PhD programs are the development of porous materials for

CO2adsorption/separation, and the catalysis of CO2 for valuable chemicals (e.g. methanol, dimethyl ether, dimethyl carbonate, and formic acid) production. So far, he has published more than 15 articles in several journals.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 27 Catalytic Hydrogenolysis of Concentrated Glucose to Propylene Glycol over Activated Cu-La2O3/ Al2O3 Mixed Oxide Yazdani Parviz1,2*, Wang B1, Kawi S2 and Borgna A1,2 1Institute of Chemical and Engineering Sciences, Singapore 2National University of Singapore, Singapore Abstract

Biomass derived glucose is a key intermediate platform chemical that can be converted into various value-added chemicals through different catalytic reactions. For instance, propylene glycol production from glucose hydrogenolysis is of great importance due to the high product value and large demand. Glucose hydrogenolysis to propylene glycol comprises of a series of cascade reactions, including isomerization, retro-aldol condensation, and hydrogenation, which are catalyzed by different active sites. Besides glucose hydrogenolysis, there are other competing reactions, such as glucose hydrogenation, dehydration, degradation and condensation. These side reactions compromise the yield of propylene glycol. Hence, the main challenge for this conversion is the design of catalysts with high selectivity towards propylene glycol [1, 2].

We developed a copper-based catalyst promoted by lanthanum oxycarbonate for the hydrogenolysis of glucose in our previous study [2]. Both copper and lanthanum oxide were supported on alumina. The developed catalyst showed significant selectivity towards isomerisation of glucose to fructose and retro- aldol condensation of fructose. Hydrogenation of the chemicals produced by retro-aldol condensation of fructose increased the yield towards propylene glycol to 24%. In this study, the catalyst is treated in an aqueous solution and activated in flowing Ar at 400°C before catalytic reactions. Interestingly, the propylene glycol yield increased to 37% using the treated catalyst. The catalysts were characterised byXRD, XPS, CO2-TPD,

CO2-DRIFT, BET and TEM. Finally, the role of the treatment on modifying the basicity of the catalyst and catalyst structure was understood and correlated with catalytic results.

References: 1. Schlaf, M. and Z. Zhang, Reaction pathways and mechanisms in thermocatalytic biomass conversion I: Cellulose structure, depolymerization and conversion by heterogeneous catalysts. 2015: Springer

2. Yazdani, P., et al., Lanthanum oxycarbonate modified Cu/Al2O3 catalysts for selective hydrogenolysis of glucose to propylene glycol: base site requirements. Catalysis Science & Technology, 2017.

Investigation of Structural, Spectroscopic and Optical Properties of Some Dinuclear Metal Carbonyls Containing Pyridyl Ligands with Alkyne Unit by Using Quantum Chemical Calculations and Quantum Chemical Approaches on the Catalytic Activities of Complexes

Sultan Erkan Kariper Cumhuriyet University, Turkey

Abstract

Transition metal carbonyl complexes are widely studied because of attracting attention in luminescence and electron transfer reactions. Metal carbonyl complexesare used as catalyst in catalytic processes and as coenzyme, the antioxidant and anticancer in medical applications. Catalytic, antioxidant and anticancer activities of metal carbonyl complexes are dependent on their molecular structure. Therefore, determination of metal carbonyl structures has an important role in chemistry. Alkyne units are versatile functional groups that cause many transformations and have interesting properties. Two or more metal centers could be held in the same molecule with the presence of alkyne units and ligands. Pyridyl bridging ligands formed by the combination of the alkyne entity have been widely used for the construction of dinuclear complexes. These complexes may serve as nonlinear optical materialsbecause they have a long π conjugation. Orbital, optical and structural properties can be calculated with the help of modern computational simulation methods.

In this study, firstly optimized geometries of[(CO) 4P(OPh)3W]2(m-DPB) and [(CO)4P(OMe)3W]2(m-BPEB) complexes were obtained using HF and DFT(B3LYP) methods with LANL2DZ and LANL2DZ/6-31G(d) basis sets in gas phase. The most suitable level were found to be B3LYP/LANL2DZ/6-31G(d) according to correlation of calculated and experimental data. All calculations for the [(CO)4LW ] 2(m-L‘) (M=W, Mo, Cr, L=CO, PMe3, P(OMe)3, PPh3 ve P(OPh)3 L‘=DPA, DPB, BPEB) were performed with the B3LYP/LANL2DZ/6-31G(d) level. The structural parameters were obtained for all

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 28 complexes. Compatibility of the optimized structures was supported with IR, NMR and UV-VIS spectrum. The bond stretching frequencies, 1H-NMR chemical shift values and UV-VIS spectra are predicted for complexes that some of theirexperimental β data are not available in the literature. Polarizability (a), anisotropic polarizability(Δa) and the first hyperpolarizability( 0) values of all complexes were calculated for nonlinear optical properties (NLO). Some electronic structure identifiers such asLUMO- HOMO energy gap (DE), hardness (h), softness (s) etc. were calculated from optimized structures. The catalytic activities of complexes were foresee with the quantum chemical approaches.

As a result of these studies, bond lengths and bond angles obtained from calculations for [(CO)4P(OPh)3W]2(m-DPB) and [(CO)4P(OMe)3W]2(m-BPEB) complexes were found to be agreement with the experimental values. Calculated bond 1 stretching frequencies, H-NMR chemical shift values and UV-VIS spectra were labelled to [(CO)4LW ] 2(m-DPB)[L=CO,

PPh3, P(OPh)3] and [(CO)4LW ] 2(m-BPEB) [L=CO, PMe3, P(OMe)3, PPh3, P(OPh)3] according to consistent with the experimental values. IR, NMR and UV-VIS spectra of the other complexes were predicted. According to polarizability (a), β anisotropic polarizability(Δa) and the first hyperpolarizability( 0) values obtained from calculations, all complexes are used as optical material. In addition, NLO properties and the catalytic activities of complexes were associated with some electronic structure identifiers.

Quantum Simulation on the Adsorption of C-C Bond Contained Lignin Related Model Compounds over the Metal Surface of the Catalyst

Chongbo Cheng1*, Dekui Shen1 and Sai Gu2 1Southeast University, China 2University of Surrey, UK

Abstract

To address the mechanism of C-C bond cleavage on the metal surface of a catalyst is desirable and vital during the depolymerization process of lignin. Density Functional Theory (DFT) calculations were performed to examine the adsorption geometry, adsorption energy and energy of C-C bond scission in three β-1 bond contained lignin model compounds (Fig. 1) adsorbed on the (100) surface of different metals (Ni, Cu, W). With regard to theC-C bond scission energy in different model compounds, the Ca-Cb scission energy was found to be lower than that of Caryl-Ca and Cb-Caryl bond. The Ca-Cb scission energy in Mo2 was the lowest, confirming the important role of the presence of the conjunctedC a-OH linkage. Mo2 were found to be adsorbed via a π configuration on the Ni(100) and Cu(100) surface, while it was anchored of the–OH group as a η configuration which was less stable on the W(100) surface (Fig. 2). The adsorption ofMo2 on the (100) surface of metals gave no significant contribution on declining theC a-Cb scission energy. Nevertheless, the model compounds exhibited a co- adsorption with hydrogen on the metal surface under the reacition conditions. The adsorption ofMo2 on the Cu(100) surface η was changed to the patterns (Fig. 3) and the Ca-Cb bond scission energy was declined on the Ni(100) and Cu(100) surface involving the coverage of hydrogen. The adsorption on W(100) had no effect on the decrease of the energy for Ca-Cb bond scission. The results from the quantum simulations confirm that the adsorption geometry ofC-C bond contained lignin model compounds are notably influenced by the surrounding hydrogen in forms of the co-adsorption, guiding the selection of catalyst for C-C bond cleavage through the ab initio method.

Figure 1: Schematics of C-C bond containedligninmodel compounds. Mo1: Bibenzyl, Mo2: 1,2-Diphenylethanol, Mo3: 2-Phenylacetophenone.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 29 Figure 2: Schematics of Mo2 adsorbed on the Ni(100), Cu(100) and W(100) surfaces.

Figure 3: Schematics of Mo2 adsorbed on the hydrogen-covered Ni(100), Cu(100) and W(100) surfaces.

Biography

Chongbo Cheng has obtained Master’sdegree in thermal engineering from Southeast University in 2015.He started the PhD study in Southeast University after then with the research topic on lignin biorefinery processes under the supervision of Professor Dekui Shen.

Sandwich-like Silica@Ni@Silica Multicore-shell Catalyst for Low Temperature Dry Reforming of Methane: Confinement Effect Against Carbon Formation

Zhoufeng Bian* and Sibudjing Kawi National University of Singapore, Singapore

Abstract

In this report, we synthesize a novel sandwich-like silica@Ni@silica multicore-shell catalyst. Firstly, Ni phyllosilicate is supported on silica nanospheres with simple ammonia evaporation method. Then this Ni phyllosilicate (NiPS) is coated with a layer of mesoporous silica to obtain a core-shell structure of Ni phyllosilicate@silica via hydrolysis of TEOS. The thickness of shell can be tuned via varying the amount of TEOS. After calcination and H2 reduction at high temperature, multiple small Ni nanoparticles (~6 nm) are generated and supported on the inner silica core but also encapsulated within the outer mesoporous silica shell. This silica@Ni@silica multicore-shell catalyst shows a high and stable conversion (~60%, GHSV=60,000 ml/hgcat) for DRM at 600°C while the pristine Ni phyllosilicate deactivates fast due to heavy carbon formation. TGA and TEM of spent catalysts have shown that there is almost no carbon formation for this novel multicore-shell catalyst. Compared with conventional Ni@silica core-shell catalyst, our multicore-shell catalyst is much easier to be synthesized and the process does not need any toxic organic solvent. We believe this strategy of making multicore-shell catalyst can be applied to more nanomaterials and extended to other catalytic reactions besides DRM.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 30 Biography

Zhoufeng Bian received his B.Eng. from Shanghai Jiaotong University, China in 2014. He joined in Prof. Kawi’s group as a Ph.D. student with the support of Chinese Scholarship Council (CSC) on August 2014. He has been working on development of nanocatalysts for H2 production including dry reforming of methane, water-gas shift and so on.

Effects of Hydrogen Co-feeding at Various Ratios in Propylene Self-Metathesis with Silica-Supported Tungsten catalyst

Jinjuta Boonchot1*, Kongkiat Suriye2, Joongjai Panpranot1 and Piyasan Praserthdam1 1Chulalongkorn University, Thailand 2SCG Chemicals, Thailand

Abstract

The effects of hydrogen co-feeding in propylene self-metathesis over 3WO /SiO2 with molar ratios of hydrogen to hydrocarbon equal 0, 0.25, 0.5, and 1 have been investigated at 550˚C under atmospheric pressure. WO3/SiO2 catalyst was prepared by the incipient wetness impregnation method. The results indicated that the addition of hydrogen had an impact on catalytic activity. Ratio 0.25 is an optimal point to improve the metathesis activity and product selectivity. At this optimum ratio, C5+ selectivity was decreased resulting in lower of coke formationHigher hydrogen to hydrocarbon ration (0.5 and 1), lower metathesis activity was observed with higher selectivity of side reactions.

Biography

Jinjuta Boonchot was born on April 1st, 1994 in Trang, Thailand. She graduated with a bachelor degree in chemical engineering from the Faculty of Engineering, King Mongkut‘s University of Technology Thonburi, Bangkok, Thailand, in May 2016. Now she is pursuing her study in master degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2016 under the SCG Chemical Co.,Ltd., (Thailand) scholarship.

Isomerization of 1-Butene to 2-Butenes Over SiO2-Al2O3 Catalysts

Poonyapa Phansook1*, Kongkiat Suriye2, Piyasan Praserthdam1 and Joongjai Panpranot1 1Chulalongkorn University, Thailand 2SCG Chemicals, Thailand

Abstract

The double bond isomerization of 1-butene to 2-butenes at 100 ˚C has been investigated over two series of silica-alumina catalysts with various silica:alumina ratio (10 and 20 wt% SiO2). crystallite silica-alumina and amorphous silica-alumina., It was found that increasing % SiO2 increased 1-butene conversion but the cis/trans ratio decreased for both amorphous and crystal silica-alumina . However, crystal alumina-silica exhibited higher 1-butene isomerization than the amorphous alumina-silica. The XRD pattern showed the typical patterns of pseudoboehmite for crystal one. The FTIR of ammonia adsorption results of silica-alumina catalysts showed both Brønsted and Lewis acid sites. Moreover, increasing % SiO2 led to higher Brønsted acid sites and lower Lewis acid sites. It is indicated that Brønsted acid are an active for 1-butene isomerization.

Biography

Poonyapa Phansook was born on October 13th, 1994 in Suratthani, Thailand. She graduated with a bachelor degree (Second class honors) in Chemical technology from the Faculty of Science, Chulalongkorn University, Bangkok, Thailand, in 2016. She continued her study in master degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand under the SCG Chemical Co., Ltd., (Thailand) scholarship.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 31

February 20 2Tuesday Scientific Session-3: Catalytic Materials & Mechanisms | Nanocatalysis

Metal-Support Interaction in Catalysis Studied Using Kelvin Probe Atomic Force Microscopy

Emil Roduner1, 2* and Tobias Kittel1 1University of Stuttgart, Germany 2University of Pretoria, South Africa

Abstract

It is well-known in catalysis that identical noble metal nanoparticles on oxide supports exhibit different activity in catalytic reactions, but because of the various possible sources of influence it has been difficult to single out the exact origin of the effect. We have decided to use Kelvin probe scanning atomic force microscopy to investigate the possible electrical polarization by charge transfer across the metal-support interface. A first scan in contact mode served to map the topography, and a second scan with the conductive tip retracted from this surface by a constant amount served to measure the electrical potential (i.e. the Kelvin signal).

Nanoparticles of Pt, Rh and Pd supported on TiO2, CeO2 and Al2O3 were measured at ambient temperature and atmosphere. In all cases, the measurements reveal an electron transfer from the metal to the support, leading to charge polarization at the Schottky-type interface analogous to that of a parallel plane capacitor. This polarization cancels out to a large extent for the Kelvin signal. On top of this there is a much smaller number of positive charges at the outer catalyst particle surface, compensated by negative charges near the oxide surface. These charges determine the constant electrical potential of the metal and are believed to reflect the relevant catalytic metal-support interaction. The effect is analogous to the application of an electrical bias in electro-catalytic reactions.

References: 1. T. Kittel and E. Roduner, J. Phys. Chem. C, 120 (2016) 8907-8916; and ibid. 8917-8926.

Biography

Emil Roduner was born in Switzerland and studied chemistry at the University of Zürich. He obtained a M.Sc. in chemistry at the Rensselaer Polytechnic Institute in Troy, NY., then returned to Zürich for his doctoral work in muonium chemistry. In 1988, he was awarded the Werner Prize by the Swiss Chemical Society “For the development of Muon Spin Rotation as a general method for studying structure and reaction kinetics of free radicals”. From 1995 until 2012 he had a chair in physical chemistry at the University of Stuttgart, and currently he is a guest professor at the University of Pretoria.

A Theoretical Study of Methane Activation and C-C Coupling on Pure IrO2 (110) and IrO2 Supported TiO2 (110) Surfaces

Jyh-Chiang Jiang National Taiwan University of Science & Technology, Taiwan Abstract

Ethylene is attracted as a chemical feedstock in recent years because of declining petroleum reserves. Additionally, the development of fracking technologies for the extraction of shale gas has efficiently increased the supply of methane and other light alkanes. Hence, the chemical conversion of methane into value-added chemical products such as ethylene would be enormous beneficial. However, the activation of the stable C–H bond in methane is a challenging task in the conversion process. Recently, methane activation on metal oxide surfaces is considered as a cost-effective method to convert methane directly into value-added chemicals. Conversely, a very weak interaction of methane with many oxides leads to search for a suitable metal oxide catalyst which can efficiently promote the activation. Here, the energetics and mechanism for methane activation as well as C–C coupling reactions on pure IrO2 (110) are investigated by using van der Waals-corrected density functional theory calculations. Also, we have explored the effects of one Ir atom and one IrO2 layer supported on TiO2 (110) surface towards the activation of methane and C–C coupling reactions. Based on the DFT calculations, the formation of ethylene could be feasible on the IrO2 (110) surface via selective CH4 dehydrogenation reactions to CH2 and a barrier-less self-coupling reaction of CH2 species. The calculated reaction barriers for CH4 dehydrogenation and C-C coupling on both Ir-doped TiO2 (110) and IrO2/

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 34 TiO2 (110) surfaces are very close to the values that of pure IrO2 surface, which indicate that this supported TiO2 (110) surface would be an efficient catalyst for the direct conversion of methane.

Figure1: Reaction path for dehydrogenation of CH4 to C and 4H on pure IrO2 and Ir and IrO2 supported /TiO2 (110) surfaces.

On the Discovery of a New Materials Class Useful in the Gas Phase Hydroformylation of Small Olefins: Platinum Group Phosphides as Interesting Catalyst Candidates

Stephan Andreas Schunk1*, Jaroslaw Mormul1, Luis AlvaradoRupflin1, Michael Lejkowski1, Sven Titlbach1, Rainer Papp2, Roger Gläser3, Maria Dimitrakopoulou4, Frank Rosowski5, Robert Schlögl4, Annette Trunschke4 and Xing Huang4 1hte GmbH, Germany 2BASF, Germany 3Universität Leipzig, Germany 4Fritz Haber Institute, Germany 5TU Berlin, Germany

Abstract

Since its discovery in 1938 by Otto Roelen the homogeneously catalyzed hydroformylation of olefins has become one of the most important large-scale industrial processes. Like in the early years of development, today cobalt carbonyl complexes are still used as catalysts for mid- and long-chain olefins, whereas for the short-chain olefins like ethylene and propylene cobalt catalysts were quickly replaced by inherently more active and selective rhodium complexes modified with phosphine or phosphite ligands. A challenge accompanied with using the distinctly more expensive noble metal in a homogeneously catalyzed process is an effective separation of the catalyst from the reaction products.

A technical solution involving a heterogeneously catalyzed hydroformylation reaction with the catalyst in the solid phase and the products in the gas phase could offer interesting alternatives which could also lead to new solutions with regard to process design. Our efforts for finding suitable solutions circled around materials that display chemical and structural environments similar to metal phosphorous interactions in bisphosphine and bisphosphite modified rhodium complexes which are used as homogeneous catalysts for hydrogenation and especially for hydroformylation reactions. Herein, we want to show the usefulness of the identified materials class of platinum group metal phosphides as catalysts for the hydroformylation of ethylene and propylene as highly active, selective and durable catalysts. Biography

Stephan Andreas Schunk holds the position of a Principal Scientist at hte GmbH and BASF SE and is one of the founding members of hte GmbH. He studied chemistry at Mainz and Frankfurt University and holds a PhD in chemistry from the

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 35 University of Frankfurt; he is guest lecturer at the University Leipzig and a member of the commission of the German Catalysis Society GeCatS. He received the Jochen Block award in 2000, the Science Prize of the Max-Planck Society in 2001 and was awarded by the WCOC in Sapporo 2005 for his work in gas phase partial oxidation catalysis.

Thermodynamic Implications of Mixed Catalytic Cycles on Catalyst Stability: The Stabilizing Effect of Water on the CeO2-Catalyst in the Harsh HCl Oxidation Reaction

Franziska Hess2,3*, Chenwei Li1,2, Igor Djerdj4, Guangtao Chai1, Yu Sun1,2, Yanglong Guo1, Bernd M. Smarsly2 and Herbert Over2 1East China University of Science and Technology, PR China 2Justus Liebig University, Germany 3Massachusetts Institute of Technology, MA, USA 4J. J. Strossmayer University of Osijek, Croatia

Abstract

We studied the stability of CeO2nano-cubes with preferential (100)-oriented facets in the HCl oxidation reaction (Deacon Process) for various reaction temperatures and the addition of small concentrations of water in the gas feed. For a reaction mixture

HCl:O2 = 1:2 we found that CeO2 chlorinates substantially below 380°C, revealing a low catalytic activity. The experimental results were rationalized by a kinetic model considering chlorination and dechlorination reactions that allow us to study catalyst chlorination as a function of temperature and gas feed composition.

The model suggests that chlorination sets in at the inlet of the catalyst bed and propagates then slowly along the catalyst bed towards the reactor outlet to fully chlorinate the CeO2 catalyst bed, which is confirmed by a dedicated experiment employing two separate catalyst layers, where only the first layer is chlorinated while exposed to the Deacon gas feed. We traced back the excessive chlorination at the reactor inlet to the absence of H2O in the gas feed using our model, as the formation of H2O by the reaction of HCl with CeO2 seems to be the leading driving force for catalyst chlorination. When running the Deacon process at 375°C, the chlorination of CeO2 nano-cubes is efficiently suppressed by the addition just 1% water in the reaction mixture, as predicted by our calculations.

Biography

Franziska Hess graduated from the Justus-Liebig-University at Giessen, Germany. She is currently a postdoctoral associate at the Department of Nuclear Science and Engineering of Massachusetts Institute of Technology. She studies (electro-) catalytic reactions on surfaces applying a combination of experiments and/or density functional theory with Kinetic Monte Carlo simulations and continuum models.

Molecular Chemistry Tools Applied to Nanochemistry: Selective Nanocatalysts in Hydrogenation and Hydrogenolysis Reactions

Karine Philippot Universite de Toulouse, France

Abstract

With the huge development of nanocatalysis, the demand for metal-based nanomaterials has been fast increasing and chemists are looking for effective synthesis methods to achieve well-defined nanocatalysts and to guarantee controllable and reproducible properties. Regarding nanochemistry in solution, the concepts of molecular chemistry allow developing efficient synthetic tools to have metal nanoparticles in a size less than 10 nm [1]. Metal-organic complexes are particularly well-suited precursors to provide well-controlled and functionalized metal or metal-oxide nanoparticles in terms of size and composition. The choice of the stabilizing agent (polymer or ligand) is of prime importance to control the characteristics of the nanoparticles and beyond, their surface properties [2]. This method can be applied for the preparation of mono- or bimetallic nanocatalysts, under the form of colloidal suspensions or supported systems. Examples of Ni and RhNiOx nanocatalysts prepared through the organo-metallic approach will be presented with their catalytic performance in hydrogenation and Hydrogenolysis reactions, respectively [3,4].

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 36 References: 1. Controlled metal nanostructures: Fertile ground for coordination chemists, C. Amiens, D. Ciuculescu-Pradines, K. Philippot, Coord. Chem. Rev., 2016, 38, 409-432. 2. On the use of Organometallic Concepts for the Synthesis of Nanocatalysts, T. Ayvali, K. Philippot, New Materials for Catalytic Applications, E. Kemnitz and V. Parvulescu (Eds.), Elsevier, 2016, Chapter 3, 41-79. 3. J. Zhang, M. Ibrahim, H. Asakura, T. Tanaka, K. Teramura, K. Philippot, N. Yan, J. Mol. Catal. A, 2016, 422, 188-197. 4. L. Zaramello, J.B. Domingos, K. Philippot, Dalton Trans.,2017, 46, 5082-5090.

Whole-Cells Biocatalysis as a Tool for Chiral P-C Compounds Synthesis

Ewa Żymańczyk-Duda* and Małgorzata Brzezińska-Rodak Wroclaw University of Science and Technology, Poland

Abstract

Chiral phosphonates are compounds of different biological activities. Among them are molecules acting as enzymes inhibitors, antibacterial, antifungal and antiviral factors, and also chelating agents. They are applied as well as in medicine and agriculture and other fields of industry. Their biological potential is due to their structure – they are structural analogues of carboxylic acids and also phosphonate moiety represents the analogy with the transition state of the enzymatic hydrolysis of peptide bond. Thus, P-C compounds are applied as enzymes inhibitors, because they can influence different metabolic pathways. Biocatalyzed synthesis of optically pure phosphonates is performed with eukaryotic (fungal) and prokaryotic biocatalysts (photo biocatalysts), mostly under gentle physical chemical conditions and with good yield. Performed experiments proved that the engineering of the biocatalytic medium and biocatalysts form allowed directing the stereo selectivity and effectiveness of the reaction. Such “green methods” are good alternative to the asymmetric chemical synthesis, because of the environmental reasons but they have some limitations such as finding the biocatalysts active towards phosphonates and scaling the processes. In the case of such compounds – mostly of inhibitory activity towards many enzymes - screening for the proper biocatalyst and setting the preparative scale experiments are not trivial research problems. Performed experiments allowed obtaining structurally different, optically pure, chiral P-C compounds with good yields. In some cases, scaling procedures were established and were based upon the models of the batch and continuous-flow reactors.

Biography

Ewa Żymańczyk-Duda has completed M.Sc. in Biotechnology in 1990, PhD in Chemistry in 1995. From 1998-2008, she worked as an Assistant Professor (2008) at Wroclaw University of Science and Technology, Poland. From 2011- 2016 and 2016-2020, she is the Vice Dean of Chemistry Department, Coordinator of teaching program in biotechnology. She has the authorship in more than 60 papers in reputed journals and chapters in monographs.

The Importance in Computational Catalysis of Coadsorbate Effect on Band Gap Oxides/Zeolites

Isabela-Costinela Man1, Ivano E. Castelli2, Vasile Parvulescu3 and Jan Rossmeisl4 1Center of Organic Chemistry of Romanian Academy, Romania 2Technical University of Denmark, Denmark 3University of Bucharest, Romania 4University of Copenhagen, Denmark

Abstract

Quantum mechanical studies have emphasized the importance of coadsorbing on oxide surfaces of two species that behaves as electron acceptor (A) and electron donor(B) and which will increase their binding energies compared to the sum of their binding energies calculated in separate cells [1,2]. It has been also shown that the presence of A on the surface has a profound influence also on the site to which B will bind, beside the influence on its binding energy [3,4]. We have investigated using density functional theory (DFT) the difference between the adsorption energies of different donor-acceptor pairs calculated when coadsorbed and the sum of binding energies of isolated fragments (named interaction energies -ΔEdiff) and its relation with the band gap of oxides. A trend was observed: with increasing the energy of the band gap it increases also the value of these energies differences [5]. A scaling relationship was derived (see Figure 1). Due to this behavior, the complexity of describing

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 37 chemical reactions on band gap oxides from first principle calculations compared to metals increases. We predict that this scaling relation combined with other scalings, can reduce the complexity in searching the new catalysts among the band gap oxides. We extended this relation to the class of zeolites that have band gap. The coadsorbate effect it manifests also on the path of transition states and also on the values of activation energies. We exemplify this for diffusion of H on oxide surfaces-MgO,

Al2O3 for which the value of activation energy changes from the case when H is alone in the unit cell and when is coadsorbed with another H. The transition path changes as well. Definitely this will reflect in the modeling of reaction kinetics.

Figure 1: Interaction energy, Ediff.as a function of the bandgap, Eg of the clean surfaces.

References: 1. Metiu, H., et al., Chemistry of Lewis Acid–Base Pairs on Oxide Surfaces. The Journal of Physical Chemistry C, 2012. 116(19): p. 10439-10450. 2. Abrahamsson, B. and H. Grönbeck, NOx Adsorption on ATiO3(001) Perovskite Surfaces. The Journal of Physical Chemistry C, 2015. 119(32): p. 18495-18503. 3. Broqvist, P., et al., NOx Storage on BaO(100) Surface from First Principles: a Two Channel Scenario. The Journal of Physical Chemistry B, 2002. 106(1): p. 137-145. 4. Chrétien, S. and H. Metiu, Acid–Base Interaction and Its Role in Alkane Dissociative Chemisorption on Oxide Surfaces. The Journal of Physical Chemistry C, 2014. 118(47): p. 27336-27342. 5. Castelli, I.E., et al., Role of the Band Gap for the Interaction Energy of Coadsorbed Fragments. The Journal of Physical Chemistry C, 2017.

Recent Advances on Laser-Generated Model Catalysts

Sven Reichenberger1*, G. Marzun1, F. Waag 1, S. Kohsakowski1, Ina Haxhiaj1, M. Lau1, B. Gökce1, B. Peng2, M. Muhler2 and S. Barcikowski1 1University of Duisburg-Essen, Germany 2Ruhr-University Bochum, Germany

Abstract

Understanding underlying structure-activity correlations in catalysis research requires the availability of suitable model catalysts hereby avoiding cross-correlations during synthesis. Often such correlations are introduced during the post-treatment of the catalysts e.g. during purification / calcination thereby eventually inducing changes in the particle size, surface area, crystal morphology or defect density [1,2]. During the recent years a scalable, surfactant-free laser-based catalyst preparation technique has shown promising results in the preparation of model catalysts for structure-activity analysis not requiring any post-treatment prior to catalytic testing, hence avoiding the previously mentioned cross-correlations [3,4,5].

Within this talk an overview on the principle itself and the current advances in understanding occurring particle formation

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 38 mechanisms during laser-based preparation will given covering the synthesis of pure and alloyed nanoparticles. Additionally, first experimental results on the laser based defect-engineering performed on semiconductor and spinell materials will be discussed. Further it will be shown that the laser-generated nanoparticles can easily be supported to e.g. defect-engineered carrier structures by electrostatic interactions at various loading maintaining the particle size. Finally, recent results on the catalytic activity and stability of these materials will be presented and discussed with respect to well characterized commercial catalysts.

Biography

Sven Reichenberger studied chemical engineering and further made his PhD in 2017 as part of the group of Prof. Barcikowski. The research of the Barcikowski group is generally focused on the laser-based synthesis of surfactant-free metal and alloy nanoparticles, their functionalization, processing or immobilization in order to prepare heterogeneous model catalysts, polymer composites and biomaterials. After his PhD, Sven Reichenberger remained in the Barcikowski group working on the tailored laser-based induction of surface defects into semiconductor materials, their functionalization with nanoparticles as well as further application in selective oxidation reactions.

Acknowledgments The authors gratefully acknowledge the funding provided by the Mercator Research Centre Ruhr(MERKCUR) project Pr-2016-0044.

References: 1. R. Siburian, T. Kondo, and J. Nakamura, “The Journal of Physical Chemistry C, vol. 117, no. 7, pp. 3635–3645, 2013. 2. Y. Guo, D. Gu, Z. Jin, P.-P. Du, R. Si, J. Tao, W.-Q. Xu, Y.-Y. Huang, S. Senanayake, Q.-S. Song, C.-J. Jia, F. Schüth, Nanoscale 7, 4920–4928, 2015. 3. D. Zhang, B. Gökce, S. Barcikowski, Chemical Reviews 117 (5), 3990–4103, 2017. 4. D. Zhang, J. Liu, P. Li, Z. Tian, C. Liang, ChemNanoMat 3 (8), 512-533, 2017 5. W. Dong, S. Reichenberger, S. Chu, P. Weide, H. Ruland, S. Barcikowski, P. Wagener, M. Muhler, Journal of Catalysis, 330, 497-506, 2015.

Microwave Catalysis under Microwave Irradiation and Study on the Microwave Catalytic Reaction Technology

Zhou Jicheng*, Wentao Xu, Zhimin You,Zhang Yanji and Su Zhimin Xiangtan University, China Abstract

Photo-chemical reactions and Photo-catalytic reactions happens when light irradiation. What happens when MW irradiation is used for chemical reactions? Since the use of MWs for synthesis reactions first appeared in 1986, numerous studies have investigated the use of MW heating or MW irradiation for organic and materials synthesis, and significant improvements that cannot be obtained by conventional heating methods have been reported. In addition, MW irradiation has been successfully applied in a range of heterogeneous catalytic reaction systems and other reaction systems. Although the use of microwave irradiation to enhance chemical reactions is growing at a rapid rate, the intrinsic nature of the effect of microwave irradiation on chemical reactions remains unclear. Recently, much interest has been focused on understanding the nature/role of MW reaction rate enhancements. However, the intrinsic reasons for the MW reaction rate enhancements are still speculative, often conflicting. In particular, there is ongoing debate in the scientific community regarding whether the observed enhancements are the result of purely thermal effects arising from rapid heating and high bulk reaction temperatures generated in the reaction medium due to the radiation field or whether some effects are connected to so-called specific or non-thermal microwave effects, which are related to interactions between the microwave electromagnetic field and the reactant molecules. The use of microwave (MW) irradiation to increase the rate of chemical reactions has attracted much attention recently in nearly all fields of chemistry due to substantial enhancements in reaction rates. However, the intrinsic nature of the effects of MW irradiation on chemical reactions remains unclear.

Here in, the highly effective conversion of NO and decomposition of H2S via MW catalysis as study cases were investigated. The temperature was decreased by several hundred degrees centigrade. Moreover, the apparent activation energy (Ea’) decreased substantially under MW irradiation. Importantly, for the first time, a model of the interactions between microwave

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 39 electromagnetic waves and molecules is proposed to elucidate the intrinsic reason for the reduction in the Ea’ under MW irradiation, and a formula for the quantitative estimation of the decrease in the Ea’ was determined. MW irradiation energy was partially transformed to reduce the Ea’, and MW irradiation is a new type of power energy for speeding up chemical reactions. MW irradiation on chemical reactions exhibited MW catalysis and MW selective catalytic effects.

It is found that MW irradiation is a new type of power energy for speeding up chemical reactions [1]. It is elucidated that the intrinsic reason for speeding up chemical reactions is the reduction in the Ea’ under MW irradiation and MW irradiation energy was partially transformed to reduce the Ea’ , and MW catalysis under MW irradiation was elucidated[1, 2, 3] we reported that the decrease in the Ea’ rather than solely the “hot-spots” hypothesis or the controversial “MW non-thermal effect” or “specific microwave effects” is a new reason for microwave-accelerated heterogeneous gas-phase catalytic reactions[4]. It is found that MW irradiation exhibited MW selective catalytic effect. Our findings challenge both the classical view of MW irradiation as only a heating method and the controversial “MW non-thermal effect” or “specific microwave effects”, and open a promising avenue for microwave catalysis in catalysis field and for the development of novel MW catalytic reaction technology.

b) a)

Figure 1a) MW irradiation is a new type of power energy for speeding up chemical reactions b) Scheme of the model of the interactions between MW and molecules

References: 1. J. Zhou,W. Xu,Z. You, et al.,Scientific Reports, 2016, 6: 25149. 2. W. Xu, J. Zhou, Z. You, et al.,ChemCatChem, 2015, 7: 450-458. 3. W. Xu, J. Zhou, Y. Ou, et al., Chemical Communications, 2015, 51: 4073-4076. 4. W. Xu, J. Zhou, Z. Su, et al., Catalysis Science & Technology, 2016, 6: 698-702.

Structure Sensitivity of CO and Soot Oxidation Over Ceria-based Catalysts

Marco Piumetti*, Tahrizi Andana, Samir Bensaid, Debora Fino and Nunzio Russo Politecnico di Torino, Italy

Abstract

A set of CeO2 nanocatalysts with different structural properties (nanocubes, nanorods, high-surface area CeO2) was prepared to investigate the shape-dependency activity for two oxidation reactions: the soot combustion and the CO oxidation. The physico- chemical properties of the prepared materials were investigated by complementary techniques. As a whole, the best performances 2 -1 in terms of soot combustion have been achieved for the CeO2-nanocubes (SBET ≈ 4 m g ), due to the abundance of highly reactive (100) and (110) exposed surfaces. On the other hand, better results in terms of the onset of soot oxidation have been obtained for 2 -1 high-surface-area materials (SBET ≈ 75 m g ), thus reflecting the key role of the surface area at low reaction temperature. Activity tests have confirmed the structure-sensitivity for the soot oxidation reaction at high temperature. On the other hand, the same reaction has appeared surface-insensitive at low temperature. Thus, the soot oxidation over ceria can be considered a reaction that displays both a surface-sensitive and surface-insensitive behavior, depending on the operating conditions. The highest CO oxidation activity has been achieved for ceria nanocubes, thus confirming the structure-sensitivity for the CO oxidation reaction over CeO2-based systems. On the other hand, high-surface CeO2 was unable to outdo the activity of nanocubes and nanorods due to the abundant presence of more stable (111) planes. In conclusion, both the oxidation reactions, kinetically described via a Mars-van Krevelen type mechanism, may exhibit a structure-sensitive behavior over Ceria-based catalysts.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 40 Biography

Marco Piumetti graduated in Chemical Engineering and received the European PhD in Materials Science and Technology from the Politecnico di Torino, Italy. In 2010 he attended the post-graduate perfectioning course in Energetic “G. Agnelli”. In 2013 he joined in the research team of Prof. Guido Saracco at the Politecnico di Torino, where since July 2013 he is Assistant Professor. His academic activity is mainly focused on the study of catalytic materials for environmental applications.

Rationalized Onion-like Non-PGM Catalyst Development for Oxygen Reduction Reaction

Lin Wang Hsing 1, 2 *, Claudia W. Narvaez Villarrubia1, Hung-Ju Yen1, Gen Chen1, Honbo Li1 and Ming Zhou1 1Los Alamos National Laboratory, NM, USA 2Southern University of Science and Technology, China

Abstract

At the cathode of the fuel cell, the oxygen reduction reaction (ORR) takes place. The state-of-the-art catalysts for this reaction are platinum (Pt)-based materials. At the fuel cell’s anode, Pt-based catalyst is also needed. The limited activation and reduction of oxygen on the cathode force to increase the loading of Pt-catalysts when compared to the anode. As a result, the practical fuel cell application is constrained by the expensive and volatile price of the Pt-market; the Pt-catalysts represent the 40% of the cost of the fuel cell.

The development of inexpensive non-Pt catalysts are the center of investigation in the last decades and the development of non-Pt group metal (Non-PGM) catalysts, nitrogen-doped carbon materials, are promising alternatives. These are, typically, synthesized from metal salts and organic nitrogen and carbon precursors. The precursors are pyrolyzed at elevated temperatures, in an inert environment, to form the active structures for oxygen reduction catalysis. N-doped onion-like carbon nanostructures have being developed to achieve ORR catalysis. However, the mechanism of formation of these structures is not very well understood nor controlled.

In this research, we aimed to rationally control the active site nano-architectures for ORR in acid media. Onion-like nano- architectures are developed as catalytic structures by handling the chemistry of the carbon and nitrogen precursors and the reaction leading to the formation of the onion-like nanostructures. These structures are inserted in a carbon-based conductive matrix that serves as electron collector. Results show these controlled nano-architectures are promising Non-PGM materials for ORR catalysis.

Biography

Hsing-Lin Wang is a Chair Professor at the Materials Science and Engineering Department, Southern University of Science and Technology. His research interests are in the: 1. Synthesis of functional molecules and their self-assemblies, and further demonstrate their applications toward energy devices. 2. Study under pinning principles of how nanoscaled structures along with metal complex impact the catalytic properties in fuel cell devices. 3. Fine tuning the electronic properties through synthetic chemistry to allow matching of the interface energy to optimize charge transfer across interfaces. He has more than 180 papers with more than 9000 citations in the above areas.

Simple Sol-Gel Route for Preparing Silica Sample with Enhanced Adsorption Capacity

Manuel Houmard*, Eduardo H.M. Nunes, Thays L.R. Motaand Ana Paula M. de Oliveira Federal University of Minas Gerais - UFMG, Brazil

Abstract

In this work we present a simple route to prepare sol-gel silica samples with an enhanced adsorption capacity. These materials were not chemically modified neither heat-treated to tailor their pore structure. The materials studied in this work were examined by N2 adsorption; scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The adsorption capacity was studied measuring the water adsorption in a humid chamber at 30 °C and atmospheric pressure. The samples prepared herein showed higher adsorption capacities than a commercial silica adsorbent. It was shown that it is possible to produce sol-gel derived materials with high adsorption capacities by controlling the sol pH. Samples obtained from

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 41 sols with a low pH presented an expressive volume of small pores, whereas those prepared from sols with no acid displayed larger pores; both cases increase the volume of pores and, consequently, the adsorption capacity of the material. It is an important finding since several works available in the literature deals with complex and multi-step procedures, commonly using pore- formers or pore-expander agents, which makes them cost ineffective and time consuming. The absence of acidic reactants in the preparation step of the adsorbent with the highest adsorption capacity represents an advantage in terms of safety and environmental sustainability, besides reinforcing the simplicity of the processing route employed herein. Since a high adsorption capacity should improve the volume of contaminant product at the material interface, such sol-gel adsorbents could have great performance in catalysis applications.

Biography

Manuel Houmard is professor of the Materials Engineering and Construction Department at the Federal University of Minas Gerais (UFMG) in Brazil since 2012. He is an engineer and doctor graduate from the Grenoble-INP university in France. After his PhD thesis, he performed a postdoctoral experience at the Lawrence Berkeley National Laboratory (LBNL - USA). His research focuses on material science and chemical engineering, especially about surface and interface science, nano- materials synthesized by sol-gel technology and fabrication of macro and mesoporous ceramic structures.

N-Heterocyclic Monodentate Ligands as Stabilizing Agents for Catalytically Active Pd-Nanoparticles

Agnieszka Krogul-Sobczak* and Patrycja Kasperska University of Warsaw, Poland

Abstract

Nanocatalysts connect advantages typical for both, heterogeneous and heterogeneous catalysts, and some additional unique catalytic properties can be gained when the size of catalyst particles is between molecular level and macroscale. A choice of stabilizing ligand is extremely important because nanoparticles (NPs) of catalysts should effectively interact with the ligands and with the reacting compound(s). For bulky ligands the access to the catalyst surface might be restricted due to steric crowding resulting in a dramatic decrease of catalytic properties. Therefore, we turned our attention to monodentate ligands, inspired by the claim of Sullivan et al. that 4-(dimethylamino) pyridine (DMAP) is an ideal ligand for stabilizing transition metal NPs.

Monodentate N-heterocyclic compounds can be applied as stabilizing agents for catalytically active palladium nanoparticles

(PdNPs) and this is a first report in which we present the effect of a series of derivatives of pyridine, X-Py with X=-CH3, -Cl, and -N(CH3)2 substituents, on the size, stability and catalytic activity of PdNPs. Our experiments indicate that NPs stabilized by 4-methylpyridine and 4-(dimethylamino) pyridine show remarkable catalytic activity, in: reduction of nitrobenzene to aniline by NaBH4, reduction of nitrobenzene to aniline by CO/H2O, carbonylation of aniline to N,N’-diphenylurea by CO/O2.

Biography

Krogul-Sobczak received her Ph.D. in chemistry at University of Warsaw with doctoral thesis entitled: “Physico-chemical properties, catalytic and cytotoxic activity of palladium (II) complexes with derivatives of pyridine” in 2012. Since 2013 she works as an adjunct at Faculty of Chemistry, University of Warsaw (Poland). She cooperates with research group of Professor A. Pombeiro from Instituto Superior Tecnico in Lisbon. She focuses mainly on sustainable catalysis by searching for alternatives for industrial catalytic processes towards added value compounds.

References: 1. Langmuir 23, 2007, 12508–12520

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 42 New Insight into the Synthesis of Co- and Ni- based Catalyst for Ethanol Steam Reforming

Serena Esposito1*, Barbara Bonelli2, Simelys Hernadez2, Ilenia Rossetti3, Gianguido Ramis4 and Guido Saracco5 1University of Cassino and Southern Lazio, Italy 2Politecnico di Torino, Italy3Università degli Studi di Milano, Italy 4Università degli Studi di Genova, Italy 5Italian Institute of Technology-Turin, Italy

Abstract

Ni and Co-based catalysts represent the most attractive catalysts for the production of hydrogen by the steam reforming of ethanol (ESR) [1-3]. The performances of such systems depend mainly on metal dispersion that in turn can be affected by several factors, including the preparative route. With the intent to tailor the materials features through the variation of the synthesis parameters, three different synthesis procedures were adopted: a conventional hydrolytic alkoxide sol-gel route (I) a surfactant assisted sol-gel route (II) and (III) a Flame Pyrolysis (FP) method. Two supports were also compared, i.e. SiO2 and ZrO2, characterized by different surface acidities and redox properties, as well as different metal loading. All the catalysts were characterized by various techniques, including X-ray powder diffraction (XRPD), N2physisorption, scanning electron or transmission microscopy (SEM-TEM-EDX) and temperature-programmed reduction (TPR). The activity testing was done in a home-made micro-pilot plant for ethanols team reforming under different process conditions. Since the coke formation during the ESR is still an issue, the physico-chemical properties were also tuned to improve low temperature performance. The high surface area obtained for a surfactant assisted sol-gel route tried to fulfill this requirement. On the other hand, the high temperature synthesis adopted for FP was able to impart suitable thermal resistance to the samples, providing a good metal dispersion and a high metal–support interaction. The preparation method resulted to be powerful tool in driving the formation of a designed material with a delicate balance between the reducibility of the metal phase and a suitable metal dispersion.

References: 1. I. Rossetti et al. ApplCatal B: Environ. 2012, 117-118, 384-396. 2. E. Finocchio et al. Int. J. HydrogenEnerg. 2013, 38, 3123-3225. 3. M. Compagnoni et al. Catal. Sci. Technol. 2016, 6, 6247-6256.

Transition Metal Doped Noble Metals–Nanocatalyst Hybrids Materials for Oxygen Reduction Reactions

Thomas Wågberg1*, Robin Sandström1, Guangzhi Hu1, 2 and Eduardo Gracia-Espino1 1Umeå University, Sweden 2TheXinjiang Technical Institute of Physics and Chemistry, China

Abstract

The activity enhancement of noble metal based catalysts for the oxygen reduction reaction (ORR) by addition of one or more carefully selected transition metals is an excellent strategy to achieve high activity yet low content of the precious metal. This improvement in precious metal utilization is essential for vehicular applications where cost and abundance of materials are of enormous concern. Here we report different routes to efficient production of various nanoparticles x(Pt Y, PdxW, Pt xFe,

PtxCo) through a microwave assisted synthesis process using a conventional household microwave oven. A fast and simple material synthesis of only few minutes provides a highly scalable route suitable for industrial interests. We show that the ORR performance shows significant improvement by addition of a minute amount of transition metals and that optimized compositions outperform that of commercial Pt-Vulcan. A vast number of experimental techniques (EXAFS, HR_TEM, XPS, Raman spectroscopy) in combination with density functional theory calculations are used to get an insight into how the nanostructure influences the performance and properties of the hybrid nanomaterials. We will also discuss some future perspectives on the field of nanocatalysts.

Biography

Thomas Wågberg is a Professor in Nanophysics and Materials and Head of Physics Department, Umeå University. He has two decades of experience in the work on nanomaterials and nanotechnology. He is leading the Nano for Energy group (http:// www.umunano.org/) with expertise in synthesis, characterisation and implementation of nanomaterials for energy applications.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 43 For the last seven years Dr. T. Wågberg has been part of the organising committee of the Umeå Renewable Energy Meeting, an annual conference which attracts more than 200 scientists in the field of renewable energy.

The Correlation between the Most Photocatalytically Active and Least Toxic Metal-Doped ZnO nanoparticles

Hangil Lee Sookmyung Women’s University, South Korea

Abstract

The doped ZnO nanoparticles (NPs) with various transition metals (TM-ZnO NPs; TM = Cr, Mn, Fe, Co, or Ni) were determined which TM would yield the best catalyst with the lowest toxicity to cells. The TM-ZnO NPs were analyzed by using various surface analysis techniques such as transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS). And the catalysis of the five types of TM-ZnO NPs on the oxidation of 4-aminothiophenol (4-ATP) by using high-resolution photoemission spectroscopy (HRPES) under UV illumination were evaluated. Moreover, in order to compare the cell toxicity levels of these TM-ZnO NPs, we injected them into cells from a lung cancer cell line and monitored the viability levels of the cells. The spectral analyses indicated Fe- and Co-ZnO NPs to exhibit the highest catalytic activities whereas the toxicity tests indicated the cells exposed to Mn- and Fe-ZnO NPs to be most stable. Taking into consideration both the catalytic activity and cell toxicity results, we conclude Fe-ZnO NPs to be the most appropriate catalyst of those tested.

Nanostructured ZnO Loaded on Ceramic Honeycomb for Municipal Solid Waste–Derived Syngas Desulfurization: Performance and Kinetic Studies

Wen–Da Oh*, Junxi Lei, Veksha Andrei, Apostolos Giannis, Grzegorz Lisak and Teik–Thye Lim Nanyang Technological University, Singapore

Abstract

The gasification process can be employed to produce electrical energy from municipal solid waste (MSW). The raw syngas generated from the MSW gasification needs to be purified from corrosive sulfur compounds prior to application. In this study, a facile seeding-growth protocol was employed to immobilize nano-structured ZnO with nanorods and nanosheets (ZnO- nS) morphologies on the cordierite–mullite honeycomb support. These supported nano-structured ZnO were characterized using FESEM, EDX and XRD indicating that the nano-structured ZnO was highly crystalline with a thickness of ~1 µm. The performances of these nano-structured ZnO-loaded honeycomb and commercial ZnO sorbents for desulfurization of MSW-derived syngas were evaluated at moderate temperature (400°C) in a fixed tubular reactor. It was found that the ZnO- -1 nS showed higher total sulfur sorption capacity and longer breakthrough time (49 mg S g ZnO, BTTS = 75 min) compared to -1 that of the ZnO with nanorods morphology (9-12 mg S g ZnO, BTTS = 23-25 min) and commercial ZnO sorbent (5 S mg -1 g ZnO, BTTS = 7 min).This is attributed to the significantly better surface coverage, lower mass transfer resistance, and higher crystallinity of ZnO nanosheets. A mechanistic kinetic model for sulfur compounds removal by ZnO-nS is also proposed. The ZnO-nS can be regenerated with 15% air, 30% steam and 55% nitrogen gas mixture at 550°C and space velocity of 4878 h-1, without losing its sorption capacity. The results indicate that ZnO-nS can be employed as a promising material with low mass transfer resistance for MSW-derived syngas desulfurization.

Biography

Oh Wen Da is a research fellow at the Residues and Resources Reclamation Centre (R3C), Nanyang Environment and Water Research Institute. He obtained his PhD from NTU in 2016. In 2012, he obtained his MSc in Environmental Chemistry from University of Science, Malaysia. His current research interests focus on the development of catalytic materials for environmental application and waste-to-energy process.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 44 + Effect of the of NH4 Ions Exchange and HCl Treatment on the Acidity and Porosity of Natural Zeolite Clinoptilolite

Hendrik Kosslick1*, Riaz Muhammad1, Raja Al-Otabi2, Faisal Alotaibi2, Axel Schulz1 and Christian Jaeger3 1University of Rostock, Germany 2King Abdul Aziz Centre of Science and Technology, Saudi Arabia 3Federal Institute of Material Research and Testing, Germany

Abstract

Clinoptilolite is one of the most abundant natural zeolites. It contains a 2-deminsional, medium sized pore system consisting of oxygen-8- membered and oxygen-10-membered rings [1]. Clinoptilolite is microporous can be acidified via ammonium ion exchange or acid treatment and is a potential acid catalyst. Clinoptilolite was modified by both the methods. The influence of the modification on the structure, morphology, acidity and, texture was studied by XRD, TEM, FTIR, XPS, TG/DSC, ammonia- TPD, 1H-, 27Al- and 29SI MAS NMR and nitrogen adsorption-desorption measurements. The catalytic activity was studied in the acid catalyzed acetalization of benzaldehyde with butandiol-1,3. The ion exchange experiments shows that ca 45% of the cations of clinoptilolite readily exchange with ammonium ions and protons supplied by acid treatment. The presence of acidic protons of medium to strong strength is confirmed by ammonia-TPD and proton NMR measurements. The sample activation causes a partial dealumination as indicated by the appearance of 5- and 6-fold coordinated aluminum. The nature of sites and its impact on the catalytic activity as well as a collaborative action of Brønsted acid sites and 5-fold coordinated aluminum is discussed. Acidic natural clinoptilolite catalysts prepared shows a positive influence on acidity and porosity. Modification creates hierarchical micro-nano porosity. The specific surface area varies between ca.452 m /g and 257 m2/g.

Acknowledgments We gratefully acknowledge the excellent assistance of Dr. A. Villinger (XRD) and Dr. M. Frank from EMZ Univ. Rostock for TEM images.

References: 1. A. Dziedziecka, B. Sulikowski, : Ruggiero-Mikulajczyk, Catal. Today, 2016, 259, 50-58.

Biography

Hendrik Kosslick received his master’s Degree from the Humboldt University zu Berlin in 1976. He received his PhD in 1984 and its Habilition in 1994 from the University of Potsdam/Germany. He started his carrier at Central Institute of Physical Chemistry of the Academy of Sciences. His research interest is preparation of porous materials as zeolites, MOFs porous, mesoporous materials and oxides for application as catalyst or catalyst supports and testing. Currently he is a topic leader for heterogeneous catalysts and testing at the Institute of Chemistry and Leibniz-Institute for Catalysis at the University of Rostock.

Development of Magnetic Nano-catalysts for the Photo-degradation of Organo-Chlorine and Organo-Phosphorus Pesticides

Jitendra R. Satam K. J. Somaiya College of Engineering, India

Abstract

The magnetically separable nano-catalysts were synthesized by Sol-gel synthesis method. Nitrate precursor salts of Fe and Zn, were used while alkoxide precursors of Si and Ti were used for the synthesis. Loading of 5 weight % to 15 weight % of various metal oxides was done on Fe3O4 (magnetite). The catalysts prepared are named as Fe3O4, 10 % ZnO/Fe3O4, 10 % TiO2/

Fe3O4, 10 % SiO2/Fe3O4. It was observed that loading of 10 weight % of different metal oxides on Fe3O4 (magnetite) found to be the best candidates for photo degradation of pesticides in water while, the best composition as photocatalyst was found to be 10% TiO2/Fe3O4. The as-synthesized nano-particle catalysts were characterized by X-ray Diffraction (XRD), Scanning electron microscopy (SEM) and Tunnelling Electron Microscope (TEM) etc. TEM images shown that average atomic size of

10 weight % TiO2/Fe3O4nano-particles is in the range of 20-30 nm.The degradation pathway of different Organo-chlorine and Organo-phosphorus pesticides was studied using as synthesized magnetically separable nano-catalysts in a Specially Designed

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 45 Photo Batch Reactor. Advanced oxidation process method was used using UV/H2O2 and UV/TBHP combinations. The effect of parameters such as, chemical oxidants, reaction time, pH, temperature, reusability of the catalysts was studied. The COD (Chemical Oxygen Demand) of water before and after the degradation reactions was performed to test further toxicity of treated water under the application of UV light and magnetic nanoparticle catalysts.

Biography

Jitendra Satam is currently working as an Assistant professor, Faculty of Applied Chemistry in K. J. Somaiya College of Engineering, Mumbai, India since 2013. Previously he has worked as senior scientist (R & D) in United Phosphorus Ltd. India from 2008 to 2012. He obtained his PhD. in catalysis from Institute of Chemical Technology, Mumbai, India. His research interest lies in Synthesis of metal oxides, nano-catalyst development especially heterogeneous catalysts. Currently he is working on the project on photocatalytic degradation and removal of organic pollutants in water. He has published 10 papers in various reputed international journals.

Switchable Flow Hydrogenation Chemoselectivity by Simple Sn-Modification of Ni Nano-Catalyst

Damian Gizinski1*, Ilona Goszewska1, Damian Giziński1, Małgorzata Zienkiewicz-Machnik1, Dmytro Lisovytskiy1, Marcin Pisarek1, Grzegorz Słowik2, Anna Śrębowata1 and Jacinto Sá1,3 1Institute of Physical Chemistry Polish Academy of Sciences, Poland 2Maria Curie-Skłodowska University, Lublin 3Uppsala University, Sweden

Abstract

Surface organometallic chemistry (SOMC) is a versatile and powerful tool to modify and control catalytic proficiencies. We applied SOMC to modify nickel catalyst (0,7 wt.%) grafted on polymeric resin with Sn, and consequently change the steric and electronic properties of the monometallic active sites. Post-modification procedure was conducted by surface reduction of tetrabuthyltin solution in micro-flow high-pressure reactor, yielding two catalysts with different tin content. The synthesized catalysts were characterized by PXRD, XPS, FT-IR and TEM after synthesis.

The monometallic and bimetallic catalysts were tested in chemoselective hydrogenation of 6-methyl-5-hepten-2-one in flow, where C=C and C=O double bonds coexist. For parent catalyst we obtained very high activity and selectivity towards product of C=C hydrogenation. The addition of small amounts of tin resulted in significantly increase in formation of C=O hydrogenation product. The extent of C=O bond hydrogenation was found to be Ni/Sn ratio dependent. Application of flow condition and the execution of the screening of the reaction using different pressures and temperatures, in the case of bimetallic catalysts, allowed to control the selectivity, and the point where the catalysts were in 100% selective only to C=C or C=O bond hydrogenation was noticed. XPS and XRD characterization after catalytic tests and catalytic measurements over extended reaction times, confirmed that the materials are stable.

This work was financially supported by National Science Centre in Poland within the project OPUS 8 (UMO-2014/15/B/ ST5/02094).

Stability of Electrocatalytic Nanoparticles in Organic Solvents

Tom Breugelmans1*, Nejc Hodnik2 and Bart Vanrenterghem1 1University of Antwerp, Belgium 2National Institute of Chemistry, Slovenia

Abstract

In recent years a lot of attention has been devoted to the synthesis of nanoparticles for several electrochemical applications such as carbon-carbon bond formation reactions. On this topic, a multitude of studies have been carried out to investigate the synthesis of tailor-made nanoparticles with an optimal activity. A measure not yet investigated is the long-term stability of these electrocatalytic materials in organic solvents. In aqueous solutions it is known that one of the predominant electrocatalysts stability issues is the growth of particles, which is accompanied by unvented decrease in electrochemical active surface area.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 46 However, this knowledge is still unknown in organic solvents. Accurate understanding of the degradation processes will open new directions towards the synthesis of long-term, stable nanoparticles in organic electrocatalysis.

In this work we will for the first time report a stability study of metal nanoparticles towards an organic reduction reaction. To give an in-depth description of the stability our approach will be threefold and show the (1) electrochemical, (2) microscopical and (3) analytical approximations. The electrochemical investigation will be carried out using cyclic voltammetry (CV) and linear sweep voltammetry in combination with a rotating disk electrode (LSV-RDE) as primary techniques. Morphological variation will be studied with identical location Scanning Electron Microscopy (IL-SEM) and In Situ Transmission Electron Microscopy (IS-TEM). This enables the morphological study of the same particles at nanoscale level. Finally, the analytical investigation will be carried out by coupling an electrochemical flow cell with ICP-MS.

Biography

Tom Breugelmans received his PhD (2010) from the Vrije Universiteit Brussel. Currently he is Professor and vice dean at the Faculty of Applied Engineering at the University of Antwerp. He is spokesman of the research group Advanced Reactor Technology. He has expertise in different electrochemical techniques (LSV, CV and EIS), electrocatalysis, electro synthesis and reactor engineering (micro- and mesoreactors, electrochemical reactors). He is (inter)nationally active in the field of electrochemistry and is Belgian regional representative of the International Society of Electrochemistry and is secretary of the working group of Electrochemistry of the KNCV. He is author of 45 ISI publications.

Microstructural Properties of ZnO Powder Nanostructures Prepared by Mechanical Alloying

Oudjertli Salah 1 *, Bensalem Rachid 1, Alleg Safia1 , J. J. Suñol2 and Mohamed Bououdina 3 1Université de Annaba, Algeria 2Universitat de Girona, Spain 3University of Bahrain, Bahrain

Abstract

Introduction: Wide band gap semiconductors (ZnO) have been studied for several years in a highly competitive international environment given their wide range of applications. In our work we prepared powder nanoparticles mechanically alloyed.

Experimental/Theoretical Study:ZnO powder nanoparticles mechanically alloyed were doped with iron to investigate their structural and microstructural properties using X-ray diffraction (XRD) , scanning electron microscopy (SEM) [1,2] and differential scanning calorimetry ( DSC ) for examined ZnO and 5% Fe doped ZnO.

Results and Discussion: The ZnO starting pure powder exhibited a hexagonal crystal structure with space group p63mc of ZnO, however with the introduction of 5%Fe in the ZnO milled powder, the hexagonal ZnO phase remained unchanged, whereas the microstructural parameters were subject to significant variations due to the introduction of Fe atoms into the ZnO hexagonal matrix to replace oxygen ones [3]. The size of crystallites and microstrains are found milling time dependent.

Conclusion: This product exhibited a hexagonal crystal structure with space group p63mc of ZnO and with c-axis preferential orientation, however with the introduction of 5 % Fe in the ZnO milled powder, the hexagonal ZnO phase remained unchanged, whereas the microstructural properties were subject to significant variations due to the introduction of Fe atoms into the ZnO hexagonal matrix to replace oxygen ones.

References: 1. B. Weintraub, Z. Zhou, Y. Li, and Y. Deng, “Solution synthesis of one-dimensional ZnO nanomaterials and their applications,” Nanoscale, vol. 2, no. 9, pp. 1573-1587, 2010. 2. Look, D.C. (2006) ‘Progress in ZnO materials and devices’, Journal of Electronic Materials Vol. 35, pp. 1299-1305. 3. S Q. B. Ma, Z. Z. Ye, H. P. He, L.P. Zhu, J.Y. Huang, Y. Z. Zhang and B. H. Zhao, Scripta Materialia.vol. 58 21-24, 2008.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 47 In situ Electrical Conductivity Studies of Ce-Pr Mixed Oxides Catalysts

Ioan-Cezar Marcu1*, Ionel Popescu1, Juan Carlos Martínez-Munuera2 and Avelina García-García2 1University of Bucharest, Romania 2University of Alicante, Spain

Abstract

Ce-Pr mixed oxides are known to be promising catalysts for environmental applications, such as N2O decomposition, CO oxidation, light hydrocarbons combustion and soot combustion. However, for explaining the fundamental origin of their catalytic properties and establishing the structure-activity correlations, complementary characterization studies are required.

A useful and highly sensitive technique to characterize the electronic and redox properties of oxidation catalysts in correlation with their catalytic performances is the in situ electrical conductivity measurement. This allows to gain insight into the key features of the redox catalysts that determine their catalytic activity to better understand the origin of the catalytic effect and the reaction mechanism involved and, consequently, to improve the catalysts on a scientific basis or to rationally design efficient new ones.

In this work, DC-electrical conductivity of the Ce-Pr mixed oxides, namely Ce0.8Pr0.2O2, Ce0.5Pr0.5O2 and Ce0.2Pr0.8O2, as well as of pure CeO2 and PrO2-δwas studied as a function of temperature and oxygen partial pressure, and temporal responses during sequential exposures to air and different gaseous mixtures containing methane, CO or 2H , in conditions close to those of their catalytic applications, were analyzed. Comparisons between the different systems and correlations between their redox and semi conductive properties and their catalytic behavior in different oxidation reactions have been established.

Biography

BSc in Chemistry & Physics in 1995 and MSc in Catalysis in 1996 at the University of Bucharest (UB). PhD in Catalysis in 2002 at the Institute of Catalysis – University Lyon 1. CNRS post-doctoral researcher at the Institute Charles Gerhardt Montpellier from oct. 2006 to sept. 2007. Habilitation in Catalysis in 2013 at UB. Associate Professor at UB from 2005, in charge of Chemical Technology and Catalytic Materials courses. Senior Researcher at the Research Center for Catalysts and Catalytic Processes of UB from 2007. Research interests cover the field of catalysis by metal oxides. More than 70 publications including a book chapter (www.researcherid.com/rid/B-1509-2008).

In situ-DRIFTS Study: Influence of Hydrogen Spillover on the Brönsted Acid Sites Evolution over Non-Reducible and Reducible Support using Ammonia as Probe Molecule

Adisak Guntida1*, KongkiatSuriye2, JoongjaiPanpranot1 and PiyasanPraserthdam1 1Chulalongkorn University, Thailand 2SCG Chemicals, Thailand

Abstract

Hydrogen spillover effect was studied to investigate the ethene hydrogenation at 40o C and atmospheric pressure. Three catalysts γ γ γ of Pt/ -Al2O3, Pt-Sn/ -Al2O3, and Pt-Sn-K/ -Al2O3 were prepared by the incipient wetness impregnation method. As revealed by characterization results from H2-TPD and NH3-TPD, role of Sn and K induces the hydrogen spillover from the Pt metal sites onto its Al2O3 support. However, the addition of Sn and K modified the acidity of catalyst, resulting in the modification of amount of hydrogen adsorbed on the catalyst surface. From the experiment results, the amount of hydrogen spillover was directly proportional to those of the acidity of catalysts, leading to higher ethene hydrogenation. In addition, when Pt-base catalyst was physically mixed with the acid diluents, the hydrogen spillover effect from Pt-base catalyst onto the acid diluents promoted by Sn and K was observed on the ethene hydrogenation as well.

Biography

Adisak Guntida was born on January 6th, 1989 in Lampang, Thailand. He has graduated with a bachelor’s degree in chemical engineering from the Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang, Bangkok, Thailand, in April 2011. And he graduated with a master’s degree of Chemical Engineering at the Faculty of Engineering,

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 48 Chulalongkorn University, Thailand, in July 2015. He continued his study in doctoral degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2015 under the SCG Chemical Co.,Ltd., (Thailand) scholarship.

Polyhedral Cu2O to Cu Pseudomorphic Conversion for Stereoselective Alkyne Semi-Hydrogenation

Mahesh Madasu*, Sourav Rej, Chih-Shan Tan, Chi-Fu Hsia and Michael H. Huang National TsingHua University, Taiwan

Abstract

Cu2O cubes, octahedra, and rhombic dodecahedra can be pseudomorphically converted into Cu crystals of corresponding shapes through reduction by ammonia borane in ethanol at 50oC or below within 3 min, demonstrating the feasibility of making challenging polyhedral metal particles from metal oxide crystals. Hydrogen gas is also produced from ammonia borane in the process. The obtained Cu crystals have slightly nanoporous interior. Addition of diphenylacetylene in the formation of Cu rhombic dodecahedra leads to complete stereoselective production of sterically hindered (Z)-stilbene. Semi hydrogenation of other alkynes also gives pure (Z)-alkenes. Cu cubes and octahedra also showed excellent (Z)-stilbene selectivity along with minor formation of (E)-stilbene and bibenzyl as compared to CuCl2 and commercial Cu2O particles. Mechanistic studies reveal low binding affinity of alkenes on the rhombic dodecahedra surfaces leads to high product selectivity. These Cu crystals act as green and low-cost catalyst for the synthesis of high-purity (Z)-alkenes with high reproducibility.

Biography

Mahesh Madasu has received B.Sc. degree from Kakatiya University, India, in 2009 and M. Sc. degree obtained from Department of Chemistry at Indian Institute of Technology Mumbai, India, in 2012. From 2012 to 2014, he worked as a Junior Research Fellow in the Department of Chemistry, IIT Bombay. Currently, he is working as a Ph.D. student under the supervision of Prof. Michael. H. Huang, Department of Chemistry, National TsingHua University, Taiwan.

Kinetics Study of Propylene Self-Metathesis Over Silica-Zeolite Supported Tungsten Catalyst

Kawin Lorattanaprasert1*, Kongkiate Suriye2 and Suttichai Assabumrungrat1 1Chulalongkorn University, Thailand 2SCG Chemicals, Thailand

Abstract

The kinetics of propylene self-metathesis over silica-zeolite supported tungsten catalyst was investigated. The catalytic reaction was carried out in a laboratory-scale packed bed reactor under atmospheric pressure in the temperature range of 773-873 K with various gas hourly space velocities (GHSV). The experiments were conducted by using various gaseous feeds. These conclude: 1-butene, ethylene mixed with 2-butene and ethylene mixed with 2-pentene in order to estimate reliable kinetic parameters. The kinetic studies were performed in the absence of mass transfer limitations. The catalyst had no deactivation after the reaction time of 16 hours. Power law rate expressions were used to describe the kinetics of the main and side reactions using steady state experimental data obtained under a range of reaction conditions. The results showed that the predicted values and the experimentally measured values are in a good agreement.

Biography

Kawin Lorattanaprasert was born on September 23rd, 1992 in Mukdahan, Thailand. He graduated with a bachelor’s degree (second class honors) in chemical engineering from the Faculty of Engineering, KhonKaen University, KhonKaen, Thailand, in April 2015. He continued his study in master degree of Chemical Engineering at the Faculty of Engineering, Chulalongkorn University, Thailand since August 2015 under the SCG Chemical Co.,Ltd., (Thailand) scholarship.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 49 γ A Comparative Study of Propane Dehydrogenation Over Pt, Pt-Sn, and Pt-In Supported on -Al2O3 and Hydrotalcite Supports

Weerachon Tolek1*, Kongkiat Suriye2 , Piyasan Praserthdam1 and Joongjai Panpranot1 1Chulalongkorn University, Thailand 2SCG Chemicals Co., Ltd. Thailand

Abstract γ Dehydrogenation of propane was investigated over Pt, Pt-Sn, and Pt-In supported on -Al2O3 (Al) and hydrotalcite γ (HT) supports at 550o C and atmospheric pressure. The second metal loading was varied at 0.3 and 0.6 wt%. On -Al2O3, addition of the second metal resulted in an increased catalytic activity of Pt catalysts, except for the Pt0.6Sn. The activity of Pt/HT was much higher than Pt/Al. However, when Pt/HT was promoted with either Sn or In, the activity was slightly decreased. Nevertheless, the deactivation trend was totally diminished on the promoted Pt/HT catalysts. Lower alkane and C5+ productions were obtained on all the promoted catalysts, suggesting the reduction of side reactions especially over the HT supports. Regardless of the supports used, increasing of Sn loading from 0.3 to 0.6 wt% resulted in lower activity than the monometallic Pt catalysts while for In, increasing loading from 0.3 to 0.6 wt%, the activity monotonically increased. On HT γ support, the activity was in the order: Pt0.3Sn Pt Pt0.6In > Pt0.6Sn > Pt0.3In whereas on -Al2O3, the activity increased in the order Pt0.6In > Pt0.3Sn >Pt0.3In > Pt > Pt0.6Sn.∼ ∼ The catalysts were also characterized by transmission electron microscopy energy dispersive X-ray spectroscopy (TEM-EDX), X-ray photoelectron spectroscopy (XPS), NH3-temperature program desorption, H2 temperature program reduction, and thermogravimetric analysis (TGA).

Biography

Weerachon Tolek was born on March 10th, 1990 in Bangkok, Thailand. He was a doctoral student in Chemical Engineering at Chulalongkorn University, Thailand. He also received his bachelor’s degree with 2nd class honors from Chulalongkorn University (Chemical Engineering). He has been awarded Scholarship which is a collaboration agreement between the Faculty of Engineering at Chulalongkorn University and the Siam Cement Public Company Limited (SCG Chemicals) to conduct a research and development on the technology for petrochemical industry. He has been studied in the field of catalyst development to understand the elementary steps involved in catalytic reactions.

Determination of Metal Nanoparticles Surface Area and Sizes through Quantitative Ligand Adsorption–Chemisorption

Matumuene Joe Ndolomingo* and Reinout Meijboom University of Johannesburg, South Africa

Abstract

The effective catalytic properties of the metal nanoparticles are mostly based on their inherent high surface area to volume ratio. The determination of the true surface area of the metal nanoparticle in catalysis represents one of the greatest challenges due to the nanoparticle surface unevenness and morphological irregularity. We report on the ligand adsorption-based technique for the determination of specific surface area of gold and copper nanoparticles on gamma alumina supports. Quantification of ligand packing density on gold and copper nanoparticles is also reported. 2-mercaptobenzimidazole (2-MBI) was used as probe ligand. The adsorption of 2-MBI on the nanoparticle surface was followed by ultraviolet-visible spectrometry. The amount of ligand adsorbed was found to be proportional to the gold and copper nanoparticles surface area. A fair agreement was found between gold and copper particle sizes obtained from ligand adsorption and transmission electron microscopy methods. The catalytic evaluation of the as-prepared gold and copper nanoparticles related to their inherent surface area was followed using the model reaction of the oxidation of morin by hydrogen peroxide.

References: 1. M.J. Ndolomingo, R. Meijboom, Applied Surface Science 390 (2016) 224–235. 2. M.J. Ndolomingo, R. Meijboom, Applied Catalysis B: Environmental 199 (2016) 142–154.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 50 Biography

Matumuene Joe Ndolomingo, studied chemistry at UJ (University of Johannesburg-RSA) and obtained his Ph.D. in 2016 under the guidance of Prof. R. Meijboom. Presently, he is a Post-Doctoral fellow at the same University in chemistry department at Prof. Meijboom’s Research Center for Synthesis and Catalysis. His current research interests include the synthesis and development of mesoporous metal oxides supported metal nanoparticles for industrial oxidation and hydrogenation reactions, and development of a simple general approach for the easy determination of the true surface area and particles sizes of a wide range of metal nanoparticles using organo-thiols as probe ligand.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 51 Scientific Session-4: Photocatalysis & Electrocatalysis

Photocatalytic Antibacteria on Ag/TiO2-CeO2 Thin Film

Yu-Wen Chen* and Benjawan National Central University, Taiwan

Abstract

Ag/CeO2‒TiO 2 was prepared by a peroxo sol-gel method for antibacterial application. The as-prepared materials were characterised by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The antibacterial activities of the samples were tested against two different bacteria: Escherichia coli (OP50), a Gram-negative organism and Staphylococcus aureus (USA300), a Gram-positive organism. The antibacterial effectiveness of the Ag/CeO2‒TiO 2 coating was >99.99%, i.e. it was extremely effective against both E. coli (OP50) and S. aureus (USA300) after either 30 min of illumination with UVA radiation or 24-hour of incubation in the dark. The Ag/CeO2‒TiO 2 coating was found to be significantly more active than pure TiO2 and TiO2 doped with CeO2 or

Ag alone. Therefore, Ag/CeO2‒TiO 2 can be used as a coating material for the disinfection of both Gram-positive and Gram- negative bacteria.

Biography

Yu-Wen Chen received PhD degree from University of Pittsburgh in 1982. He joined National Central University, Taiwan,in 1983. He developed several catalysts which has been commercialized in Taiwan. He has published 275 journal papers and filed 82 patents. He is the fellow of AIChE and RSC. He is the adjunct professor of Nanjing University in China and inviting professor of Tomsk State University in Russia. He was the president of Taiwan Institute of Chemical Engineers in the last 2 years.

Electrolytic H2 for Ffuel Enrichment

Dominic Walsh1*, Liam Wrigley, Tom Russel2, Katherine Fielden2, Chris D. Bannister1 and Salvador Eslava1 1University of Bath, UK 2Advanced Fuel Technologies, UK

Abstract Hydrogen has the highest energy density per unit mass of any form of chemical fuel source, when burnt in a combustion engine with O2 or used to power a fuel cell it releases only water. For hydrogen fuel not to have a carbon footprint a clean source of hydrogen production is needed. An exciting way to do this would be electrochemical water splitting powered by renewable electricity such as wind and solar. Many studies have previously been undertaken and reported hydrogen evolution reaction (HER) catalysts include metal carbides (e.g. W2C, Mo2C), phosphides (e.g. Ni2P), nitrides (e.g. W2N), bimetallic alloys (e.g. CuTi) and sulphides (e.g. MoS2). Platinum is known to be the superior catalyst in terms of efficiency, however Pt use is limited by its high cost. Here we report on the synthesis and testing of reduction catalyst materials key to converting protons liberated by electrolysis of water into hydrogen gas. We have investigated catalytic activity of graphene oxide supported bimetallic carbides and nitrides of titanium and molybdenum prepared by novel methods which used synthesized TiMo oxo- cage clusters as precursors. These oxo-cage material allowed synthesis of high surface area nitrides and carbides on rGO by heating under ammonia or argon. Nano-MoS2 as an HER catalyst was also investigated by preparing decorated graphene oxide and also a range of biopolymer derived carbon-MoS2 composites. Furthermore, enzymatic processing of biopolymer-MoS2 solutions was used to form stable MoS2 nanosuspensions for use as HER cathode coatings. Measured electrocatalytic activity was close to that of Pt was obtained. Biography

Dominic Walsh is a researcher on materials for solar energy and fuels, including photocatalytic water splitting and hydrogen production. Dr Walsh has previously researched nanoparticle catalyst materials - in particular transition metal oxides, ceramics and composites at the School of Chemistry, Bristol University and NIMS Institute, Tsukuba, Japan. Dr Walsh is now based at the Chemical Engineering Department, University of Bath.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 52 Charge-Transfer Effect of GZO Film on Photochemical Water Splitting of Transparent ZnO@GZO Films by RF Magnetron Sputtering

Sujun Guan*, Leo Yamawaki and Xinwei Zhao Tokyo University of Science, Japan Abstract

The transparent conducting oxides (TCOs) have gained much attention owing to their potential applications in several optoelectronic devices such as light emitting diodes, solar cells, and thin film transistors for the flat panel displays, and optical detectors as well as flexible displays. However, ZnO also suffers from the drawback that limit efficient water splitting, such as the low photo-corrosion resistant, wide band gap energy of 3.37 eV and rapid recombination rate due to the formation of unwanted species that act as trapping sites. To improve water splitting performance, suppressing the recombination is the most commonly used strategy by charge transfer via coupling with that of better conductivity.

With the purpose of enhancing the photochemical water splitting performance, GZO film has been used to increase the charge transfer of ZnO film by RF magnetron sputtering. The characterization of ZnO film and the ZnO@GZO films was carried out by X-ray diffraction, DRUV-vis spectra, X-ray photoelectron spectroscopy, atomic force microscope, photoluminescence spectroscopy and photochemical water splitting. X-ray patterns reveal that ZnO@GZO films show a related highlyc -axis peak (002). DRUV-vis results show that the GZO film with wide band gap would not affect the band gap of ZnO@GZO films. Photoluminescence spectra reveal that the recombination of electron and hole decreased via the increased charge transfer by GZO film. Compared with that of ZnO film, the ZnO@GZO films could efficiently enhance the photochemical water splitting performance via the increased charge transfer by GZO film. Biography

Guan is an associate professor working in the Solar Energy Group in the Department of Physics at Tokyo University of Science. Prior to this; he gained his PhD in Department of Mechanical Engineering at Chiba University working on enhancement of visible-light absorption and photocatalytic activity of metal oxide coatings. His current research focuses on the transparent conducting oxides thin film with hetero-junction photocatalysts for water splitting and solar cell.

Metal Oxide-Graphene Hybrids: New Multifunctional Materials for Photocatalysis

Raphaël Schneider1*, Hatem Moussa1, Atef Riahi2 and Batukhan Tatykayev3 1Université de Lorraine, France 2Physique des Matériaux Lamellaires et Nano-Matériaux Hybrides, Tunisie 3Al-Farabi Kazakh National University, Kazakhstan Abstract

In recent years, numerous strategies have been developed to improve the photocatalytic performances of metal oxide semiconductors (MOS). Among them, the association of MOS with graphene-based materials is of high interest. Indeed, if MOS are well associated to graphene-based materials, the latter will not only act as a sink of the photo-generated electrons but will also allow their migration and thus hinder the charge recombination and improve the photocatalytic efficiency. Moreover, the heterojunction constructed between MOS and graphene-based materials will also increase the optical absorption of the photocatalyst in the visible region and thus enhance the photocatalytic activity under simulated solar light irradiation.

In this communication, we report the preparation via hydro- or solvothermal processes of photocatalysts associating reduced graphene oxide (rGO) or graphitic carbon nitride (gC3N4) with zinc oxide ZnO or perovskite materials like LaFeO3. The photocatalytic activities of these materials under simulated solar light or under visible light irradiation either for water decontamination or for hydrogen production via water splitting will be discussed. Biography

Raphaël Schneider is professor of organic chemistry of the University de Lorraine and develops his research in the “Reactions and Chemical Engineering Laboratory (LRGP, UMR CNRS-UL 7274)” at Nancy. He is the co-author of more than 140 papers linked to nanomaterials. His research interests include quantum dots, metal-organic frameworks, catalysis, and photocatalysis.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 53 Enhanced Photoactivity Hydrogen Generation by Electron Tunneling via Flip-Flop Hopping Over

Iodinated Graphitic C3N4

Gongxuan Lu Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, China

Abstract

In this work, the significant electron tunneling over iodine-decorated graphitic carbon nitride (I-g-C3N4) was achieved by - - I3 andI5 cluster doping. The flip-flop electron tunneling takes place via strong Rashba spin-orbit coupling in p orbitals of doped polyiodides. The electron tunneling and hopping bridged the easier transfer route between far-located carbon atoms of g-C3N4 through the polyiodides p orbitals. By taking the advantage of this tunneling, the conductivity of I-g-C3N4/Ag photocatalyst was remarkably increased and the lifetime of photogenerated charges was largely prolonged, evidenced by I-V characteristics and the photoluminescence (PL) spectra. With the help of these properties, the obtained I-g-C3N4/Ag photocatalyst present a highly active for hydrogen generation under visible light irradiation. 104.3 µmol H2 was evolved over I-g-C3N4/Ag photocatalyst in 3 h, about three time higher than that of un-iodine doped g-C3N4/Ag, and no remarkable decay of activity was observed in 900 min reaction. The highest AQE value of 7.3% was achieved at 520 nm.

Biography

Lu obtained his PhD in Physical Chemistry in 1993 from the Chinese Academy of Sciences. He became a member of State Key Laboratory for Oxo Synthesis and Selective Oxidation (OSSO) in 1986. His research interests include environment– friendly catalysis, catalytic hydrogen production, reusable energy sources conversion, solar energy conversion and storage via photocatalysis. He has published more than 350 papers in those fields. Currently, he is the deputy chief editor of the Journal of Molecular Catalysis (China), fellow of Chinese Renewable Energy Society (Photochemistry Committee), Chinese Chemical Society, and Chinese Catalysis Society.

Tuning Photocatalysis by Band Gap Engineering and Defect Design of Metal Oxides using Molecular Layer Deposition

Roie Yerushalmi The Hebrew University of Jerusalem, Israel

Abstract

Metal Oxides (MOs) are central in a wide range of fields and for numerous applications including catalysis, photo catalysis, sensing, photonics, optoelectronic devices, renewable energy, electrochemistry and more. The use of Molecular Layer Deposition (MLD) in the context of photocatalysis opens new routes towards non-stoichiometric oxides for tuning and optimizing the reactivity and performances of MO catalysts. Specifically for MOs, oxygen vacancies (OV) are important structural defect that alter the reactivity of MOs by introduction of new electronic states within the band gap (BG). The use of MLD for defect design offers additional valuable handles for optimizing MO electronic structure further to control over the crystalline phase and impurity doping. A widely studied MO in the context of OV is non-stoichiometric Titania, TiO2-d. The electronic structure, charge transport, and surface properties of TiO2-d are closely related to the details of the defects and OV. Hybrid organic- inorganic Ti-Ethylene glycol (Ti-EG) thin films prepared by MLD are demonstrated for attaining oxygen-deficient Titania with control over the electronic defect states and electronic bands positions. In my talk I will present our current understanding of the electronic structure evolution that takes place when annealing hybrid films leading to the highly photocatalytic oxide thin films. The correlation of OV details and band positioning with the unique photocatalytic performance demonstrated for annealed films will be discussed.

Biography

Roie Yerushalmi is a member of the Institute of Chemistry and the Harvey M. Krueger Center for Nanoscience and Nanotechnology at the Hebrew University of Jerusalem. His research interests include design and synthesis of hybrid nanostructures, nanoscale doping of semiconductors, and photocatalysis. The research includes the development of new surface chemistries, synthesis and surface modification of hybrid nanostructures, ex-situ doping of nanostructures, nanostructure array assembly, and comprehensive characterization of complex nano systems by application of analytical methods.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 54 Spectral Selective Solar Light Enhanced Photocatalysis: Multilayer TiO2/VO2 and TiO2/TiAlN Films

Lars Osterlund Uppsala University, Sweden

Abstract

The possibility to increase human comfort and reduce the global footprint of buildings is a powerful driving force for introduction of new building technology. Introduction of functional coatings in buildings can meet some of these demands. We demonstrate here that photocatalytic films can be tailored such that they can be up-scaled and used for indoor air cleaning and self-cleaning coatings with sustained and increased activity. Three approaches to achieve these improved functions are presented. First, enhanced photocatalytic activity is obtained by synthesis of controlled amount of <001> preferential orientation of nanostructured anatase TiO2 films by reactive dc magnetron sputtering [1]. The preferentially oriented films imply a textured surface that expose up to 40% of {001} surfaces, and whose reactivity towards oxidation of acetaldehyde increases non-linearly with fraction of <001> orientation. About 10-fold increased reactivity and enhanced resilience towards deactivation is observed for the film exhibiting 40% <001> orientation. In a second approach, chemical surface functionalization of TiO2 by means of photo-fixation of SO2 and NO2 are done to bind sulphate and nitrate groups to the surface, and hence acidify the surface [2, 3]. By doing so bonding of weak acidic intermediates from VOC photo-degradation and subsequent surface deactivation is avoided. Atomic scale insight into the sulphate surface functionalization and the bonding of strongly bonded intermediates, and formic acid in particular, are obtained by interplay between in situ Fourier transform infrared spectroscopy, in vacuo infrared absorption spectroscopy and density functional theory calculations. Furthermore, the wetting properties of the TiO2 films are [4, 5] also modified . In the third approach, TiO2 is deposited on visible-infrared light absorbing film, whereby heat generated in the underlying light absorbing film heats the TiO2 film. We show that increasing the temperature of the TiO2 film results in an increased photocatalytic activity by two mechanisms: thermal activation to increase reaction kinetics, and by shifting the water gas-surface equilibrium coverage to free surface sites for reactant molecules. We generalize the results and discuss their implications for green building technology and possible scenarios for their implementation.

References: 1. B. Stefanov, G. Niklasson, C.G. Granqvist, L. Österlund, J. Mater. Chem. A2015, 3, 17369-17375. 2. B. I. Stefanov, J. Maibach, Z. Topalian, G. A. Niklasson, C. G. Granqvist, L. Österlund, ACS Catal., submitted. 3. Z. Topalian, B. Stefanov, C.G. Granqvist, and L. Österlund, J. Catal. 2013, 307, 265-274. 4. Z. Topalian, G. Niklasson, and L. Österlund, ACS Appl. Mater. Interfaces 2012, 4, 672−679. 5. L. Österlund, Z. Topalian, J. Phys.: Conf. Series2014, 559, 012009.

Acknowledgements This work was funded by the European Research Council under the European Community’s Seventh Framework Programs (FP7/2007-2013)/ERC Grant Agreement No. 267234 (“GRINDOOR”), Grant Agreement No. NMP4-SL-2013-608950 (“SESBE”), and Swedish Research Agency (VR) contract no. 2015-04757.

Photocatalytic Activity of Nitrogen and Silica Doping on Titanium dioxide and its Grafted onto PMMA Film

Piyasan Praserthdam1*, Rachan Klaysri1, Varistha Preechawan1, Noppongsathorn Thammachai1, Joongjai Panpranot1 and Okorn Mekasuwandumrong2 1Chulalongkorn University, Thailand 2Silpakorn University, Thailand

Abstract

Doping of titanium dioxide with nitrogen and/or silicon is typically described as an efficient way for the enhancement of visible light photocatalytic activity. However, the disadvantage of using titanium dioxide as a powder in the liquid media is difficult for reusability. In this paper, nitrogen-, and silicon-doped titanium dioxide photocatalyst as powder and grafted onto PMMA film, by using atom transfer radical polymerization (ATRP), have been prepared and investigated for the photocatalysis towards methylene blue degradation under UV and visible light irradiation. The samples were characterized by using X-ray

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 55 diffraction (XRD), UV-visible spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), scanning electron microscope with energy dispersive X-ray (SEM-EDX) and photoluminescence (PL). The kinetics were used to investigate the performances of grafted film of doping titanium dioxide compared with pristine titanium dioxide grafted PMMA. The results showed that kinetic constant parameters of nitrogen- and silica-doped titanium dioxide were improved both as powder and grafted film.

Biography

Piyasan Praserthdam graduated Dr.lng. in Industrial Chemistry from I.N.S.A.Toulose, France, 1979. He joined Chulalongkorn University as a lecturer in Chemical Engineering department since 1976. His work has been focused on catalysis field such as environmental catalysis, catalysis deactivation by coking, polymerization catalysis and hydrogenation catalysis. He has international publications in catalysis field and others more than 350 publications. Moreover, he also worked as a catalyst consultant for oil companies in Thailand for many years.

Strongly Facet-Dependent Photocatalytic Properties of Semiconductor Crystals

Michael H. Huang National Tsing Hua University, Taiwan

Abstract

We have synthesized sharp-faced Cu2O and Ag2O cubes, octahedra, and rhombic dodecahedra exposing respectively {100}, {111}, and {110} faces to examine their facet-dependent photocatalytic activities towards the photodegradation of methyl orange. While Cu2O rhombic dodecahedra are far more photocatalytically active than octahedra, Cu2O cubes are inactive even after surface deposition with some Au nanoparticles. These results can be understood from the presence of an ultrathin surface layer with different degrees of band bending for the various crystal faces. The presence of this thin layer with dissimilar band structures for different surfaces also explains the observations of facet-dependent electrical conductivity and optical properties of Cu2O and other semiconductor crystals. The photocatalytic inactivity of Cu2O cubes has been examined using EPR, electron, hole, and radical scavenger tests, showing lack of photoexcited charge carriers reaching the {100} crystal faces. Remarkably,

Ag2O crystals having the same crystal structure as Cu2O exhibit opposite photocatalytic behaviors for the respective surfaces, showing a modified band diagram is a better way to understand these phenomena than consideration of their surface structures and surface energies. Photocatalytic inactivity also appears when ZnO nanostructures are deposited on Cu2O cubes and octahedra. Preferential growth of the ZnO (101) planes on the {111} faces of Cu2O should create a bad heterojunction with unfavorable band alignment causing the dramatic photocatalytic activity suppression. Additional recent examples of complete photocatalytic suppression will be presented to show the strong facet effects to charge transport at the semiconductor crystal surfaces or interfaces.

Biography

Michael H. Huang received his Ph.D. degree from UCLA in 1999. After conducting postdoctoral research at UC Berkeley and then UCLA, he joined the Department of Chemistry, National Tsing Hua University as an assistant professor in 2002. He was promoted to associate professor in 2006 and professor in 2010. He has received Outstanding Research Award from National Science Council of Taiwan in 2011. He was on the list of Top 100 Materials Scientists released by Thomson Reuters

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 56 in 2011, and among the 300 most cited researchers in materials science and engineering in 2016 by Elsevier Scopus data.

Solar Light-Driving Photoconversion of CO2 into Renewable Hydrocarbon Fuels

Yong Zhou Nanjing University, China

Abstract

In recent years, the increase of carbon dioxide (CO2) in the atmosphere has become a global environmental issue because of the serious problems, such as the “greenhouse effect”. The idea of mimicking the overall natural photosynthetic cycle of chemical conversion of CO2 into useful fuels has been consistently gaining attention for more than thirty years. Such artificial photosynthesis allows direct conversion of CO2 and water on photocatalysts into valuable hydrocarbon using sunlight at room temperature and ambient pressure to serve to reduce atmospheric CO2 concentrations while providing on a renewable carbon fixation and energy storage.

In this presentation, we will report the utilization of solar energy to highly efficient conversion of CO2 into renewable hydrocarbon fuel over nanostructures. The geometric shape and exposure of specific crystal planes of the nanostructures as well as Z-scheme configuration are a requisite for efficient charge separation, and subsequently high level of photocatalytic reduction of CO2.

Biography

Yong Zhou studied chemistry and physics at the University of Science and Technology of China (USTC), received his Ph.D. degree there in 2000. After working in Kyoto University in 2000–01, Max Planck Institute of Colloids and Interfaces in 2002–03, the National Institute of Materials Science (NIMS, Japan) in 2003–04, National Institute of Advanced Industrial Science and Technology (AIST, Japan) in 2004–08, and National University of Singapore (NUS) in 2008–09, he joined as a full professor in Nanjing University, China. His research now focuses on design and fabrication of solar-light driven clean energy materials for photocatalysis and flexible solar cells.

Photo-Degradation of N-Containing Pollutants in Waste-Water

Francesca S. Freyria1, 2*, Matteo Compagnoni3, ElnazBahadori3, Tanveer Ahmed Gadhi1, Marco Armandi1, GianguidoRamis4, Ilenia Rossetti3 and Barbara Bonelli1 1Politecnico di Torino, Italy 2Massachusetts Institute of Technology, MA, USA 3Universitàdegli Studi di Milano and INSTM Unit Milano-Università, Italy 4Universitàdegli Studi di Genova and INSTM Unit Genova, Italy

Abstract

In aquatic environments, such as rivers, lakes, etc.., it is possible to find a noteworthy number of emerging pollutants (EPs), which are compounds that are not commonly removed but they might cause negative ecological and human health effects by entering the environmental system. Among these, N-containing pollutants, such as simazine, phenyl urea, diazepam, azo and tracer dyes are particularly interesting due to their being recalcitrant to the standard remediation methods and for the their subproducts toxicity have been studying their degradation under illumination, in presence of mesoporoustitania (MT) with different loading of transition metals, such as Fe (X-MTd). A template-assisted synthesis has been used for X-MTd samples in order to red-shift the band-gap of the catalyst and to harvest more solar light. For comparison, MT and commercial Titania (Degussa P25) have been considered, both as such and after impregnation of the transition metals (X-MTiand X-IT respectively). Several techniques have been used to physico-chemical characterize the samples, such as X-ray powder diffraction,

N2 adsorption isotherms, Energy Dispersive X-ray Spectroscopy, Diffuse Reflectance UV-Vis Absorption, Mossbauer Spectroscopy and X-ray Photoelectron Spectroscopy. Directly synthesized samples show nanoparticles (≈15 nm diameter) of pure anatase, with remarkably high specific surface area (SSA, 120 – 150 m2 g-1) and, in presence of the transition metal, a band gap lower than pure MT.

The effect has been studied either at different H2O2 concentration or at different kinds of illumination. Different reaction

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 57 mechanisms have been found, depending on both chemical composition and preparation method.

Biography

Francesca S. Freyria, after a MEng in Environmental Engineering, received the European Ph.D. degree in Materials Science and Technology at Politecnico of Torino (Italy), under the supervision of Prof. Barbara Bonelli. During 2014, she joined the Prof. Bawendi’s group at Massachusetts Institute of Technology (Cambridge, USA) as postdoc. During the 2016 she started again to work with Bonelli’s group about new catalysts for N-containing pollutants abatement. Her broader research interests include the study of new heterostructured nanomaterials and mesoporous materials and how to endow them with new properties for environmental remediation and for solar energy applications.

Eutectic Photoanode for Photoelectrochemical Water Splitting

Jaroslaw Sar1*, Katarzyna Kolodziejak1, Konrad Wysmulek1, Pawel Osewski1, Marta Radecka2 and Dorota Anna Pawlak1,3 1Institute of Electronic Materials Technology, Poland 2AGH University of Science and Technology, Poland 3University of Warsaw, Poland

Abstract

The increasing energy consumption requires new and efficient energy sources. Hydrogen is considered a promising energy source, especially when produced by direct conversion of solar energy in so-called photoelectrochemical cells (PEC). The aim of this work is to show the possibility of using eutectic composite as an active photoanode material for PEC. Eutectic composites are promising materials for solar-energy conversion due to: (i) high crystallinity, (ii) sharp interfaces between phases, (iii) wide variety of possible composites, and (iv) ability to modify properties by: doping, annealing and/or etching. This work focuses on fabrication of eutectic composites by directional solidification using the micro-pulling down method in example of SrTiO3- 1 2 2 TiO2 system . The highest photocurrents of 8.5 mA/cm were obtained upon 600 mW/cm light irradiation after 30h of continuous analysis. The optical and photoelectrochemical properties as well as stability of the composites prove that eutectic composites can compete with heterostructures and other composites made of the same components.

Biography Jarosław Sar obtained his double doctoral degree from University of Lisbon, Portugal in Materials Engineering and University of Grenoble, France in Electrochemistry in 2014. His Ph.D. thesis concerned energy production in solid oxide fuel cells and solid oxide electrolyser cells. As a PhD student, he performed 6-months internship in European Institute for Energy Research in Karlsruhe, Germany. Currently, he is an assistant professor in Laboratory of Functional Materials of the Institute of Electronic Materials Technology in Warsaw, Poland. His main research interest is electrochemical and photoelectrochemical hydrogen production.

TiO2-WO3 Self-Organized Eutectic Composite for Photoelectrochemical Water Splitting

Katarzyna Kolodziejak1*, Jaroslaw Sar1, Konrad Wysmulek1, Pawel Osewski1, Krzysztof Orlinski1 and Dorota A. Pawlak1,2 1Institute of Electronic Materials Technology, Poland 2University of Warsaw, Poland

Abstract Eutectic composites are two or multiphase materials formed during cooling of a mixable melt with a eutectic composition. The possibility of considering versatile combinations of various component materials in eutectics provides a broad palette for many applications [1-3]. Eutectics obtained by the self-organization mechanism also seem to be very attractive as energy- generating materials [4,5]. They have potential as photoactive materials, due to their multiphase character – various available photoactive component phases, multiple band gap energies and high crystallinity.

Titanium dioxide and tungsten trioxide eutectic is a new composite material, obtained via directional solidification (DSE - Directionally solidified eutectics) by the micro-pulling-down method (m-PD). Such mixed materials made of two semiconducting phases with bandgaps enabling absorption of UV-Vis wavelengths (TiO2 – UV light, WO3 – visible light) may be promising for photoelectrochemical applications – especially as materials for PEC photoanodes. The growth and

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 58 characterization of the eutectic microstructure from a TiO2-WO3 system (36 at.% TiO2 and 64 at.% WO3), will be presented together with the photoelectrochemical measurements performed on fabricated photoanodes.

References: 1. D. A. Pawlak, K. Kolodziejak, S. Turczynski, J. Kisielewski, K. Rozniatowski, R. Diduszko, M. Kaczkan, M. Malinowski, Chem. Mater. 18 (2006) 2450-2457. 2. D. A. Pawlak, Self-organized structures for metamaterials in Applications of Metamaterials (Metamaterials Handbook), Capolino F., Ed.; CRC Press, 2009, Vol II, Chapter 31. 3. D. A. Pawlak, S. Turczynski, M. Gajc, K. Kolodziejak, R. Diduszko, K. Rozniatowski, J. Smalc and I. Vendik, Adv.Funct. Mat. 20 (2010) 116-1124. 4. K. Kolodziejak, J. Sar, K. Wysmulek, P. Osewski, M. Warczak, A. Sadkowski, M. Radecka, D. A. Pawlak, J. Catal. 352 (2017) 93–101. 5. K. Wysmulek, J. Sar, P. Osewski, K. Orlinski, K. Kolodziejak, A. Trenczek-Zajac, M. Radecka, D. A. Pawlak, Appl. Catal. B Environ. 206, (2017) 538–546.

Biography

Katarzyna Kolodziejak holds a master’s Degree in Material Science from the Warsaw University of Technology (Poland). Currently, she is a research assistant in the Department of Functional Materials of the Institute of Electronic Materials Technology, Warsaw, Poland, where her activities include directional solidification and fundamental research of new materials for photo-electrochemical water splitting.

Silica-Titania Coatings: Photocatalysts for Air and Water Cleaning

Nataša Novak Tušar1,2*, Andraž Šuligoj1,3 and Urška Lavrenčič Štangar3 1National Institute of Chemistry, Slovenia 2University of Nova Gorica, Slovenia 3University of Ljubljana, Slovenia

Abstract

Organic compounds and volatile organic compounds (VOC) are the main class of pollutants emitted from various industrial processes, transport and consumer products. Photocatalysis is one of the most efficient advanced oxidation processes (AOP) for removal of organic pollutants from indoor-air or waste water. Titanium dioxide (TiO2) is the most used semiconductor for photocatalytic removal of organic pollutants due to its interesting characteristics: low cost, safe, high stability shows high photocatalytic activity, it can promote ambient temperature oxidation of the major class of organic pollutants. A common 2 -1 2 -1 approach to enhance the photocatalytic activity of TiO2 is also to increase its surface area (100–200 m g to 400–1000 m g ) and to introduce the mixed oxide synergetic effect. This can be achieved by immobilization ofTiO 2 on the porous supports such are porous silica or porous carbon and the preparation of such a catalyst in the form of film using appropriate carrier. Porous silica is superior support for accommodating photocatalysts nanoparticles because they are chemically inert, possess high surface areas, are transparent to UV radiation, have great physical stability, and have hydrophobic character. We have recently evaluated the photocatalytic efficiency of porous silica supported TiO2 in the form of powder for removal of organic pollutants from indoor-air and wastewater. Here, an overview on the design and development of silica supported TiO2in the form of coatings for removal of organic pollutants from indoor-air and wastewater will be presented and benefits and drawbacks will be outlined.

Biography

Nataša Novak Tušar received her PhD in Chemistry from the University of Ljubljana, Slovenia in 2000. She was a post PhD researcher in 2003-2004 as an Individual Marie Curie Fellow at synchrotron ELETTRA and University of Trieste, Italy. Beginning in 2013 she has been working at the Department for Inorganic Chemistry and Technology at the National Institute of Chemistry in Ljubljana, Slovenia as a group leader for catalysis. Since 2006 she has been lecturing at the the University of Nova Gorica, Slovenia, from 2012 as associated professor. She is a member of management committees in ENMIX and EFCATS.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 59 Enhanced UV Flexible Photodetectors and Photocatalysts based on TiO2 Nanoplatforms

D. Nunes1*, A. Pimentel1, A. Araujo1, T.R. Calmeiro1, S. Panigrahi1, J.V. Pinto1, P. Barquinha1, M. Gama2, E. Fortunato1 and R. Martins1 1Universidade NOVA de Lisboa, Portugal 2University of Minho, Portugal

Abstract

The tendency towards the development of environmentally friendly materials that can be applied in multifunctional purposes has become more intensive in recent years, especially when it involves low cost production routes. Titanium dioxide

(TiO2) is included in such materials, as it has elevated stability and photoactivity, non-toxicity, and earth-abundance. TiO2 has been extensively studied for applications ranging from photocatalysis, solar cells to sensors [1-3]. In the present study,

TiO2nanostructured films were grown on bacterial nanocellulose, polyester and tracing paper substrates using a hydrothermal method assisted by microwave irradiation without any seed layer. The selected substrates are inexpensive, reliable, recyclable, flexible, lightweight, and when associated to low temperature synthesis (80oC) and absence of seed layer, they become suitable for several low-cost applications. Structural and morphological characterization was carried out by scanning electron microscopy (SEM) coupled with X-ray energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and by Raman spectroscopy. The microwave synthesis totally covered the substrates, forming uniform nanostructured films while maintaining the substrates flexibility. Fine nanorod aggregates forming TiO2 flower-like structures were observed and regarding the substrate used, different nanostructured films were obtained. The photodetection behaviour of each material was studied by Kelvin probe force microscopy (KPFM) experiments with a clear relation between contact potential difference shift and their photosensitivity/ photocatalytic activities. The time resolved photocurrent of each material in response to the UV turn on/off was investigated. The material photocatalytic activities were evaluated from rhodamine B degradation under solar radiation.

References: 1. Nunes, D.; Pimentel, A.; Santos, L.; Barquinha, P.; Fortunato, E.; Martins, R. Photocatalytic Tio2 nanorod spheres and arrays compatible with flexible applications.Catalysts 2017, 7, 60. 2. Nunes, D.; Pimentel, A.; Pinto, J.V.; Calmeiro, T.R.; Nandy, S.; Barquinha, P.; Pereira, L.; Carvalho, P.A.; Fortunato, E.; Martins, R. Photocatalytic behavior of Tio2 films synthesized by microwave irradiation. Catalysis Today 2016, 278, Part 2, 262-270. 3. Hara, K.; Sayama, K.; Ohga, Y.; Shinpo, A.; Suga, S.; Arakawa, H. A coumarin-derivative dye sensitized nanocrystalline Tio2 solar cell having a high solar-energy conversion efficiency up to 5.6%.Chemical Communications 2001, 569-570.

New Platinum-Containing Electrocatalysts with High Activity and Stability

Vladimir Guterman*, Anastasia Alekseenko, Sergey Belenov, Ivan Novomlinskiy and Vladislav Menshikov Southern Federal University, Russia

Abstract

Platinum-containing catalysts are one of the most important components of membrane-electrode assemblies in commercially available low-temperature fuel cells with a polymer membrane. The task of increasing the functional characteristics of such catalysts is very important. New Pt-containing electrocatalysts, exceeding commercial Pt/C catalysts in their stability and/or mass-activity in the reactions of oxygen electroreduction and methanol electrooxidation (MOR), are obtained in this work. The high characteristics of the catalysts for the oxygen electrode of PEMFC are due to the gradient architecture of bimetallic nanoparticles in which the platinum concentration increases from the core to the surface of nanoparticles. Dealloying of such nanoparticles by means of the catalysts post treatment causes the development of their surface. Residual alloying component influences positively to the activity of the surface. The highest rate in MOR is demonstrated by catalysts in which platinum nanoparticles are deposited on a composite nanostructured SnO2/C carrier prepared by a patented method. The presence of direct contact between platinum nanoparticles, 2-3 nm in size, and SnO2 nanoparticles, 3-4 nm in size, anchored on the surface of the carbon carrier, facilitates the oxidation of the intermediate products forming in MOR.

The study was carried out using the XRD, X-ray fluorescence analysis, TEM, EDX elemental mapping, CV and LCV on RDE. Also, the results of comparative tests of some catalysts in the membrane-electrode assemblies of hydrogen-air fuel cells are presented. Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 60 Biography

Vladimir Guterman is a professor of Southern Federal University (Rostov-on-Don, Russia), a member of International Society of Electrochemistry since 1999, PhD and Dr.Sci. in Chemistry. He is the author of more than 200 publications and Head of the scientific and educational center “Chemistry and physics of functional and nanostructured inorganic materials” of Southern Federal University www.nanolab.sfedu.ru. He is the Head of research grants of Russian Scientific Foundation, Ministry of Education and Science, Russian Foundation of Basic Researches. His research interests are electrocatalysts for low temperature fuel cells.

Carbon Based Electrode Materials for Electrolysis Performance and Stability

Saskia Heumann1*, Youngmi Yi1, Pascal Düngen1 and Robert Schlögl1,2 1Max Planck Institute for Chemical Energy Conversion, Germany 2Fritz Haber Institute of the Max Planck Society, Germany

Abstract

The energy challenge is the major challenge for today’s society and future generations. Chemistry plays a central role in the energy challenge, since most energy conversion systems work on (bio) chemical energy carriers and require for their use suitable process and material solutions. The enormous scale of their application demands optimization beyond the incremental improvement of empirical discoveries. For this reason, we work on the development of knowledge-based systematic approaches to arrive at scalable and sustainable solutions. The difficult elementary steps in the water splitting process, to gain hydrogen as chemical energy carrier, are in the oxygen evolution reaction at the anode side.

Water electrolysis requires active and long-term stable electrode materials such as commercial Pt, IrO2 or RuO2 based materials. Replacement of non-abundant, environmental friendly, cheap alternatives is needed to overcome the global demand. Here, carbon-based electrodes can play a major role in the future as sacrificial electrodes. Thorough investigation of carbon structures is mandatory if they are applied in catalysis. Comprehension of the structure-property relations requires knowledge about the presence and quantity of different species of functional groups. The detailed investigation of the carbon-based systems allows a fundamental understanding of the occurring processes during water splitting. Different degradation mechanism of glassy carbon in alkaline and acidic media could be revealed, showing once again that the reaction conditions highly influence the performance and stability in catalysis [1].

Reference 1. Youngmi Yi, Gisela Weinberg, Marina Prenzel, Mark Greiner, Saskia Heumann, Sylvia Becker, Robert Schlögl, Catalysis Today, Volume 295, 2017, Pages 32-40.

Improved Electrocatalytic Activity of Nitrogen Doped–Graphene Oxide Modified GCE Towards Electrochemical Detection of 2-Nitrophenol in Water

Bulelwa Ntsendwana*, Kholiswa Yokwana and Edward Nxumalo University of South Africa (UNISA), South Africa

Abstract

Nitrophenols are an important group of environmental pollutants, which emanates from manufacturing of insecticides, pesticides, dyes, plastics and explosives. Due to their carcinogenicity, stability and bioaccumulation, the US Environmental Protection Agency (EPA) lists nitrophenols as one of priority pollutants. Thus, the development of rapid and cost-efficient method for detecting nitrophenols at trace levels is highly desirable and urgently necessary for the environment and health protection. It is therefore, in this light that, nitrogen doped graphene oxide nanosheets (NGO) were synthesized and employed to enhance the electrochemical sensitivity of glassy carbon electrode towards detection of 2-nirophenol. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Raman spectroscopy were used for to elucidate the effect of nitrogen on the morphological and structural properties of graphene oxide. The SEM images revealed a change of the morphology as the nitrogen loading increased from 1-3 wt% forming flake-like particles. In addition, the Raman results displayed enhanced intensity of the D band induced by doping confirming a good insertion of nitrogen into

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 61 graphene oxide lattice. Furthermore, the N- doped graphene oxide was immobilised on the glassy carbon electrode using drop- dry method. The nitrogen doped –graphene oxide modified GCE exhibited more facile electron kinetics in the presence of -3/-4 [Fe(CN)6 ] redox probe and enhanced current of about 60% when compared to the unmodified glassy carbon electrode. The modified electrode was used for the detection of 2-Nitrophenol. Under the optimum conditions, the oxidation peak current of 2-Nitrophenol varied linearly with concentration over a wide range suggesting improved electrocatalytic activity.

Biography

Bulelwa Ntsendwana is a Senior Lecturer at the Nanotechnology and Water Sustainability Research Unit (NanoWS), College of Science, Engineering and Technology, University of South Africa, South Africa. She is currently a member of International Electrochemistry Society (ISE) Dr. Ntsendwana’s research interests involve qualitative and quantitative heavy metal determination from soil and water samples. She also acquired expertise on development of advanced carbon based electrocatalyst support materials for Direct Methanol Fuel Cell application, materials development for Mg-based Hydrogen storage unit, fabrication of novel electrode materials for photoelectrochemical degradation of organic pollutants in water and development of electrochemical sensors. She is involved in advanced oxidation processes which are characterised as green approach towards (photocatalysis, electrochemical and photoelectrochemical) effective water treatment methods. She aspires on embarking on fuel cell energy systems as the new research focus area at NanoWS research unit.

Fabrication of 1-Dimensional g-C3N4 Hollow Carbon Nanofibers Incorporated with S, N-Doped Graphene and MoS2 for the Application of Artificial Photosynthesis Suhee Kang*, Joonyoung Jang and Caroline Sunyong Lee Hanyang University, Korea

Abstract

Solar energy is an endless source of sustainable and alternative energy production. Over the past few decades, photoactive materials in various applications, such as organic pollutant photodegradation, photoelectrochemical water splitting, or artificial photosynthesis, have been widely studied, not to mention that the numerous studies on these photoactive materials have been proposed to design innovative structures with superior performance. Among these materials, graphitic carbon nitride

(g-C3N4), a non-metallic semiconductor having a band gap of 2.6 eV, has been attracting much attention due to its easiness to manufacture as well as its environmentally benign and high thermal stability. However, g-C3N4 suffers from high recombination rate of charge carriers, low surface area and poor light absorption. To overcome these drawbacks, and one-dimensional (1-D) structured nanofiber can be considered to be an effective accelerator of the electrons as well as separators of the electron-hole pairs. Moreover, sulfur/nitrogen doped graphene (SNG) and MoS2 can be applied to improve the surface area while improving light absorption in the visible region, respectively. In the present work, hollow carbon nanofibers (HCFs) covered with metal- free g-C3N4, were prepared by electrospinning followed by thermal condensation methods. The prepared g-C3N4HCFs with

SNG and MoS2 are synthesized in-situ by a hydrothermal process at relatively low temperature. The morphologies by SEM, TEM and XRD analysis, was used to characterize this fabricated sample. Raman, FT-IR and XPS were measured to distinguish its chemical compositions according to their properties. Photoelectrochemical analysis was performed with as-prepared samples to observe the photoresponse under illumination. The H2photocatalytic evaluation of g-C3N4 HCFs with SNG and MoS2 was carried out under visible light and it was compared with that of g-C3N4 HCFs only. As per author’s knowledge, this is the first report on g-C3N4HCFs/SNG/MoS2heterostructures. The obtained heterostructures could be applied more in various fields including artificial photosynthesis, solar cell, bio-application, Li-ion battery cell and electrocatalysis.

Biography

Suhee Kang received her Master’s degree in Materials Engineering in 2016, from Hanyang University in South Korea. She is now graduate student under the supervision of Dr. Caroline Sunyong Lee in Materials and Chemical Engineering, Hanyang University, South Korea. Her current research interests mainly focus on the design novel structures as multi-structures using photocatalysts and applicable in artificial photosynthesis fields.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 62 Synergistic Interaction of Au-Mo Modification on Ni/GDC for the H2O Electrolysis Reaction in SOECs

D.K. Niakolas1*, Ch. Neofytidis1,2, E. Ioannidou1,2 and S.G. Neophytides1 1 FORTH/ICE-HT, Greece 2University of Patras, Greece

Abstract

High quality H2 (~100% H2) can be produced by the electrochemical conversion of H2O to H2 and O2 through water electrolysis at low or high temperatures. Water electrolysis at temperatures above 500 ˚C, with steam, using Solid Oxide Electrolysis Cells (SOECs) is a promising and fast-growing technology. SOECs have identical configuration with Solid Oxide Fuel Cells (SOFCs) but reverse operation. The latter relation is quite advantageous compared to low temperature technologies, because SOECs can be built based on the significant SOFCs development, which has seen a significant research. Specifically, novel modified Ni-based fuel electrodes are continuously being processed for fuel cell (H/Cs: Natural Gas, Biogas) and electrolysis (H2O, CO2 and H2O+CO2) applications with improved performance and stability of the state-of-the-art Ni-based electrodes.

The presented study deals with the effect of Au-Mo modification on the electrochemical andphysicochemical characteristics of Ni/GDC for H2O electrolysis conditions in a single SOEC. Comparative electrocatalytic measurements with I-V curves and Electrochemical Impedance Spectra (EIS) analysis are presented in the range of 800-900 °C between electrolyte supported cells that comprise Ni/GDC, 3wt% Au-Ni/GDC and 3wt.% Au- 3wt.%Mo-Ni/GDC as the steam/hydrogen electrode, by applying different pH2O/pH2 ratios. Complementary physicochemical characterization was also performed both in the form of powders and as half cells with ex-situ and in-situ techniques, including specific redox stability measurements in the presence of 2H O.

Different structural and activity properties were observed for each cermet, where the cells comprising the Au-Mo modified electrodes exhibited better electrochemical performance. This improvement can be ascribed to the formation of a surface Ni-

Au or Ni-Au-Mo solid solution, which causes weaker interaction of H2O and of the resulting adsorbed Oads species with the modified cermet. The outcome is an electrode with a lower degree of surface oxidation and increased “three phase boundaries” length, where the charge transfer and electrode processes are enhanced for the H2O electrolysis reaction.

Biography

Dimitrios K. Niakolas is an associate research scientist at FORTH/ICE-HT. He holds a MSc in Business Administration and a PhD in Chemistry. His research interests focus on the areas of heterogeneous catalysis, solid state electrochemistry (ceramic materials, fuel cells, low and high temperature electrolysis technologies), chemical and electrochemical kinetics. Moreover, his areas of expertise cover the fields of strategic management of innovation, competitiveness and technology evaluation. He has co- authored more than 19 publications in peer-reviewed international scientific journals and he is one of the responsible persons for the preparation and scientific progress in 7 European funded projects.

Effect of the Nature of Metal Particles on the Photocatalytic Degradation of Rhodamine B

Ahmad S. Alshammari*, Naif Alarifiand Abdulaziz Al Sayigh King Abdulaziz City for Science and Technology, Saudi Arabia

Abstract Toxic waste generated by several natures of dyes (e.g. Rhodamine B) is found to be one of the greatest harms, which is affecting our global environment. For instance, it leads to some serious problems to sea life and many other health issues. Therefore, there is a need to deal with such concerns and treat wastewater discharge using more effective treatment technologies. Numerous methods (e.g. adsorption, coagulation, membrane process etc) have been used in order to remove the dyes from water. However, such types of techniques have some disadvantages such producing waste solid, which needs complicated processes in order to purify absorbed materials. Thus, photocatalytic oxidation of dye using supported metal nanoparticles (MNPs) appears as a real and economic unusual method because of the formation of active oxygen-containing species under the UV-visible light helps to destroy the dyes. In the present work, several type of MNPs (e.g. Pd, Pt, Ru) supported on commercially titania were successfully synthesized aiming to realize the influence of the nature of such metal particles on the degradation of Rhodamine

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 63 B. Catalysts properties were also evaluated by deep characterization techniques using different spectroscopic and microscopic methods including Inductively-coupled plasma (ICP), N2 physisorption,

X-ray diffraction (XRD), transmission electron microscopy (TEM), Solid-state ultraviolet-visible (UV-Vis). The photocatalytic activity showed that among different tested metal particles, Pt nanoparticles supported on titania is found to be the best catalyst with great efficiency.

Biography

Ahmad Alshammari received his Ph.D. (2010) from Leibniz Institute for Catalysis at the University of Rostock, Germany with Prof. Axel Schulz and Dr. Andreas Martin. In 2011, he joined the Material Science Research Institute (MSRI), King Abdulaziz City for Science and Technology (KACST), Riyadh, where among other things his principle research field is focused on the application of nanomaterials in various areas such as catalysis, photocatalysis, etc. He was a visiting scholar at UC Berkeley (2014-2016) with Professor Omar Yaghi. He is currently Associate Professor of Chemistry at MSRI at KACST. He published more than 20 articles and has 8 patents.

Catalytic oxidation of Elemental Mercury Over Cu Modified Vanadium-Based SCR Catalysts

Hongyan Wang*, Baodong Wang, Yonglong Li, Qi Sun and Wayne Qiang Xu National Institute of Clean-and-Low-Carbon Energy, China

Abstract

Cu modified vanadium-based SCR catalysts (Cu/VWTi) prepared by an impregnation method were studied to determine their efficiencies of mercury (Hg0) oxidation in the simulated flue gas. In this study, 7% Cu/VWTi was found to be an optimal catalyst with an oxidation efficiency of over 98% at temperatures in the range of 280-360°C. In addition, the denitration efficiency was not affected. X-ray diffractograms (XRD), Brunauer–Emmet–Teller (BET) measurements, X-ray photoelectron spectroscopy (XPS) and incorporation model were used to characterize the catalysts. The results indicated the distribution of metal oxide on the catalyst surface is good, and no obvious agglomeration occurs, which is close to single layer distribution.

Gaseous O2 was important for the oxidation process, because it regenerated the lattice oxygen and replenished the chemisorbed 0 0 oxygen, which boosted Hg oxidation. NO and SO2 could remarkably promote Hg oxidation over Cu/VWTi catalyst. SO2 0 exhibited a promotional effect on Hg oxidation at low SO2 concentrations. However the effect became weaker at higher 0 SO2 concentrations. NH3 competed for active sites with Hg and consumed surface oxygen, which caused a significantly deteriorated effect on Hg0 oxidation. However, high performance of Hg0 oxidation can be achieved if the catalyst is installed at the downstream of the SCR reactor. Mercury oxidation over Cu/VWTi catalysts was significantly enhanced when HCl was added to the simulated flue gas Mercury oxidation by HCl over Cu/VWTi catalysts follows the Eley-Rideal mechanism, in which gas-phase Hg0 reacts with active surface chlorine species generated from HCl dissociation.

Biography

Hongyan Wang is a R&D engineer at National Institute of Clean-and-Low-Carbon Energy (NICE). Dr. Wang has a Ph.D. degree in Materials Physics and Chemistry from Beihang University and M.S./B.E. degrees from Kunming University of Science and Technology. Her research interest includes environmental catalysis and control of pollutant in plant. In NICE, she mainly focuses on the development of DeNOx&Hg Catalysts.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 64 In Situ Study on Electrodeposited MnOx Films During Electro-Catalytic Water Oxidation Using Soft X-Ray Absorption and Emission Spectroscopy

Maryam Shaker1, 2*, Marc F. Tesch1, Shannon A. Bonke1, Alexandr Simonov3, Leone Spiccia3 and Emad F. Aziz1, 2 1Helmholtz-Zentrum Berlin für Materialien und Energie, Germany 2FreieUniversität Berlin, Germany 3Monash University, Australia

Abstract

Manganese oxides (MnOx) based catalysts are promising candidates that mimic the natural catalytic complexes in photosystem II, especially the water oxidation half reaction, which is mandatory to produce hydrogen from water. In order to understand the catalytic efficiency of MnOx, a comprehensive knowledge about its electronic structure is necessary. Soft X-ray spectroscopy is a powerful tool to study the electronic structure of transitions metal oxides. However, such studies are usually restricted to ex situ measurements unable to unambiguously identify structural and electronic changes of the material occurring at real working conditions, i.e. applying a potential. Here, we present an in operando study using X-ray absorption spectroscopy

(XAS) and resonant inelastic X-ray scattering (RIXS) at the Mn L-edge of electrodeposited MnOx films while applying potentials during and beyond the water oxidation process. The results show clear, potential dependent spectral changes related to variations in the Mn oxidation state. The XAS spectra takenin operando are compared to ex situ XAS measurements. Thein operando RIXS measurements revealing distinct changes in the structure of the occupied valence state, in terms of facilitation of the charge transfer between O and Mn in MnOx. The calculated theoretical data for the XAS and RIXS are in-line with the experimental data. The structural and electronic changes are believed to be crucial for efficient electro-catalytic oxidation which can be relevant for future industrial applications.

Biography

Maryam Shaker, a Ph.D. researcher at the physics department, Freie Universität in Berlin, Germany since August 2015.

CO2 to Value: The Single Step Electro-Reduction of CO2 to Hydrocarbons in its Elemental Steps

Bernhard Schmid1,2*, Christian Reller1, Ralf Krause1, Nemanja Martic1,2, David Reinisch1,2, Romano Dorta1 and Guenter Schmid2 1Siemens AG – Corporate Technology, Germany 2Friedrich Alexander University Erlangen Nuernberg, Germany

Abstract

Switching from fossil based to renewable power generation requires the installation of large overcapacities of wind and solar due to their intermittency. Storage or conversion possibilities are essential due the volatility of electricity. Economic feasibility is difficult when considering the low fossil energy carrier prices and the physical efficiency limitations of the processes. Therefore, we choose to focus on high volume materials, of which the value as a chemical resource vastly exceeds their heating value.

Depending on the electro catalytic system, CO2 can be reduced to carbon monoxide, methane, ethylene and various other hydrocarbons and oxygenates. CO could be obtained with faradic efficiencies over 90% at current densities of several kA/m2 with total energy efficiency up to 50%.

Faradic efficiencies up to 57% for ethylene could be obtained using in-situ-deposited nano-structured copper electro catalysts. Faradaic Efficiencies for Ethanol of up to 23% could be achieved simultaneous along with variety C1-C3 products. The origin of this wide and interesting product scope for this catalyst was found to be its profound versatility in electro-organic functional group conversion and its ability to further reduce CO once formed.

Biography

Bernhard Schmid studied Molecular Science and Chemistry at the Friedrich-Alexander-University-Erlangen-Nuernberg (FAU) and received his master’s degree in chemistry in 2015. His main interests are catalysis and organometallic preparative chemistry. He is currently finishing his thesis on the mechanistic and electro catalytic aspects of the CO2-reduction under

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 65 industrial and application relevant high conversion rate conditions. The experimental work is conducted at the Corporate Technology of the Siemens AG in the department Research for Energy and Electronics – Storage Solutions (CT REE STS). The thesis is supervised by Prof. Romano Dorta (FAU).

Hybrid Carbon Nanomaterials as Active Electrocatalysts for Hydrogen Production from Water Electrolysis

Mohammad Tavakkoli*, Tanja Kallio, Esko I. Kauppinen and Kari Laasonen Aalto University, Finland

Abstract

Among current technologies for hydrogen production, water splitting has been attracted increasing attention since it is also a promising technique to store intermittent electrical energy from renewable resources such as solar and wind energy in the form of H2 fuel. Water splitting can be divided into two half reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). For HER and OER, efficient and stable non-precious catalysts are required. We have shown that modified carbon nanotubes (CNTs) have a great performance for producing highly active HER and OER electrocatalysts.

We have synthesized Fe@graphene core-shell nanoparticles supported on CNTs through a novel fast one-step synthesis technique. These materials have shown the most similar performance among non-noble metal catalysts for HER in acidic media to that of commercial Pt/C. Furthermore, CNTs decorated with Fe@C nanoparticles could be electrochemically modified to be activated for OER in alkaline media.

For alkaline water electrolysis, we have functionalized CNTs with special types of nitrogen functionalities to synthesize active metal-free electrocatalysts for both HER and OER. CNTs have been also utilized to immobilize organometallic Ni complexes for producing ultra-high active electrocatalysts toward OER.

An atomic-scale Pt catalyst system increases the relative amount of surface active-site atoms while minimizes the Pt loading on the catalyst support. We have introduced single-walled CNTs (SWNTs) as promising supports to immobilize individual atoms or subnano clusters of platinum, in order to produce highly active electrocatalysts toward HER with a similar performance to that of commercial Pt/C with a significantly higher ( 66−333-fold) Pt loading. The pseudo-atomic scale Pt is decorated on the SWNTs through a simple electroplating method. ∼ Biography

Mohammad Tavakkoli has recently completed his PhD in Chemistry and Materials Science at Aalto University in Finland. He has been working on the development of electrocatalyst materials for a wide range of electrochemical reactions as well as electrode materials for Li-ion batteries and supercapacitors. His current research is on synthesis and functionalization of carbon nanomaterials such as carbon nanotubes, graphene, fullerene, and development of metal@C core-shell nanoparticles for energy conversion and storage applications.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 66 The Mechanism of Plasma - Catalytic Reduction of Nitrogen Oxides (NOX)

Byeong Ju Lee*, Jin Oh Jo and Young Sun Mok Jeju National University, South Korea

Abstract

Even though it is well known that plasma substantially enhances the selective catalytic reduction (SCR) of NOX, the mechanisms involved in the plasma-SCR hybrid process have not yet been clearly explained. This work has focused on the γ NOX reduction pathways for the SCR enhanced by plasma. The catalyst, 20-nm spherical Ag supported on -Al2O3, was in direct contact with plasma created by dielectric barrier discharge (DBD). The feed gas flow rate was 2 L/min, which consisted C of n-heptane 257 ppm (reducing agent), NOX 300 ppm, water 3%(v/v) and O2 10%(v/v). At 250° , the NOx removal efficiency obtained with the SCR alone was less than 10%. In comparison, when the SCR was combined with the DBD plasma, the removal efficiency greatly increased to approximately 90%. So as to understand this phenomenon, the decomposition products of the reducing agent (i.e., n-heptane) in the presence of plasma were analyzed by gas chromatography and infrared spectroscopy. The major decomposition products were found to be short-chain aldehydes such as acetaldehyde and propionaldehyde. Several sets of NOx removal experiments have clearly shown that the NOX removal efficiency with an aldehyde as a reducing agent is higher than that with n-heptane. The results also exhibited that the higher the molecular weight of the aldehydes, the higher the NOx removal efficiency. Previous plasma-SCR studies have interpreted the enhancement of NOx removal by the formation of NO2. Different from the previous studies, however, the formation of NO2 was found to decrease the SCR performance. To conclude, the enhanced NOX removal can be attributed to the decomposition of n-heptane into oxygenated hydrocarbon like aldehydes rather than the oxidation of NO to NO2.

Acknowledgment: This work was financially supported by The Project Management Center Cultivating Smart Grid & Clean Energy Manpowers (CK-I), Jeju National University.

Biography:

Byeongju Lee was born in 1993. He is majoring in Chemical Engineering at Jeju National University. His research interest includes the application of non-thermal plasma to catalytic NOx removal and seawater treatment.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 67 Scientific Session-5: Catalysis and Energy

Nanoparticles of Ce, Sr, Co in and out the Multi-Walled Carbon Nanotubes Applied for Dry Reforming of Methane

Martin Schmal1, 2*, Camila Emilia Figueira1, Paulo Firmino Moreira Junior1, Reinaldo Giudici1 and Rita Maria de Brito Alves1 1Universidade de São Paulo (USP), Brazil 2Universidade Federal do Rio de Janeiro (UFRJ), Brazil

Abstract

In chemical terms one of the most attractive properties of CNTs is their ability to encapsulate metal nanoparticles and to confine them inside the cavities. In spite of the synthetic difficulties met when trying to access the CNTs cavity, this work aims to synthesize nanocomposites on multi-walled carbon nanotubes (MWCNTs), with Ce and Sr nanoparticles inside and Co nanoparticles outside the CNTs, taking the advantage that Cerium allows the material acting as oxygen storage. As reference we prepared the Ni@MWCNT/Ni catalyst. We obtained the insertion of CeSr and Ni particles inside the wall nanotubes with diameters below 30 nm and Co or Ni outside the nanotubes for CNTs. These catalysts were characterized by N2 adsorption (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). The activity of the catalysts synthesized was tested through the dry reforming reaction of methane to produce synthesis gas at various temperatures (500-700 ˚C) and showed that the CeSr@MWCNT/Co synthesized exhibited high conversions and very similar to the Ni@MWCNT/Ni catalyst.

Biography

Martin Schmal is a Professor at University of São Paulo and Federal University of Rio de Janeiro. His Research interests are Catalysis, Nanotechnology, and Energy. He has 285 publications and more than 6000 Citations.

Degradation of the Catalyst in a low Pt Loading Membrane Electrode Assembly

Radenka Maric1*, Haoran Yu1, Leonard Bonville1 and Andrea Casalegno2 1University of Connecticut, CT, USA 2Politecnicodi Milano, Italy

Abstract

The catalyst durability at low Pt loading remains a barrier for industrial commercialization of the proton exchange membrane fuel cell. Degradation of low loaded Pt catalyst not only reduced the electrochemical surface area but also revealed a Pt depletion zone adjacent to the cathode/membrane interface where about 80% of the Pt was lost due to dissolution and migration into the membrane. Extensive research on the Pt/C degradation mechanisms identified five possible processes for Pt surface area loss, namely, Pt dissolution, Ostwald ripening, Pt agglomeration, Pt detachment, and carbon corrosion. The main focus of this study is on the degradation due to Pt dissolution at the cathode and subsequent transport of the Pt ions to the electrolyte membrane for the low Pt loading of 0.1 mg/cm2. For the control cells, a low Pt- loaded cathode (0.1 mg/cm2) was found to experience similar loss of electrochemical surface area ECSA and Pt mass in the cathode during AST cycles as that for the high Pt-loaded cathode reported in the literature. In particular, a Pt depletion zone was observed adjacent to the cathode/ membrane interface where about 80% of Pt mass was lost due to Pt dissolution and migration of the dissolved Pt ions toward the membrane. A gradient cathode approach was investigated to mitigate the loss of Pt ECSA and mass in this depletion zone.

Biography

Radenka Maric, is University of Connecticut’s Vice President for Research where she oversees the University’s $250M+ research enterprise at all campuses. Dr. Maric is also Named Professor in Sustainable Energy in the Department of Chemical &Biomolecular Engineering. She graduated from the Kyoto University in Japan in 1996. Her research interests include fundamental understanding of the effect of structure, defects, and microstructure on transport and electrical properties of surfaces and interfaces. She has received numerous awards for innovation and leadership in Japan, Canada and the U.S. Dr. Maric is an elected member of the Connecticut Academy of Science and Engineering.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 68 Ni Based Nano-Oxyhydrides for Hydrogen Production from Bioethanol with Scarce Carbon Formation

Louise Jalowiecki-Duhamel1*, Yann Romani1, Yaqian Wei1, Wenhao Fang1,2, Cyril Pirez1 and Sébastien Paul1 1UCCS - Unité de Catalyse et Chimie du Solide, France 2Yunnan University, China

Abstract

At the world level, people are concerned by their health and even life degraded by environmental pollution. Therefore, the potential benefits of a hydrogen economy coming from renewable resources are creating a large consensus and increased attention is focused on hydrogen production technologies. So far, hydrogen has been produced by reforming, partial oxidationand oxidative reforming reactions. The endothermic steam reforming reaction extracts more hydrogen atoms; however, additional energy supply is needed. One alternative way of supplying heat is to add oxygen or air to the feedstock and simultaneously to burn a portion of it. Moreover, in complement, some chemical energy can be also brought using a “smart” catalyst, such as anano-oxyhydride, allowing the use of the chemical energy released from the reaction between hydride species stored in the nano-material and O2. Well tuning the preparation, formulation and conditions applied, different series of nickel based nano- oxyhydrides (Ni-Ce-(Al,Zr)-O and Ni-Mg-Al-Ocatalysts were developed for the highly efficient and sustainable2 H formation from ethanol (and water) in the presence of oxygen with low energy input. Continuous complete conversion of ethanol can be obtained with simultaneous production of H2and scarce carbon formation with an oven temperature at only 50°C. The influence of different parameters on the activity and selectivity was analyzed, such as the reaction temperature, feed compositions, as well as Ni content and in-situ pre-treatment in H2 of the catalysts. Moreover, different physico-chemical characterizations were performed allowing a discussion on active site and mechanism.

Biography

Louise Jalowiecki-Duhamel obtained her doctoral degree in 1984 and her “Habilitation” in 1996 at the University of Lille 1. She is a CNRS (Centre National de la RechercheScientifique) researcher since 1984, working in the heterogeneous catalysis field. Studying various catalytic reactions such as hydrogenation, isomerization, hydrotreatment, selective oxidation reactions, she has proposed some relationships between catalytic orientation and active site structure involving hydride species and anionic vacancies. She is the author and co-author of more than 80 scientific articles, 8 patents, and more than 100 communications in international and national congresses.

Alkaline Ceramics as Possible Captors and Catalytic Materials for the CO2 Chemisorption and Conversion to Added Values Products

Heriberto Pfeiffer Universidad Nacional Autónoma de México, Mexico

Abstract

In the last 20 years different lithium and sodium ceramics have been proposed as potential CO2 captors, at different temperatures (30 - 820°C) under different physicochemical conditions. Moreover, in the last two years, it has been evidenced that some of these alkaline ceramics can be used as possible bifunctional materials for CO2 capture and subsequent catalytic conversion to added value products. This kind of alkaline ceramics have been tested in different catalytic reactions, where the

CO2 previously chemically trapped on these ceramics reacts with methane (CH4), producing syngas (H2 + CO), through the methane reforming process. All these reaction processes (capture reactions and the subsequent methane reforming process) are environmentally important, as CO2, CO and CH4 are catalytically converted into an added value product, the syngas. Moreover, it has been evidenced that these ceramics can be used for the CO oxidation-capture process, which would be highly useful in the hydrogen enrichment.Therefore, the aim of this presentation is to show the most recent advances obtained about the next three different aspects: 1) CO2 capture on alkaline ceramics; 2) the use of these ceramics as bifunctional materials for the CO oxidation-capture process; and 3) The methane reforming reaction for the syngas production, using the CO2 chemically trapped in the alkaline ceramics.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 69 Biography

During the last 10 years, Heriberto Pfeiffer has been working on different sorption processes and heterogeneous catalysis.

His research is mainly focused on CO2 capture and its possible catalytic conversion to added value products. At the same time, he works on the CO oxidation-chemisorption process, as a possible syngas (CO+H2) separation mechanism, using captor and membrane materials. Additionally, Heriberto Pfeiffer works in the biodiesel production and has experience with different thermal, volumetric and gravimetric, techniques.

APPtec – A New Generation of Spray Pyrolysis Technology to Produce Advanced Catalysts

Lars Leidolph* and Thomas Jähnert Glatt Ingenieurtechnik GmbH, Germany

Abstract

APPtec stands as acronym for Advanced Powder Process technology and allows controlling the product properties of new types of powders, impacting or changing the particle structure, composition or surface properties. The thermodynamic conditions of our technology are excep­tional and perfect to create highly functional inorganic catalyst materials.

A pulsating stream of hot gas is the core of the technology. This pulsating hot gas stream brings turbulences into the reaction chamber and these lead to new and exciting product properties. Through the turbulences the heat transfer between gas stream and reactant is five to ten times higher than in a conventional spray pyrolysis. It also leads to a very homogeneous temperature across the reaction chamber and practically gets rid of the retention time gradient, leading to very homogeneous powders. The specially designed combustion chamber produces a strictly pulsating stream of hot gas, whose amplitude, temperature and pulsation-frequency can be freely adjusted to tailor the products properties and functions to the customers’ wishes.

APPtec is a versatile technology that can not only produce simple metal oxides, but also mixed oxides, doped oxides and coated particles. The pore size of the particles is adjustable and particle sizes from nano to micro can be achieved. The big advantage of the APPtec for catalysts comes also from its ability to generate particles with amorphous morphologies and large specific surface areas.. Biography

Lars Leidolph is the manager of advanced powder processing at Glatt Ingenieurtechnik GmbH. He studied technical mineralogy in Leipzig, where he also made his doctorate. He has been working in the field of powder synthesis and processing for more than 15 years and is one of the leading experts in the field.

Mg(OH)2 Films Prepared by Ink-Jet Printing and Their Photocatalytic Activity in CO2 Reduction and

H2O Conversion

E. Luévano-Hipólito* and L. M. Torres-Martínez Universidad Autónoma de Nuevo León, México Abstract

Ink-jet printing is a technology for the fabrication of thin films and devices due to its low cost, scalability, and applicability to a wide variety of deposited materials and substrates. In this work, Mg(OH)2 was deposited by a facile ink-jet method by first time using an organic-based ink and commercial aluminum foil as substrate. The obtained films were evaluated as photocatalyst for H2 generation by using an adequate reactor under visible light. The inks were characterized by thermogravimetric and differential analysis, particle size distribution by laser diffraction, and their zeta potential by dynamic light scattering. The films were characterized by XRD in grazing angle mode, UV-Vis, photoluminescence, linear sweep voltammetry, and their thickness by using a profilometer. The effect of the number of layers and the type of pattern deposited was investigated for photocatalytic -1 -1 H2 generation. The highest reaction yield (268 µmol g h ) was obtained with the film composed with 30 layers of Mg(OH)2, and with the line pattern. In addition, the photostability of the films was studied by fourier transform infrared spectroscopy.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 70 Biography

Leticia M. Torres-Martínez has a wide investigation trajectory and is the head of Ecomaterials and Energy Department of UANL in Mexico. She has published more than 165 papers, 5 patents, and 8 books. She has directed more than 70 postgraduate Theses, 360 international conferences, 21 technological developments, 54 research projects, and so on. Professor Torres-Martinez received a certified Leader in Applied Renewable Energy and Efficiency by Harvard University. Her research interests are related to renewable energy sources focused in the application of photo (and electro) catalysis in the generation of solar fuels, and materials science particularly phase diagrams of semiconductor oxides.

The Role of Thermal-Conducting Materials in Highly Exothermic Catalytic Reactions

Eun Duck Park*, JiEun Kim, Tae Wook Kim and ThienAn Le Ajou University, South Korea Abstract

Most commercial catalysts are supported catalysts except for metal gauze and metal monolith catalysts. The supported catalysts provide a high catalytic active surface area by increasing dispersion of metal or metal oxides. These catalysts are also beneficial for suppressing sintering at high temperatures. The typical supports for these supported catalysts are alumina, silica, activated carbon, etc. However, these supports are generally insulators with a low thermal conductivity. Therefore, hot spots can be generated easily for highly exothermic reactions resulting in sintering of active metal or low yields to desired products, which is not plausible for the practical applications. In this presentation, we utilized two different supports containing high thermal-conducting materials to prepare supported Ru and Ni catalysts which were applied to highly exothermic reactions such as preferential CO oxidation in H2 and CO2 methanation. For comparison, the typical supports such as alumina and silica were also utilized as supports to prepare the similar catalysts. Various techniques such as N2 physisorption, H2 chemisorption, temperature-programmed reduction with H2, CO2 chemisorption, temperature-programmed desorption of CO2, temperature- programmed oxidation, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy were employed to characterize the catalysts. It was revealed that these supports with a characteristic of high thermal-conducting property were effective to increase the dispersion of active metal and to widen the operating temperature window to show a high catalytic activity. Biography

Eun Duck Park is the Professor in the Department of Energy Systems Research at Ajou University in Korea. He received his Ph.D. degree in 2001 from Pohang University of Science and Technology in Chemical Engineering. In 2004, he joined Ajou University after two years of research experience in heterogeneous catalysis at LG Chem. Professor Park is an associate editor of Korean Journal of Chemical Engineering and served as a guest editor for Catalysis Today (2016). His research interests include the synthesis and the structural characterization of heterogeneous catalysts for chemical reactions in energy conversion, petrochemical synthesis, and environmental control.

Structural and Acidic Nature of Phosphotungstic Acid at the Surface and in the Bulk of Silica: Towards a Heterogeneous Catalyst for Quinolones Synthesis

Palraj Kasinathan* and Eric M. Gaigneaux University of Catholique de Louvain, Belgium

Abstract

Quinolones are one of the most commonly prescribed classes of antibacterials in the world. Their market value over the decades has grown due to their therapeutic efficacy and tolerable side-effects; they even challenge the predominance of well- established β-lactam antibiotics [1]. Though, over the years the drug has evolved by substituting the different sites in the quinolones molecule, the synthesis of the compound is still constrained to the traditional homogeneous acid catalysts like AlCl3,

P2O5, triflic acid etc; less attention is paid towards heterogeneous catalysts for the synthesis. In pharmaceutical industry, chloro- substituted quinolones such as 8-chloro-3-benzyl-2-quinolone (economically synthesized from cinnamanilide) is an important molecule in this class of drug. Our persistent effort to utilize heteropolyacids as heterogeneous catalysts in the field of acid catalysis [2, 3], has urged interest in employing phosphotungstic acid (PTA) as catalyst for the transformation of cinnamanilide

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 71 to 8-chloro-3-phenyl-2-quinolone (CPQ). In the present work, heteropolyacids, which generally acts as homogeneous catalysts in polar solvents, is supported on silica in the sake of heterogenization, using two techniques: impregnation (which deposits PTA at the surface of silica) and sol-gel (which embeds the PTA into the bulk of silica). Our aim would be to understand the behavior of PTA on silica in terms of stability, catalytic activity and regenerability; specifically, we wish to differentiate its behavior when present at the surface (obtained by impregnation) from that when they are located in the bulk (obtained by sol- gel). The catalytic properties of the catalysts have been measured and their characterization performed to describe the physico- chemical properties of fresh vs spent catalysts and ensure the development of true heterogeneous catalysts for CPQ synthesis.

(A)

17-PTA-SiO2-SG Intensity (a.u)

9-PTA-SiO2-SG

(B)

17-PTA-SIO2-IM

Intensity (a.u) 9-PTA-SIO2-IM

600 700 800 900 1000 1100 1200 wavenumber(cm-1) .

Figure 1: Raman spectra of catalysts synthesized by sol-gel (A) and impregnation (B): 9-PTA-SiO2-SG, 17-PTA-SiO2-SG,

9-PTA-SiO2-IM & 17-PTA-SiO2-IM.

Table 1: Catalytic results obtained at 200oC with catalysts synthesized by sol-gel and impregnation.

Surface area ICP (wt%, 1st Conv. (1st ICP (wt%, 2st Conv. (2st Catalyst 2 (m /g) cycle) cycle) cycle) cycle)

9-PTA/SiO2–SG 330 8.83 53% 8.37 49%

17-PTA/SiO2–SG 320 16.6 76% 15.91 72%

9-PTA/SiO2–IM 439 9.03 66% 5.98 51%

17-PTA/SiO2 –IM 367 16.75 82% 7.58 67%

References: 1. G. S. Bisacchi, J. Med. Chem. 2015, 58, 4874−4882 2. G Raj, C Swalus, A Guillet, M Devillers, B Nysten, EM Gaigneaux, Langmuir 2013, 29, 4388-4395 3. N. G. Waghmare, P.Kasinathan, A. Amrute, N. Lucas, S.B. Halligudi, Catal. Commun. 2008, 9, 2026–2029 4. V. Dufaud, F. Lefebvre, G. P.Niccolai, M.Aouine, J. Mater. Chem. 2009, 19, 1142-1150

*This work is financially supported by the Beware program. We acknowledge UCB pharma for providing the microwave reactor and technical support.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 72 Improved Combustion Behavior of Heavy Oils Using Oil-soluble Copper-based Catalyst in In-situ Combustion Process

Mikhail A. Varfolomeev*, Chengdong Yuan, Muneer A. Suwaid and Dmitrii A. Emelianov Kazan Federal University, Russia

Abstract

In this work, oil-soluble metal-based catalyst was synthesized. Its pyrolysis and oxidation behavior at nitrogen and air atmosphere, respectively, were investigated by TG-FTIR and DSC. Its catalytic effect on combustion was evaluated using high-pressure differential scanning calorimetry (HP-DSC) and adiabatic reaction calorimeter (ARC). Kinetic parameters were calculated using different models and model-free methods to quantitively characterize the catalytic effect. Simultaneously, SEM and XRD were employed to analyze the variation of catalysts before and after oxidation with/without crude oils to better understand the catalytic mechanism.

The oil-soluble metal-based catalyst significantly improved the combustion behavior of heavy oils including shifting reaction intervals into lower temperature range, reducing activation energy, improving combustion efficiency of high-temperature oxidation (HTO), and decreasing ignition temperature and induction time. TG-FTIR, DSC, XRD and SEM results showed that the metal-based catalyst was totally decomposed during oxidation, and metal oxides nanoparticles were in-situ formed. The high catalytic activity can be attributed to the highly dispersed state of copper stearate and in-situ formed metal oxides. Simultaneously, the high surface area of in-situ formed metal oxides nanoparticles is believed to play an essential role in the process of coke formation and combustion. The significant improvement of the combustion efficiency of HTO and reduction of ignition temperature and induction time indicated that oil-soluble metal-based catalyst not only has a great potential for improving the stability of combustion front, but also can promote ignition process behaving as an initiator in a real in-situ combustion process. Biography

Mikhail Varfolomeev is Assoc. Prof. and Director of Strategic Academic Unit “Ecooil - Global Energy and Resources for Materials of the Future” at Kazan Federal University (Russia). He is Chief of Research Center “Thermal Catalytic Methods for Enhanced Oil Recovery” of Kazan Federal University. He is the Author of more than 80 papers in peer-reviewed journals. He is the Member of Editorial Board of “Petroelum” Journal.

Rapid Hydrogen Generation from the Reaction of Aluminum Powders and Water Using Catalyst Aluminum Hydroxides

Hong-Wen Wang*, Samikannu Prabu, Shih-Chieh Hsu and Jing-Syuan Lin Chung-Yuan Christian University, Taiwan Abstract

Many catalysts were tested on the chemical reaction of aluminum (Al) and water for the generation of hydrogen. Aluminum hydroxides, Al(OH)3, is proved to be a very effective promoter to the generation of hydrogen in Al/water system, however, only when its morphology is favor for the water dissociation. An synthesized, nano-sized Al(OH)3 can reduced the activation energy of Al/water reaction from 158 kJ/mol to less than 75 kJ/mol. The special synthesized Al(OH)3 powders was in plate- like structure and having a high surface area much higher than those spherical particles obtained by a traditional precipitation method. The aluminum hydroxides synthesized from sodium aluminate and ethanol using NaBH4 as an additive exhibits a distinct reduced size and exerts an excellent effect on the hydrogen generation of Al/water system. By taking advantage of its exothermic reaction, it was found that 95% yield of hydrogen can be produced from a 1g Al/ 10g water system within 30 s using these specially synthesized Al(OH)3. The waste Al metallic scraps can also react with water using these effective catalysts and generates hydrogen as much as 90% yield in 5 mins.

Biography

Wang received his B.S. degree from Department of Metallurgy and Materials Science, National Cheng-Kung University (1985), M.S. degree from Department of Materials Science and Engineering, National Tsing-Hua University (1987) in Taiwan and Ph.D. degree from Materials Science Centre, University of Manchester in U.K (1993). Before joining Chung-

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 73 Yuan Christian University in 1999, He was a scientist in Industrial Technology Research Institutes (ITRI), Hsinchu, Taiwan. He became a full professor in 2007 and was the Director of Center for Nanotechnology at CYCU during 2007-2009. He has published more than 70 SCI/EI scientific papers and filed 10 patents.

γ Effect of Water Vapor on the CO Catalytic Combustion over 0.5%PdZrO2/ -Al2O3Catalyst

Xiaojing Lv1, 2* and Yiwu Weng1 1Shanghai Jiao Tong University, China 2University of Cambridge, UK

Abstract γ A study on the deactivation phenomena affecting of water vapor on the 0.5% PdZrO2/ -Al2O3 catalyst was undertaken in this work. The influence of water vapor on the CO catalytic combustion was assessed under different experimental conditions. The results were obtained by analyzing the CO conversion rate under different conditions of reaction temperature, volume fraction and reaction time. The entire experiment process was carried out on the established catalytic combustion experimental rig. Results show that when the concentration of CO are 0.63%, 1.58%, 2.2%, respectively, 8% volume fraction of water vapor makes the ignition temperature and burnout temperature of CO both increased by15-30°C. Changing CO concentration from 0.5% to 3.0%, CO conversion rates will be decreased by 10-60% with the addition of water vapor from 0% to 20.0%, respectively. For the catalytic combustion reaction time of CO, water vapor makes the CO complete reaction time increased by 5-15s.

Remarkable Support Effect on the Reactivity of Pt Based Catalysts for Steam Reforming of Methanol in Microreactors

Vetrivel Shanmugam* and Gunther Kolb Fraunhofer Institute of Microtechnology and Microsystems, Germany

Abstract

Highly efficient hydrogen production from liquid fuels with high energy density has been recognized as one of the most readily viable and alternative strategy to develop clean and efficient power sources. Methanol is an attractive candidate as liquid fuel for hydrogen carrier due to various advantages such as hydrogen rich, sulfur free and easy availability and transport. Herein, a series of catalysts about Pt and In2O3 co-supported on different mesoporous metal oxides (MOx) such as Al2O3, CeO2 and

ZrO2 supports have been developed. Effect of supports over Pt/In2O3/MOx have been investigated by methanol steam reforming in microreactors, which reduce the heat and mass transfer limitations under endothermic conditions, in the temperature range of 300-375°C. Results demonstrated that Pt/In2O3/CeO2 catalysts exhibited the superior catalytic performances and excellent stability, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized hydrogen fueled systems.

Biography

Vetrivel Shanmugam is currently working as scientist in Fraunhofer Institute of Microtechnology and Microsystems, Germany. He received his PhD in chemistry from Anna University, India. He has been post-doctoral fellow at National Taiwan University of Science and Technology, National Central University, Taiwan and Eindhoven University of Technology, Netherlands. His research is focused now on synthesizing novel heterogeneous catalysts for hydrogen production via steam reforming of alcohols as logistic fuel for mobile fuel cell applications.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 74 Fischer Tropsch Synthesis Catalyzed by Co-Anisotropic Nanostructures

K. Soulantica1*, J. Harmel1, A. Berliet2, L. Peres1, S. Maury2, A. Fécant2, B. Chaudret1 and P. Serp1 1Université de Toulouse, France 2IFP Energies Nouvelles, France

Abstract

In the context of constantly fluctuating fuel prices the Fischer-Tropsch reaction is of high importance for the future fuel production either from gas, solid or liquid carbon sources. Cobalt is one of the classical metals that catalyze the Fischer-Tropsch reaction [1]. The catalytic activity depends on various parameters among which, cobalt crystallite size and morphology, support employed, and reactor type. Recently density functional theory-based kinetic studies have shown that for CO activation in the presence of hydrogen, hcp-Co catalysts have higher intrinsic activity than fcc-Co catalysts [2]. Cobalt anisotropic nano-objects can be produced in solution by the organometallic approach [3]. By controlling the reaction conditions we prepared new model supported catalysts, by directly growing cobalt nanowires of hcp structure on mesoporous Al2O3-SiO2 supports, as well as on metallic foams. These model catalysts have been tested either in slurry or fixed bed reactors. The catalytic performances of these systems are very promising in terms of stability and selectivity.

References: 1. Khodakov, A. Y.; Chu, W.; Fongarland, P. Chem.Rev.2007, 107, 1692-1744. 2. Liu, J.-X.; Su, H.-Y.; Sun, D.-P.; Zhang, B.-Y.; Li, W.-X., J. Am. Chem. Soc., 2013,135, 16284-16287. 3. Cormary, B.; Li, T.; Liakakos, N.; Peres, L.; Fazzini, P.-F.; Blon, T.; Respaud, M.; Kropf, A. J.; Chaudret, B.; Miller, J. T.; Mader, E. A.; Soulantica, K., J. Am. Chem. Soc., 2016, 138, 8422-8431.

Biography

Katerina Soulantica, PhD, received her PhD in Chemistry from the University of Athens (Greece). After a post‐doctoral fellow in the University of Valladolid (Spain) she joined the group of B. Chaudret in the Laboratoire de Chimie de Coordination (Toulouse) and worked on the synthesis of metallic nanoparticles. She then joined the Laboratoire de Physique et Chimie des Nano-Objets. She is interested in the synthesis and formation mechanism of nanocrystals, in the tailoring of their physical and chemical properties through their structure, as well as in the design of multifunctional nanosystems for applications spanning from magnetic recording and biosensing to catalysis.

Mechanisms for Redox Enzymes

Per Siegbahn Stockholm University, Sweden

Abstract

The understanding of redox-active enzymes has been a major target in biochemistry for decades. This group of enzymes contains some of the most important enzymes in nature: for example, photosystem II, the main enzyme in water oxidation in photosynthesis, cytochrome c oxidase, the main enzyme in the respiratory chain of humans, responsible for conserving the energy in oxygen reduction, and nitrogenase, the main enzyme in converting nitrogen in the air to ammonia. Since about a decade, quantum chemistry has evolved as one of the most important tools to understand these enzymes. Examples will be given in the present talk mainly from photosynthesis and nitrogenase.

Biography

Per Siegbahn was born in Stockholm, Sweden in 1945. He has completed Ph.d. thesis in 1973 in Stockholm. He is a Professor at Stockholm University from 1983. From 1970-1990, his main research activity is development of ab initio methods. From 1995 the activity has changed to the computational modeling of redox active enzymes using density functional methods

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 75 Reforming of Toluene with Bimetallic Catalysts Supported on Alumina and Synthesized by an Aqueous Sol-Gel Process

Stéphanie D. Lambert1*, Cédric Wolfs1, Vincent Claude1 and Claire Courson2 1University of Liege, Belgium 2University of Strasbourg, France

Abstract

The thermochemical method called “biomass gasification” is generating emphatic interest for the production of bio-Syngas

(CO+H2) since this process presents the advantage of being renewable without emitting CO2. However, in practical applications, there are still some technical problems due to high concentration of tars in the outlet gas, which can condensate and clog the pipes. Previous studies have highlighted the fact that the tar elimination via catalytic reforming seem to be the more practical and economical solution. γ Catalysts were synthesized by an aqueous sol-gel process to develop -Al2O3 doped with 10 wt.% of nickel and 2 wt.% of a second dopant (Co, Cu, Fe, Mn, Mo). Before their adding in AlOOH sol, metallic dopants were complexed with (OCH3)3-Si-

(CH2)3-NH-(CH2)2-NH2 (EDAS) to increase their dispersion by cogelation between EDAS and AlOOH clusters.

All the samples were tested for toluene reforming at 650°C for 300 min. No previous reduction step has been realized. Each 15 min, injection was sent to a GC Compac for analysis.

For samples Al2O3-10Ni-2Mn and Al2O3-10Ni-2Mo, the addition of Mn or Mo allows increasing the toluene conversion up to 100%, whereas all other samples present lower toluene conversion (around 30%). Taking into account the benzene selectivity, it is observed that Mn and Mo are both elements that favor the degradation of aromatic groups. In term of carbon -1 deposit during catalytic test, sample Al2O3-10Ni-2Mn is the most interesting doping since only 0.04 gcarbon gcata is depicted by TG-DSC measurement after catalytic test.

Biography

Stéphanie D. Lambert is a FRS‐FNRS research associate and an associate professor in the Department of Chemical Engineering (DCE) of the University of Liege since 2009. She obtained her Ph.D. in Applied Sciences in 2003. After an engineer position in a Belgian chemical company (Nanocyl) (2004‐2005), and two postdoctoral stays at the DCE of the University of Illinois at Chicago in 2006, and at the Institute Charles Gerhardt in Montpellier in 2007, she joined the DCE of the University of Liege, in which she develops heterogeneous catalysts for sustainable chemistry. She has published over 75 publications and 12 book chapters.

Photocatalytic Aerobic Oxygenation of Hydrocarbons by Electron Transfer

Kei Ohkubo Osaka University, Japan Abstract

Photochemical hydroxylation of benzene with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and water occurs under visible light irradiation to yield phenol and DDQH2.The yield of phenol was 99% with 99% conversion (>99% selectivity). The mechanism of the photochemical hydroxylation of benzene with DDQ was clarified by time-resolved transient absorption spectroscopy. The photochemical reaction was initiated by the photo induced electron transfer from benzene to the triplet excited state of DDQ (3DDQ*) toproduce benzene p-dimer radical cation and DDQ•−. The free energy change for electron 3 * transfer from benzene to DDQ is largely negative (DGet= −0.70 eV), as determined from the one- electron oxidation potential 3 * of benzene (Eox = 2.48 V vs. SCE) and the one-electron reduction potential of DDQ (Ered= 3.18 V vs. SCE). Then, benzene radical cation reacts with H2O to produce an OH-adduct radical of benzene. Finally, phenol was produced by hydrogen atom •– transfer from the OH-adduct radical to DDQ . Photo induced oxygenation of cyclohexane in the presence of O2 also occurred under visible light irradiation of DDQ which acts as a super photooxidant. The products detected by GC and NMR analyses were cyclohexanol, cyclohexanone and cyclohexane hydroperoxide with 70, 40, and 210% yields, respectively. When cyclohexane was replaced by n-butane, n-pentane and 3-methylpentane, the oxygenation reactions also took place to form the corresponding oxygenated products under the otherwise same photochemical reaction conditions.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 76 Biography

Kei Ohkubo is a Professor of Chemistry of Division Innovation Research for Drug Design, Institute of Academic Initiatives, Osaka University, Japan. Kei Ohkubo earned his Ph.D. degree from Graduate School of Engineering, Osaka University in 2001. He was working as a JSPS fellow and JST research fellow at Osaka University (2001-2005), a designated associate professor in Osaka University (2005-2014) and a specially appointed professor at Osaka University (2014-2017). He has been a full professor at Osaka University since 2017.

N-Doped Graphitized Carbon Nanohorns as New Forefront Electrocatalyst in the Highly Selective

O2 Reduction to H2O2

Michele Melchionna1*, Paolo Fornasiero1 and Maurizio Prato1,2 1University of Trieste, Italy 2Nanobiotechnology Laboratory, Basque Foundation for Science, Spain

Abstract

Electrochemical oxygen reduction (ORR) is a challenging approach to the sustainable production of hydrogen peroxide

(H2O2), as well as being a reaction of relevance in fuel cell applications. Carbon nanostructures have emerged over recent years as intriguing components in the assembly of nanostructured composites for heterogeneous catalysis applications. Here we discuss the properties of an outstanding metal-free electrocatalyst for the unexpectedly selective ORR to H2O2. The material consists of graphitized N-doped single-wall carbon nanohorns and can operate either at acidic pH with H2O2 Faradaic efficiency as high as 98%, and at physiological or alkaline pH. Moreover, the observed very positive onset potentials at all investigated pH values (+0.40 V, +0.53 V, +0.71 V vs RHE at pH 1.0, 7.4 and 13.0 respectively), the good stability and the excellent reproducibility make this material a new benchmark catalyst for the ORR to produce H2O2. The outstanding activity arises from the combination of several factors, such as the CNH-dependent facilitation of electron delivery, suitable porosity, and a favorable distribution of the types of N atoms.

Biography

Michele Melchionna completed his PhD in chemistry at the University of Edinburgh in 2007. He then carried out post- doctoral research both in academia (University of Helsinki, Finland and Palacky University, Czech Republic) and industry (Advanced Molecular Technologies, Australia) focusing in organic synthesis and catalysis. He currently holds a position as senior post-doctoral fellow at the University of Trieste, working on carbon nanostructure-based catalysts for energy applications.

New Strategies to Alcohols via Artificial Photosynthesis and Photoelectrocatalytic Reduction of CO2 and Water

Huanwang Jing1,2*, Yuqian Zhang1, Bo Han1, Yanjie Xu1, Yongjian Jia1, Rong Nie1, Yapeng Dong1, Jianguo Wang2 and Zhenping Zhu2 1Lanzhou University, China 2Institute of Coal Chemistry, Chinese Academy of Sciences, China

Abstract

Novel artificial photosynthesis systems (APS) are devised as cells of dye/Pd/NR-MOx (M=Ti, Zn)½½CoPi/BiVO4 that convert efficiently 2CO to alcohols. The photocathodes are amino functionalized, palladium-deposited, and in situ sensitizednano-

TiO2 or ZnO/FTO electrodes that are evaluated by electrochemicaltechniques. TheseAPS cells generate alcoholswithhigh quantum efficiency (0.56-0.95%) under 0.6 V. The selectivity for alcohols of multi-functionalized semiconductors is discussed. Methanol and oxygen was the products thatcould be detected in the liquid and gas phase. The main active species in this APS system were proven using EPR spectroscopy to be hydroxyl radicals releasing O2 gas via H2O2. Moreover, the carbon source 13 18 was validated using a CO2 labeling experiment; O2 was determined tocome from H2O using GC-MS. The optimal CO2 -1 -2 reduction was carried out using Pd/NR2@TiO2 as the working electrode yielding methanol at a rate of 106 mM h cm .

The multifunctional photocathodes can simultaneously mimic the photosystem I (PS I) and Calvin cycle; a CoPi/W:

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 77 BiVO4 photoanode mimics the photosystem II (PS II), and anexternal silica solar cell mimics the membrane voltage. The chelate ligand like salen-type improves the C-C coupling to yield long-chain alcohols. The metal plays a very important role in making active hydrogenatoms by seizing protons and accepting photoelectronsand external electrons. The absolute conduction- band energylevel can be shifted by multi-modifications. These APS systems provide a new viewpoint in CO2 reduction and have potentialindustrial application as alternative to traditional methods invirtue of the energy crisis and environmental issues.

Biography

Huanwang Jing was born in Yongji, Shanxi Province, China and studied Chemistry at Lanzhou University, Lanzhou, where he obtained his B.S., M.S. and Ph.D. (1998). Following 26 months postdoctoral research with SonBinh T. Nguyen in Northwestern University (2000-2002), he was appointed to the Associate professor. His research interests involve the design, synthesis, and mechanistic studies of complexes that catalyze the coupling of epoxides and CO2. Now, the major focus of his group has been on the development of photoelectric catalysts for the CO2 reduction and artificial photosynthesis. Professor Jingreceived his Famous Teacher Award in 2016.

Selective Hydrogenolysis of Glycerol to 1,2-Propanediol over an Effective Copper-Zinc Bi-Metallic Catalyst in a Continuous and Slurry Batch Reactor

Prakash Biswas*, Dinesh Kumar Pandey and Smita Mondal Indian Institute of Technology Roorkee, India

Abstract

Hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) is an attractive route for the value addition of excess glycerol (~10 wt.%) obtained in the biodiesel industry. 1,2-PDO is an important commodity chemicals and the estimated global demand of 1,2-PDO is ~1.5 MMTPA with an annual growth rate of ~4%. In this work, highly active and selective copper-zinc bi-metallic catalyst supported on basic oxides (CaO and MgO) was synthesized by co-precipitation method. The catalytic activity were evaluated and compared forthe selective conversion of glycerol to 1,2-PDO in a slurry batch and in a continuous flow reactor, respectively. Experimental results depicted that, MgO supported bimetallic catalyst was more active and selective to 1,2-PDO 2 -1 -1 in both the reactors because of high specific surface area (56 m g ), surface acidity (0.72 mmol NH3. gcatalyst ) and basicity -1 (0.32 mmol CO2. gcatalyst ) retained on the catalyst. In the slurry batch reactor, maximum glycerol conversion of 98.7% was achieved with 93.7% selectivity to 1,2 PDO after 12 h of reaction at 210°C and 4.5 MPa. However, in the continuous packed bed reactor, very high conversion of glycerol (98.3%) was achieved with ~89 % selectivity to 1,2 PDO at much lower reaction pressure of 0.75 MPa. Fresh and used catalyst characterization results revealedthat, very small metal particle (~ 9 nm) uniformly distributed over MgO support and synergetic interaction between copper, zinc and magnesium oxide was solely responsible for higher selectivity to 1,2-PDO. Catalyst stability was verified by performing the time-on-stream study in the continuous packed bed reactor. Results demonstrated that, Cu-Zn/MgO catalyst showed constant activity and selectivity (~89%) to 1, 2-PDO for 84 h.

Biography

Prakash Biswas received his PhD in Chemical Engineering from Indian Institute of Technology Kanpur, India in 2007. In 2009, after his postdoctoral work at the University of Cincinnati, Ohio, USA, he joined as a Faculty in Chemical Engineering at Indian Institute of Technology Roorkee, India, where he is working as an Associate Professor at present. His research group is currently working on the basic and applied aspect of heterogeneous catalysis process involved for the value addition of biomass derived compounds to fuels and chemicals and reaction kinetics.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 78 Synthesis of Methacrylic Acid from Biomass Derived Itaconic Acid Over High Surface Area Solid Base Catalysts

Ashish Bohre*, Venkata D.B.C. Dasireddy, Uroš Novak, MihaGrilc and Blaž Likozar National Institute of Chemistry, Slovenia

Abstract

Conversion of biomass derived substrate to monomer is an increasingly important topic. We herein reported a bio-based route to methacrylic acid (MAA) via decarboxylation of itaconic acid over solid base catalysts. High selectivity of MAA (50 %) was achieved under relatively mild reaction condition. The reported MAA yields is the highest ever achieved with alkaline base free and noble metal free heterogeneous catalyst for decarboxylation of itaconic acid. The effect of temperature, catalyst mass, pressure, substrate concentration, on itaconic acid conversion and methacrylic acid yield was determined. The fresh and used catalysts are characterized by XRD, N2 physisorption, CO2 TPD, CO- Chemisorption, XPS and SEM-EDX. The selectivity of MAA was higher for solid base catalyst with compared to other commercial catalysts such as Pd/C, Pd/Al2O3, BaO and Zeolite-Y under similar reaction conditions. In the end, an overall reaction pathway for the conversion of the itaconic acid to methacrylic acid via decarboxylation reaction is proposed.

Biography

Ashish Bohre received his Ph. D in 2012 from Dr. H. S. Gour Central University, India. Immediately after completed his Ph. D, he has joined as a post-doctoral fellow in Dr. Basudeb Saha’s research group, University of Delhi. Currently, he is working as a researcher at the Department of Catalysis and Chemical Reaction Engineering, National institute of chemistry, Ljubljana. The main focuses of his research are catalytic conversion of lignocelluloses biomass into next- generation biofuels and fine chemicals.

One-dimensional Modeling and Simulation: Catalytic and Non-catalytic Gasification of Petroleum

Coke with CO2

Cornelius Agu* and Britt Moldestad University College of Southeast Norway, Norway

Abstract

The gasification of carbon with 2CO is energy intensive due to high activation energy of the reaction. The use of catalysts can reduce this energy barrier and thus improves on the conversion. Modelling of chemical reaction systems is also gaining weight for understanding the system behavior at different operating conditions as well as achieving efficient reactor designs. However, the complexity of fluid-solids interaction is a challenge in developing accurate models for such systems. Using the simulation of a one-dimensional model, this paper shows the effect of catalyst on the gasification of petroleum coke with CO2.

The study assumes that the bed is fixed within a control volume at any given time. The 5 cm diameter bed is initially filled with 75 µm petroleum coke particles to a height of 20 cm. The model is developed for a non-isothermal system and simulated using MATLAB. The effect of catalyst is represented with the appropriate kinetic rate constant for different concentration of iron (III) chloride. The results are interpreted using the conversion factor and specific energy consumption in each of the catalytic and non-catalytic cases. The simulated results are compared with experimental data from literature.

Biography

Cornelius Agu is a PhD research fellow at University College of Southeast Norway, and his main research area is biomass gasification based on the bubbling fluidized bed technology. Prior to his PhD studies, he has worked extensively on the measurement of flow rate in open channel systems. In addition to his research experience, he was with Heineken Brewery subsidiary in Nigeria as an engineer for six years. He has earned a master’s degree in Process Technology from my current institution, and a bachelor’s degree in Mechanical/Production Engineering from Nnamdi Azikiwe University, Nigeria.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 79 Activated Carbon Impregnation Method via Chemical Solutions for Pre and Post- Combustion CO2 Adsorption Technology in a Fixed Bed Reactor Process

Douglas Soares dos Santos* and Joseph Wood University of Birmingham, UK

Abstract

Solid adsorbents are potentially viable for application as the next generation of carbon capture technology instead of the proposed aqueous amine technology for chemical absorption processes. Activated Carbon (AC) Norit® was selected for this study, accepting its high adsorption rates and the affinity with carbon dioxide molecules when it is exposed in a mixed gas flow.

The AC was modified via different chemical solutions, such as KOH, ZnCl2, H3PO4 and amine solutions (MEA, DEA, TEA, TEPA and combinations with MDEA) using impregnation process, aiming to obtain high adsorption rates and performance, focusing on the surface area and pore modifications, and to improve the solid/gas interaction. Additionally, the process has been tested via pre (25 °C/25 bar) and post-combustion (70 °C/10 bar) methodology, evaluating the performance for the adsorbents in a fixed bed reactor process via Pressure Swing Adsorption (PSA) methodology. Thermogravimetric analysis (TGA) was applied to test the adsorption capacity under ambient conditions with pure flow of carbon dioxide. High-Pressure Volumetric Analyzer was applied to obtain the gas volume adsorbed for the sample at pre-combustion conditions, producing adsorption- desorption isotherms system under nitrogen and carbon dioxide. Brunauer-Emmett-Teller analysis was used to determine the textural properties and thus to compare the pore-size and the volume adsorbed. Some of the adsorbents modified show promise as materials for carbon capture, such as activated carbon modified via MEA (2.18 mmol/g of CO2, post-combustion conditions) and by KOH (2.70 mmol/g of CO2, pre-combustion conditions) solution when compared with the unmodified sample (2.24 mmol/g, pre-combustion conditions) analysed on TGA.

Biography

Douglas Soares dos Santos, is a PhD Candidate in Chemical Engineering at the University of Birmingham (UK). His research interest is on Adsorption Technology for Carbon Dioxide Capture in a Fixed Bed Reactor Process and modeling this process using gProms software. This project is sponsored by CNPq/Brazil, previously, as a Master Student in the H2CIN group at Federal University of Rio de Janeiro/Brazil.

Enhanced Dehydrogenation of NH3BH3 during its Catalytic Hydrothermolysis Under Action of Transition Metal Chlorides Solution

A. M. Gorlova1, 2*, N.L. Kayl1,2, O.V. Komova1, O.V. Netskina1,2, G.V. Odegova1 and V. I. Simagina1 1Boreskov Institute of Catalysis, Russia 2Novosibirsk State University, Russia

Abstract

The creation of compact safe system of hydrogen storage is the main problem of hydrogen energy. Ammonia borane

(NH3BH3, AB), a promising stable H2 storage material, is the object of intense studies now.

In this study, a catalytic hydrothermolysis of AB was investigated. In this process the highly exothermal hydrolysis of a part st nd of NH3BH3 (1 step) is coupled to its thermolysis (2 step). This leads to the high efficiency of this process. Note that catalytic route of hydrothermolysis of AB has not been studied in the literature yet.

It was shown that addition of metal chloride solution (M = Co, Ni, Cu, Fe) to a solid-state bed of AB particles leads to formation in situ a catalytically active nanosized phase. Measurements of the temperature of the reaction layer together with the amount of evolved hydrogen and ATR-FTIR study of products have shown that at external heating 85 °C there was st nd acceleration of the 1 step, which resulted in a stronger heating of the reaction layer and a start of 2 step. The 2H generation rate and H2 yield depend on the temperature of external heating, the mole ratios AB/MCl2 and AB/H2O and the nature of M. -1 -1 High values of H2 storage capacity (7.5 wt%) and average H2 generation rate (39 ml∙gcomposition min ) were achieved at 85 °C in this study. Note that organization of hydrogen production by supplying a limited quantity of catalyst precursor solution to the

NH3BH3 provides for stability of NH3BH3 in the cartridge.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 80 Biography

A. M. Gorlova is a master’s degree student (chemistry) and has completed Bachelor of Chemistry in 2017 from Novosibirsk State University, specialized in catalysis and adsorption.

A New Approach to Renewable Methane Production: Combining Direct Air Capture and Sabatier Reaction

Janna Veselovskaya1, 2*, Pavel Parunin3, Olga Netskina1 and Aleksey Okunev1, 2 1Boreskov Institute of Catalysis SB RAS, Russia 2Novosibirsk State University, Russia 3Skolkovo Institute of Science and Technology, Russia

Abstract

Large scale integration of renewable wind and solar energy into the electrical grid is challenged due to volatility of power supply. Power-to-Gas (P2G) process is a perspective approach to renewable energy storage in chemical media. The first step of P2G process is hydrogen generation through electrolysis of water using renewable electrical energy. Considering safety issues regarding hydrogen transportation and storage, it is reasonable to use it on site for methane production via catalytic Sabatier reaction: CO2 + 4H2® CH4 + 2H2O. Incorporation of the Direct Air Capture (DAC) unit with into P2G system offers an opportunity to use atmosphericCO2 as a sustainable feedstock to produce renewable fuel, which can be used for numerous industrial applications.

[1-3] The novel process, combining direct CO2 capture from ambient air using K2CO3/Al2O3 composite sorbent and CO2 methanation via Sabatier reaction in the presence of the 4% Ru/Al2O3 catalyst, has been performed in a cyclic mode. The o thermal regeneration of the composite sorbent in these cycles has been carried out in H2 atmosphere at T = 325 C with the gas flow going straight from the adsorber outlet to the preheated catalytic reactor. Performance of the ruthenium catalyst in CO2 methanation process has improved upon cycling, apparently due to in situ activation of the supported component. It has been demonstrated that the use of the activated catalyst makes it possible to transform the desorbed carbon dioxide to methane with conversion >98% at T = 325-400oC.

Biography 1. Veselovskaya J.V., Derevschikov V.S., KardashT.Yu., Stonkus O.A., Trubitsina T.A., Okunev A.G. // Int. J. Greenhouse Gas Control, 2013, Vol. 17, p. 332–340. 2. Sivtsova O.N., Eremenko O.I., Derevshchikov V.S., Veselovskaya J.V. // Russ. J. Phys. Chem., 2017, Vol. 91, No. 5, p. 807-813. 3. Veselovskaya J.V., Parunin P.D., Okunev A.G. // Catalysis Today, 2017, In Press, Corrected Proof, doi: 10.1016/j. cattod.2017.05.044

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 81 Selective CO2 Hydrogenation to Higher Hydrocarbons Over TiO2 Supported Fe-Based Bimetallic Catalysts

Nuttakorn Boreriboon1, 2*, Xiao Jiang1, Chunshan Song1 and Pattarapan Prasassarakich2 1Pennsylvania State University, PA, USA 2Chulalongkorn University, Thailand

Abstract

Catalytic CO2 hydrogenation to higher hydrocarbons has become an approach to reduce both CO2 emission and dependence on fossil fuels. This research aims at developing the supported Fe-based catalysts that are efficient for CO2 hydrogenation to higher hydrocarbons. A comparative study on the CO2 hydrogenation activities and product selectivities of monometallic and Fe-based bimetallic catalysts was carried out. The titania-supported monometallic and bimetallic Fe-based catalysts were prepared and tested for CO2 hydrogenation in a fixed-bed reactor. The combination of Fe and a small amount of second metal

(Co and Cu) showed the synergetic promotion effect on the CO2 conversion and the space-time yields (STY) of hydrocarbon products. Moreover, the incorporation of K and La as promoters could further improve the activity and product distribution to higher hydrocarbons. Detailed characterization by temperature-programmed desorption (TPD) demonstrated that the presence of K and La promoter significantly changed theadsorption properties of adsorbed 2H and CO2 on the catalyst surface. The changes in adsorption properties could optimize the product distribution to higher hydrocarbons as products.

Biography

Nuttakorn Boreriboon was born on December 23, 1991 in Bangkok, Thailand. He received his B.Sc. (1st class honors) degree from Department of Chemical Technology, Chulalongkorn University in 2014. He continued pursuing Ph.D. in Chemical Technology under Prof. Pattarapan Prasassarakich at Chulalongkorn University and received the Royal Golden Jubilee Scholarship (RGJ) from Thailand Research Fund.He hascarried out his Ph.D. research at Clean Fuel and Catalysis Program (CFCP) at the EMS Energy Institute of the Penn State (US) under the guidance of Prof. Chunshan Song.

Strong Metal - Support Interaction of Pd Supported TiO2 Catalysts Prepared by Single-Step Sol-Gel for the Catalytic Hydrodeoxygenation of Guaiacol

Siriporn Jongpatiwuta* and Tepin Hengsawad Chulalongkorn University, Thailand

Abstract

Catalytic hydrodeoxygenation of guaiacol has been studied and gained attention in connection with biofuel production by bio-oil upgrading due to its oxygen rich model compound (methoxyphenly components) generated by fast pyrolysis of lignocellulose biomass. In this work, a series of Pd supported TiO2 catalysts were prepared by incipient wetness impregnation (IWI) and single-step sol-gel (SSSG) methods with different reduction temperature to investigate the influence of strong metal - support interactions (SMSI) on the catalytic activity and selectivity of hydrodeoxygenation of guaiacol to aromatic products in a continuous flow fixed bed reactor. It was found that the degree of SMSI in Pd/TiO2 catalysts drew a significant effect on the catalytic performance. All Pd/TiO2 catalysts were characterized by N2 adsorption-desorption isotherms, X-ray diffraction

(XRD), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS).

Biography

Tepin Hengsawad is a Ph.D. candidate in the Petroleum and Petrochemical College at Chulalongkorn University. She received a full-scholarship from the Royal Golden Jubilee (RGJ) Ph.D. Program under the Thailand Research Fund (TRF) and the Fulbright Junior Research Scholarship for doing research at School of Chemical, Biological and Material Engineering, the University of Oklahoma, USA for a period of one year. Her research interests are development of heterogeneous catalysts for bio-fuels production (bio-diesel and bio-jet) and bio-oil upgrading. Tepin worked with a comparative analysis of CO2 separation technologies in offshore natural gas processing (2013-2014). This project was sponsored by Brazilian Petroleum, Gas and Biofuels Institute (IBP). She graduated in Industrial Chemistry from Severino Sombra University (2008-2012).

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 82 Hydrotreatment of the Heavy Phase Fraction of Beech Wood Pyrolysis Oil Over Nickel Catalysts

Caroline Carriel Schmitt*, Michael Rapp, Klaus Raffeltand Nicolaus Dahmen Karlsruhe Institute of Technology, Germany

Abstract

The application of biomass as a feedstock for fuels and chemical production has been investigated over the last years. Due to the environmental issues related to fossil based products, new technologies should be developed in order to reduce our dependency of non-renewable resources. The fast pyrolysis process converts biomass into pyrolysis oil at high temperature (~500 °C), ambient pressure and inert atmosphere. The final product, a brown viscous liquid, shows a complex chemical composition and can naturally separate in two phases. While the lighter phase is rich in water, sugars, ketones and small oxygenated molecules, the heavier phase contains lower water and oxygen content and higher content of depolymerized lignin products, such as phenolic compounds and pyrolytic lignin. Upgrading treatment is required in order to improve the bio-oil properties. Hydrotreatment of these fractions individually can result in a final product with even better properties, especially in the case of the heavy phase.

In the present work, the heavy phase of a beech wood bio-oil was hydrotreated applying two nickel-based catalysts at different temperatures and hydrogen pressures. The influence of the hydrotreatment conditions are correlated with the upgraded products composition. Furthermore, the selectivity, activity as well as deactivation of the catalysts were investigated.

The results obtained provide valuable insights about the application of nickel-based catalysts for bio-oil hydrotreatment, specially related to the hydrodeoxygenation of the heavy phase. The characterization of the catalyst before and after the reaction was also addressed, providing relevant information for further catalytic process development.

Biography:

Caroline Carriel Schmitt studied chemical engineering at University of Joinville Region, Brazil in 2011, finishing her Masters in chemical process development at Federal University of Paraná, Brazil in 2013. Currently she is a PhD student working at the thermochemical conversion of biomass group, under the supervision of Dr. Klaus Raffelt and Prof. Dr. Nicolaus Dahmen at the Institute for Catalysis Research and Technology (IKFT) located at Karlsruhe Institute of Technology (KIT), Germany. Her research topic involves the upgrading of pyrolysis oil through hydrodeoxygenation reactions applying nickel- based catalysts.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 83

February 21 3Wednesday Scientific Session-6: Environmental Catalysis | Catalysis for Renewable Sources

No More Noble Metals in Catalysts! History of a Revolutionary Substitution

A. Glisenti*, M.M. Natile and P. Canu University of Padova, Italy

Abstract

Sustainable development means, among other, pollutants’ abatement, sustainable energy storage and conversion, green hydrogen production. Perovskites, general formula ABO3, are among the most studied mixed oxides in heterogeneous catalysis. Beside the first applications in oxidation reaction and NO reduction their use is nowadays so diffused to make them considered a serious alternative to Platinum Group Metals (PGMs).

We developed several perovskite based noble metals free catalysts. The successful PGMs’ substitution was reached through perovskite doping, in the A and B site, and nanocomposition. In this contribution the results obtained starting from economically and environmentally sustainable perovskites (manganite, ferrites, cobaltates) will be presented and compared. The insertion of dopants into the perovskites was always verified by XRD; moreover, XPS and EDX results allowed to study the effect of doping on surface segregation. The reducibility was monitored by means of TPR, morphology by SEM. Perovskite-based materials characterized by high Oxygen mobility/exchange capability, oxygen vacancies, mixed ionic electronic conductivity, were developed. Different reactions and reaction environments were tested revealing, consequently, the great effect of the activation strategies (doping, nanocomposition), in different fields: CO oxidation, CO assisted NO reduction, NO decomposition, VOC elimination, reactivity toward automotive exhausts (for TWC application), soot oxidation, dry reforming, alcohol steam and auto- thermal reforming, methane oxidation. High conversions have been observed (also under difficult conditions) validating perovskites’ activation strategies for noble metal substitution. A great success was also obtained in electro-catalysis. The development of PGMs’-free electrodes for innovative Solid Oxide Fuel Cells (SOFCs): Intermediate Temperature-SOFCs, Reversible-SOFCs, Biofed-SOFCs, Single Chambers- SOFCs.

Biography

A. Glisenti has completed Masters in Chemistry in 1988 from University of Padova. From 1988-1993, he has done PhD in Chemical Science. From1993-1994, he has done post-doct research activity in the Advanced Magnetic Recording Laboratory (IBMSanJose-CA); In 1994 he has joined as a Researcher in University of Padova. From 2010, he is a Professor at University of Padova. His H-index is 26 (>150 contributions) and research interests are 1. Electrodes for Intermediate Temperature, reversible, symmetric, bio-fed SOFC/SOEC 2. PGM free catalysts for TWC 3. Sustainable catalysts for green hydrogen

Electronic State of Cu, Ag and Au in Cu/ZnO, Ag/ZnO and Au/ZnO Catalysts and its Effect on Diesel Particulate Matter Oxidation: An XPS Study

María Griselda Corro Hernández Benemérita Universidad Autónoma de Puebla, Mexico

Abstract

Diesel particulate matter (DPM) oxidation activities of Cu, Ag and Au deposited on ZnO (n-type semiconductor) were investigated. The catalysts were characterized by XRD, XPS and DRS. Results indicated that the performance of metal- semiconductor catalysts depends on the electronic interactions at metal-semiconductor interface. The high activity of Cu/ZnO is explained by the formation of stable Cu1+-Cu2+ sites at the copper-ZnO interface, enhancing contact efficiency of DPM 2+ - 1+ on Cu and the generation of superoxide ions (O2 ) on Cu . The high stability of bifunctional sites is associated to electronic interactions between copper and ZnO at their interface. As the work function of Cu1+ (5.27 eV) is higher than that of ZnO (4.5 eV), an electronic transfer might have occurred at the Cu/ZnO interface, increasing stability of Cu1+ sites.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 86 The high activity of Au/ZnO, is explained by the formation of stable Au0-Au3+ sites at the gold-ZnO interface. As the work function of Au0 (5.3 eV) is higher than that of ZnO (4.5 eV), an electronic transfer might have occurred at Au/ZnO interface, increasing the stability of Au0 sites.

Ag/ZnO did not present activity for DPM oxidation. As the work function of Ag (4.26 eV) is lower than that of ZnO (4.5 eV), an electronic transfer might have occurred form Ag to ZnO at Ag/ZnO interface, increasing the stability of Ag1+, which is not active for DPM oxidation.

Biography

Grisel Corro was born in Puebla, a sunny city in Mexico, in front of Popocatepetl, a big volcano always showing its presence. Grisel Corro obtained a PhD in Poitiers, France in Physical Sciences. Her research deals with Catalysis for pollution abatement and for renewable energy generation.

Dynamics and Selectivity of N2O Formation during Regeneration Phase of Pt-Based Catalysts

Lidia Castoldi*, Roberto Matarrese and Luca Lietti Politecnico di Milano, Italy

Abstract

Nitrous oxide (N2O) appears as one of the undesired by-products in exhaust gases emitted from diesel engine after treatment systems, such as diesel oxidation catalysts (DOC), lean NOx trap (LNT, also known as NOx storage and reduction (NSR)) or selective catalytic reduction (NH3-SCR and HC-SCR) and ammonia slip catalysts (ASC, AMOX, guard catalyst). N2O acts as a greenhouse gas, damages the ozone layer and causes many environmental and human health problems.

In the LNT catalysts, during the transient mechanisms associated to the reduction of stored NOx N2O formation is observed. In particular, N2O evolution is apparent upon switch from lean to rich mode but also during the transition from rich to lean. It has been suggested that N2O observed at the Lean-to Rich (L/R) transition is formed at the regeneration front, due to the presence of oxidized/not fully reduced metal sites which are in a close proximity to NOx ad-species. On the other hand, the N2O formation upon the Rich to Lean transition (R/L) has been associated to the reaction between NOx and residual surface reductive species. Both the understanding of the pathways leading to N2O formation in LNT catalysts and the catalytic

N2O decomposition (deN2O) to nitrogenand oxygen serve as available options for the removal of N2O emissions.

For this purpose, a fundamental study on homemade model LNTs catalysts has been carried out by coupling microreactor reactivity data and operando FTIR spectroscopy, in order to study both the N2O formation and the N2O decomposition.

Biography

Lidia Castoldi graduated in Industrial Chemistry at University of Milan. After a Post-Degree Master in Polymers Science at Politecnico of Milan (Italy), she got the PhD Degree cum laude in Industrial Chemistry and Chemical Engineering at Politecnico of Milan (Italy). In 2015 she became Associate Professor at Politecnico of Milan.Her scientific activities can be framed in the branch of catalytic processes especially relating to environmental sector. She has a consolidated experience about NOx catalytic reduction using storage/reduction techniques. Her studies are documented by many scientific articles published on international journals and by the many presentations done during international congresses.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 87 The Future of Automotive Emission Control Catalysis

Andy Walker Johnson Matthey Plc, UK

Abstract

Catalyst systems have been used to control the emissions from motor vehicles for over 40 years now, and have made a massive contribution to providing clean air for billions of people worldwide. These systems are now used on cars, buses, trucks, construction and agricultural machinery, ships etc across the globe.

The incoming catalyst systems for gasoline vehicles will comprise the latest generation Three Way Catalysts in association with coated Gasoline Particulate Filters, and will be unrecognizable from the first generation systems to control the emissions from gasoline vehicles introduced in the mid 70s. The latest generation Diesel emission control systems comprise up to four catalyst components, fulfilling different, but critical roles in the overall after treatment architecture - with similarities, and differences, between the catalyst requirements for passenger car and bus/truck applications.

This presentation will outline the evolution of emission control regulations, which focused for many years on the so-called criteria pollutants, carbon monoxide, hydrocarbons, oxides of nitrogen and Particulate Matter, and which now increasingly focus on Global Warming contributors such as carbon dioxide, nitrous oxide and methane. We will look at the implications of current and future legislation on the characteristics required of the next generation emission control catalyst systems, and will show how such systems are key enablers to reduce further the impact of transportation on the environment, both in terms of criteria pollutant and Greenhouse Gas emissions. We will end by looking at the future evolution of the automotive powertrain, and the changes required enabling this future.

Biography

Andy Walker is the Technology Director for Johnson Matthey’s Clean Air Sector. Within this global role he leads a worldwide team responsible for developing, demonstrating and scaling up emission control catalysts for the transportation and stationary source markets, covering applications including passenger cars, buses, trucks, agricultural and construction machinery, ships and power plants. Andy was educated at Cambridge University in the UK and has worked at Johnson Matthey in a variety of roles for 25 years. He has published over 90 peer reviewed papers and is a Fellow of the Society of Automotive Engineers.

Manganese-Base Catalysts for Catalytic Wet Air Oxidation of Phenolin Waste Water

Bing-Hui Chen*, Changjian Ma, YaoYaoWen, Paul Fasan, Nuowei Zhang and JinbaoZheng Xiamen University, China

Abstract

Phenol is one of the common water contaminants. Decomposed phenol into CO2orat least less harmful compounds has profound significance. Catalytic wet air oxidation (CWAO) isone of the most promising methodto degrade phenol in waste water. Many previous studies have shown that MnCeOx catalysts demonstrating remarkable activity for the degradation of phenol. However, the MnCeOx generally has stability problem when it is used for CWAO of phenol in water. Herein, we have developed and prepared a novel MnCeOx catalyst that has high activity as well as stability by modifying preparation methods and optimizing the Mn-Ce composite. Furthermore, the mechanism of high efficiency and stabilityfor the as-prepared catalysts δ were also studied. Developing a new approach, a -MnOx was synthesized, which demonstrate a higher activity and stability δ than the MnCeOx to degrade phenol at Furthermore, a highly reactive and stable -MnO2 catalyst has been synthesized for CWAO of phenol at70 °C, a lowest temperature on reported literature. It was found that the high activity of the catalyst is mainly due to itshigh concentration of Mn4+ and high reactivity of surface oxygen species. The high resistance to Mn leaching 4+ δ and easy self-recovery of Mn species from low valence Mn is responsible for the stability of -MnO2 catalyst. The activity and stability of the catalysts weredetermined by TOC, HPLC and AAS. Different techniques including XRD, BET, H2-TPR, O2- TPD, XPS, TEM and elemental analysis were used to characterize the chemical and structural distinctions between different catalysts.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 88 Biography

Bing-Hui Chen received PhD degree in Chemical Engineering from University of Leeds (UK) in 1998 supported by full Scholarship of British Council, master’s in chemical Engineering from Zhejiang University in 1990, and bachelor’s in chemical engineering from Huaqiao University in 1984. Currently, he is a fullprofessor of College of Chemistry and Chemical Engineering, and also the head of the Department of Chemical & Biochemical Engineering at Xiamen University. He has wonseveral awards including the National Academic and Innovation Award in 1997 and the Sinopec Science and Technology Progresses Award (1996 and 1997).

Degradation of Pyrene and 14C Pyrene in the Artificial Contaminated Soil by Hemoglobin and Hydrogen Peroxide

Guyoung Kang* and Seoungjong Lee Hankuk University of Foreign Studies, South Korea

Abstract

Hemoglobin is a member of heme-protein with catalytic non-specific chain reaction in the presence of hydrogen peroxide. The catalytic ability of hemoglobin to degrade pyrene in pyrene contaminated soil was demonstrated using 14C pyrene. Three 14 bench scale laboratory tests were performed using soil contaminated with C pyrene in the presence of buffer, H2O2, or hemoglobin with H2O2 through catalytic reaction for 24 hr. The initial pyrene concentration in contaminated soil was 11 mg/ 14 kg and 5,495,033 dpm of C pyrene. Results showed that about 17% of pyrene was degraded by H2O2 and 38% of pyrene 14 was degraded by hemoglobin with H2O2 through catalytic reaction after 24 hrs. After 24 hrs of reaction, 0.1% of C pyrene 14 14 in contaminated soil was mineralized by H2O2 while 1.2% of Cpyrene was mineralized by catalytic reaction. No CO2 was detected in buffer control test. High performance liquid chromatography for14 C material present in acetonitrile fraction revealed that 15.9% of 14C pyrene was composed of polar intermediate products. After the catalytic reaction, the intermediate was found 25 compounds by fraction analysis. These results suggest that hemoglobin catalysis could be used to treat pyrene contaminated soil as a novel catalytic technology for remediation of hazardous material in soil.

Biography

Guyoung Kang is a professor in the department of Environmental Science at Hankuk University of Foreign Studies, Republic of Korea. Ph.D. received on 1993 under Dr. David K. Stevens, Department of Civil & Environmental Engineering at Utah State University, Logan, USA.

Enhanced Photocatalytic Hydrogen Evolution of Chalcogenide through Ruthenium and Copper Modification

Jerry J. Wu*, Gang-Juan Lee and Yu-Hong Hou Feng Chia University, Taiwan

Abstract

Ru and Cu co-doped ZnS nanoparticles were successfully synthesized in DI water and ethanol solvent by a microwave assisted solvothermal method using citric acid surfactants in aqueous medium. Dopants act as an electron sink which diminishes the electron-hole pair recombination, which resulted in further improving the photocatalytic activity. Cu-doping into the lattice or interstitial of ZnS provides suitable impurity energy levels, which make it easier for the excited electrons from the valence band of ZnS to inject into the conduction band of ZnS. Ru3+ ion is another dopant element which can make its own energy level, depending on the band edge position of host matrix, at forbidden band gap region as efficient center for recombination of excited carriers. Therefore, Ru and Cu co-doped into ZnS could improve the photocatalytic activity. Hydrogen evolution from -1 1 an aqueous solution containing 0.1 M Na2S at pH 3 and 0.15 g L of Ru4CuZnS photocatalyst had the maximum of 1,533 μmol h-1 g-1. In addition, 1Ru4CuZnS photocatalyst has a smaller charge transfer resistance than bare ZnS. Thus, Ru and Cu co-doped ZnS photocatalysts exhibit much higher photocatalytic activity.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 89 Biography

Jerry Wu received his bachelor’s degree in 1989 from the Department of Environmental Engineering in National Cheng Kung University and master’s degree in 1991 from the Graduate Institute of Environmental Engineering in National Taiwan University, Taiwan. Further he obtained his Ph.D. in 1998 from the Graduate School of Civil and Environmental Engineering, Michigan State University, USA. He is an editorial board member of American Journal of Environmental Engineering and Frontiers in Environmental Engineering. He is currently a professor at Feng Chia University in Taiwan. Prof. Wu’s research interests include ozonation and advanced oxidation processes for water and wastewater treatment. In addition, he is also interested in the nanomaterials synthesis and various applications, including decontamination, electrochemical sensor, energy conversion, and hydrogen production from water splitting.

Environmentally-Friendly Enzyme Immobilization onto MOF Materials with High Enzyme Capture Efficiency and Excellent Biocatalytic Activity

Victoria Gascón*, Mayra B. Jiménez, Rosa M. Blanco and Manuel Sánchez-Sánchez Instituto de Catálisis y Petroleoquímica (ICP), Spain

Abstract

Metal-Organic Framework (MOF) materials are a revolution in terms of porous materials applicability. They potentially can be used in separation, storage and catalysis, among other applications. Since their discovery in 1999, more than 20,000 new structures have been synthesized thanks in part to their high versatility. However, only some of them are really stable in water (both in liquid and vapour phase). Furthermore, biocatalysis field has been demanding a “universal support” able to encapsulate/ immobilize in-situ any kind of enzyme in a straightforward methodology capable of keeping its enzymatic catalytic activity. This requisite has been a big challenge considering the drastic synthesis conditions required for most of the MOF materials. So, a compromise between the development of a well-formed material support and an acceptable enzymatic activity had to be achieved in order to be able to obtain active biocatalysts, ideally prepared in just one step and under sustainable conditions. In this work, we describe how to synthesize MOF materials in water, under mild conditions and practically instantaneous in the presence of a variety of enzymes. This in-situ or one step methodology uses a semi-crystalline Fe-BTC MOF material (similar to the commercial Basolite F300) allowing the development of efficient active biocatalysts (97% with respect to the free enzyme in the case of CALB lipase). Particularly, this enzyme support improves the benefits given by some other MOF-based supports

(like NH2-MIL-53(Al) or MIL-53(Al)) having at the same time more active biocatalysts and lower enzyme leaching, what brings these catalysts closer to their industrial use.

Biography

Victoria Gascón is a Doctor in Chemistry as Interdisciplinary Science. Her main research interest is on porous materials field, particularly focusedon different topics like water decontamination, biocatalysis, green chemistry and materials for energy storage. She has two University degrees in Industrial Chemical Engineering and Environmental Sciences, as well as, a Master’s degree in Advance Chemistry. All her degrees were highly recognized with different awards. Additionally, after finishing her PhD (2014, ICP-CSIC), again with Excellent achievements, in the area of design of new biocatalysts, she started her first post- doc developing new sustainable MOF materials as enzyme supports. Her second post-doc has been hosted inside the Bernal Institute (UL, Ireland) in Bioelectrochemisty & Biocatalysis group. Currently, she has just joined the Crystal Engineering group led by the worldwide recognized Prof. Zaworotko.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 90 End-of-Pipe Flue Gas Cleaning Technologies for NOx

Rasmus Fehrmann*, Leonard Schill, Susanne Mossin, Peter Westergaard Jacobsen and Anders Riisager Technical University of Denmark, Denmark

Abstract

Due to deactivation of the commercial deNOx SCR catalyst in the flue gas from biomass as fuel in power plants and the demand of a catalyst working at lower temperatures in waste incineration plants and onboard ships, research efforts have grown to develop alternative catalysts or new technologies for flue gas cleaning end-of-pipe.

The present study investigates the effects of different support materials 2(Al O3, TiO2) and methods of preparation (wet impregnation, deposition precipitation) on the activity and water resistivity of MnFe containing low temperature SCR deNOx catalysts. Deposition precipitation results in more active catalysts, regardless of the support material. No major difference in activity was seen between alumina and Titania supported MnFe. Water at levels of 20 vol. % has a strong inhibiting effect. Due to the high fraction of labile surface oxygen induced by deposition precipitation this kind of catalyst is also attractive for other applications like e.g. removal of volatile organic compounds (VOC).

Another approach for end-of-pipe deNOx technologies is absorption and catalytic conversion of NO by ionic liquids. Thus the ionic liquid BMIM (butyl-methyl-imidazolium) nitrate has proven surprisingly efficient for absorption and catalytic conversion of NOx to nitric acid which can be desorbed in a successive separation step forming commercial grade concentrated nitric acid and a fully regenerated absorber. Our recent results regarding optimization of this technology applying the SILP (Supported Ionic Liquid Phase) concept forming porous, ionic liquid impregnated solid filters for selective NOx removal will also be addressed.

Biography

Rasmus Fehrmann is professor at DTU Chemistry, The technical University of Denmark and head of the Centre for Catalysis and Sustainable Chemistry. He has long experience in bridging fundamental understanding of materials with catalytic properties to their applications for gas cleaning in addition to selective gas absorption by ionic liquid technology. He has published 150 scientific papers, 25 patents and several books and book chapters. He has supervised around 40 PhD students so far. He is member of 10 international chemical societies and has among others served during 10 years as member of the Danish National Committee for Chemistry.

Adsorptive Desulfurization of Dibenzothiophene in Hexadecane over Supported TiO2-ZrO2 Adsorbents Using Light Irradiation

Sukanya Thepwatee1*, Pawnprapa Pitakjakpipop2, Nitipon Chekuntod1, Atisayapan Chanchawee1 and Jonggol Tantirungrotechai3 1King Mongkut’s University of Technology North Bangkok, Thailand 2National Metal and Materials Technology Center (MTEC), Thailand 3Mahidol University, Thailand

Abstract Dibenzothiophene (DBT) adsorption under light irradiation has gained a great attention in the last few years because of its mild operation condition and no need of using peroxides as an oxidant. Light irradiation was used to enhance adsorption capacity and selectivity of the adsorptive desulfurization process for ultra-low sulfur diesel fuel production. Our previous study showed that TiO2-ZrO2 has a great performance on desulfurization of diesel fuel by converting DBT to DBT-sulfone (DBTO2) and adsorbed DBTO2 under light irradiation. In this work, we have studied the impact of supports such as fumed silica, zeolite, and alumina on the desulfurization performance of the TiO2-ZrO2. 10 wt% of TiO2-ZrO2on each support was prepared by wetness impregnation method. 300 ppmS of DBT in hexadecane (DBT/C16) was used as a model fuel. Desulfurization experiments were performed under light irradiation at ambient condition using a 40 W UV light (365 nm). The material function as a DBT adsorbent and as a photocatalyst for DBT oxidation was compared with bulk TiO2-ZrO2. Their surface acidity, chemical phase composition, surface area, porosity, and band gap energy were characterized by usingNH3-TPD, XRD, N2 adsorption-desorption, and UV-Vis spectroscopy. Their function on DBT removal was correlated with their physicochemical properties.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 91 Biography

Sukanya Thepwatee is currently a faculty member at the Department of Industrial Chemistry, King Mongkut’s University of Technology North Bangkok, Thailand. She received her Ph.D. degree in Energy and Mineral Engineering (Fuel Science option) from the Pennsylvania State University, USA, in 2016 with her research in the field ofdeveloping light-active adsorbent for adsorptive desulfurization of diesel fuel from Prof. Chunshan Song’s group. Her current research interest is related to heterogeneous catalysis and adsorbent for environment and sustainable energy. Her current project has strongly collaborated with Dr. Pawnprapa Pitakjakpipop, a researcher from National Metal and Materials Technology Center (MTEC) and Assist. Prof. Dr. Jonggol Tantirungrotechai from Mahidol University, Thailand.

Oxidation of Dichloromethane over Pt Supported on Various Titania-Zirconia Mixtures

Satu Pitkäaho1*, Lenka Matejova2, Ivana Troppova2, Lucie Obalova2 and Riitta L. Keiski1 1University of Oulu, Finland 2VSB-Technical University of Ostrava, Czech Republic

Abstract

Dichloromethane (DCM) is among thethree most commonly used chlorinated solvents (CVOCs) in Europe and it is emitted into air mostly as a part of emissions from various industrial processes (e.g. production of pharmaceutics). Catalytic oxidation represents the cost-efficient and environmentally acceptable way to reduce CVOC emissions. The development of γ highly efficient catalysts is still a matter of keen scientific interest. Contrary to -AlO3-based catalysts, TiO2-based catalysts have been less studied in the DCM oxidation even though titania mixed with some other metal oxides, e.g. ZrO2introducing surface acidity and increasing thermal stability, could also be a promising catalyst support. Hence, in this study the TiO2-

ZrO2supports with various Ti:Zr molar ratios were synthesized by a specific sol-gel method and calcined at 550°C. All supports were impregnated with ~1 wt% of Pt. For comparison, also Pt/TiO2 and Pt/ZrO2 catalysts were prepared. Catalysts were characterized by nitrogen physisorption, CO chemisorption, ICP, XRD, H2-TPR, and NH3-TPD techniques. This set of catalysts was tested in DCM total oxidation with the aid of light-off tests to study the effect of support composition on the activity and selectivity of the catalysts. Based on the tests, it is evident that all Pt/TiO2-ZrO2 catalysts were significantly more active than parent Pt/TiO2 and PT/ZrO2. Catalysts showed good HCl selectivity over the Pt/TiO2-ZrO2 catalysts ranging from 79 to 91%. The DCM total oxidation to desired CO2 and HCl occurred best with the Pt/Ti0.3Zr0.7On and Pt/Ti0.9Zr0.1On catalysts, when only traces of CH2O (1 ppm) and CO (2 ppm) were detected.

Biography

Satu Pitkäaho has research expertise in catalysis in the fields of VOC abatement and utilization, and in water purification. During her doctoral studies, she carried out VOC oxidation research in close cooperation with industry. She defended her doctoral thesis in 2013. She did her postdoctoral study period at the University of California, Berkeley ( Jan–July 2015) where she was working in Professor Gabor Somorjai’s group preparing model nanoparticles and building a catalyst testing device for gas phase testing. Currently, she is supervisingthree doctoral students in the fields of VOC oxidation, sulfate removal and REE metals in catalytic applications.

Improvement of Diesel Particulate Filter system in Terms of Balance Point Temperature and Reduction Characteristics with Respect to Various Filters and DOC/DPF Combinations

YoungminWoo1*, Ahyun Ko1, Jinyoung Jang1, Yongjin Jung1, Oh Seuk Kwon1 and Young Jae Lee1 Korea Institute of Energy Research, South Korea

Abstract Regarding the country wide air quality issue (in terms of loss of clarity in sky view or ultra-fine particle encompassment), diesel vehicles are frequently ascribed to be one of the reasons for that. As a matter of fact, diesel vehicles produced prior to Euro 5 regulation are not equipped with on-board particulate filtration system (DPF; Diesel particulate filter) so particles generated during combustion might be expelled from the tail pipe. To mend this problem, DPF is also recommended to be implemented before the tail pipe of the in-use vehicles and an appropriate regeneration of the filter system is required so that the filter can function properly to avoid manual regeneration. In this study, various filters and DOC/DPF combinations were investigated

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 92 on the 5 cylinder 2.7 liter passenger diesel engine to draw low BPT (Balance Point Temperature) and resultantly to get easy and prompt natural regeneration of DPF. The test after-treatment systems cover different pore sizes and cell densities, catalyst compositions and combinations in DOC and DPF layouts. The emission characteristics were also reviewed via vehicular tests on chassis dynamometers.

Biography

Youngmin Woo is currently working as asenior research at KIER (Korea Institute ofEnergy Research) and his research fieldincludes combustion in the internal combustionengines and vehicles, especially withnew and renewable fuels to mitigate climatechanges and draw out both better energy efficiency and emissions.

Catalytic Hydro-treatment of Oil Produced by Thermo-Catalytic Reforming of Biomass for Renewable Chemicals and Fuels

Nina Schmitt1*, Andreas Apfelbacher1, DaschnerRobert1 and Andreas Hornung1-3 1Fraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Germany 2University of Birmingham, UK 3Friedrich-Alexander University Erlangen-Nuremberg, Germany

Abstract

Due to the climate change conference 2020 new ways are needed to produce CO2 neutral fuels and chemicals. At Fraunhofer

UMSICHT a novel process has been developed to convert residue waste biomass into renewable fuels and chemicals by a CO2 neutral way. This conversion procedure consists out of two-steps: The first one is a thermo-chemical conversion (TCR®) of biomass into organic oil. The second step, a catalytic hydro-treatment, produces hydrocarbons.

The outstanding composition of the dark brown TCR® bio-oil offers the opportunity of a successful further processing step. The high thermal stability of the TCR® oils allows a thermal treatment of these oils like e.g. distillation or hydration.

For catalytic hydroteatment different standard catalysts like NiMo/Al2O3, CoMo/Al2O3, ZSM-5, and Ru/C, are used. In a laboratory scale batch reactor at temperatures up to 380°C and pressures to 170bar the mentioned catalysts lead to different promising products. Most heteroatoms of the former TCR® oil could be removed by the hydration, generating a colorless liquid with a lower density than the TCR® bio-oil. Depending on the used catalyst the ratio of aliphatic and aromatic compounds varies. Analyses show that that the products meet diesel and gasoline standards like EN 228 and EN 590. Summarized it can be said that a new way was found to produce renewable, CO2 neutral chemicals and fuels from waste biomass and biological residues.

Biography

Nina Schmitt is a PhD student working on hydrotreatment of oil produced by TCR® process, since 2015.

The Influence of Lattice Distortion in PtFe and PtMn Nanoclusters on Surface Electronic Reconfiguration and Catalytic Performances in Liquid Phase Oxidation

Xin Jin*, Hao Yan, Yibin Liu, Xiaobo Chen, Xiang Feng and Chaohe Yang China University of Petroleum, China

Abstract Fine control of morphologies for alloy and core-shell crystals remains a grand challenge in the field of heterogeneous catalysis. While conventional theories and experimental methodologies are primarily focused on tuning composition and nanostructures, advances in nanoscience and nanotechnologies have discovered that tunable atomic arrangement is a key for enhanced catalytic performances and innovative catalyst design. We use a controllable thermal annealing technique to synthesize intermetallic and lattice distorted PtFe and PtMn bimetallic nanocatalysts, which show exceptional liquid phase oxidation performances in facile biomass conversion to carboxylic acid derivatives. Surface characterization by TEM and XPS show that the lattice mismatch between Pt and Fe/Mn is the intrinsic driving force for lattice distortion and phase transformation, while experimental studies confirm that such uniquely structured clusters exhibit approximately ten-fold enhancement in catalytic

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 93 activity compared with monometallic Pt catalysts. Furthermore, computational studies reveal the electronic reconfiguration in bimetallic clusters for PtFe and PtMn systems lead to a d-band center shift and changes for Pt-PtPt-Fe and Pt-Mn bond strength. The combined experimental with computational studies provide insights into plausible surface reaction mechanism and optimized catalyst structures for green carboxylic acid synthesis from biomass feed stocks.

Biography

Xin Jin received his PhD and did postdoc work in The University of Kansas under the supervision of Professor Raghunath V. Chaudhari. His research area is focused on nanocatalyst design for biomass and shale gas conversion to chemicals, and multiphase kinetic modeling. He is the recipient of North America Catalysis Society Young Scientist Award for International Congress on Catalysis, Richard Kokes Award, Organic Reaction Catalysis Society Young Researcher Award, North America Symposium on Chemical Reaction Engineering Young Researcher Award and Frank Bowdish PhD Research Award.

Hydrotalcite based Catalysts for the Hydrogenolysis of Glycerol

Jiří Kolena*, Lenka Soukupová, Jaroslav Kocík and Jaromír Lederer Unipetrol Center for Research and Education, Czech Republic

Abstract

In recent years, glycerol, available as a side product from the biodiesel production, attracted attention not only as the raw material for specialties production but also as an intermediate for the commodities production. For example, it can be converted to 1, 2-propanediol by a catalytic reaction with hydrogen. Various types of catalysts can be effective in this reaction; the hydrotalcite-like structures containing Cu and at least one other transition metal have been proved to be good precursors of the catalysts for this purpose. Though various metals have been tested as modifiers, Zn in combination with Al has been evaluated as having the best effect on the catalyst activity and selectivity. The hydrotalcites are converted to active forms of catalysts by calcination and subsequent reduction of the oxides generated by the calcination. Characterization by conventional methods revealed the dependence of catalyst structure, which influences its performance, on the content of modifying metals as well as on the conditions of preparation mainly in the calcination step.

Biography

Jiri Kolena, graduated in 1975 in the Institute of Chemical Technology Prague. He finished his PhD study at the same institute in 1985, hydroformylation of alkenes being the theme of his dissertation. From 1975, he worked in the Research Center of Chemopetrol Litvinov dealing with the research aimed at catalytic transformation of oxygenates and (later on) hydrocarbons. Since the year 2000 he worked at the Institute of Inorganic Chemistry Usti nad Labem as the head of petrochemistry department. Currently, he works in development of catalytic processes for transformation oxygenates from renewables in Unipetrol, Center for research and Education.

Does a Strong Oxophilic Promoter Enhance Direct Deoxygenation? A Study of Ni-based Catalysts in p-Cresol Conversion

Chi-Ying Hsieh*, Yu-Chuan Lin, Pei-Ju Hsu and Jia-Wei Jiang National Cheng Kung University, Taiwan

Abstract

A bifunctional catalyst, composing of a hydrogenation-active metal and an oxophilic promoter for CAR-O bond weakening, is effective in deoxygenation of lignin derivatives due to a contact synergy. A systematic comparison of the physicochemical properties of Ni-based catalysts promoted by metal oxides (i.e., FeOx, MoOx, and WOx) with different oxophilicities was conducted, and their catalytic behaviors were evaluated in conversion of p-cresol. Ni-promoted by WOx, which possesses the highest oxophilicity among the promoters, is intrinsically more active than NiMo and NiFe in direct deoxygenation (DDO), possibly related to its great hydride mobility. However, in a H2-pressured system, Ni-promoted by MoOx, which has a moderate oxophilicity among employed promoters, generated higher DDO product (toluene) than NiFe and NiW. The discrepancy of toluene yield and promoter’s oxophilicity is discovered to be related to the different hydrogenation rates of toluene: toluene-

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 94 derived from DDO of p-cresol can be subsequently hydrogenated into methylcyclohexane over NiW catalyst more rapidly than NiMo and NiFe catalysts do. Hence, both the oxophilicity of promoter and the inertness of hydrogenation of DDO product should be considered for designing a bimetallic catalyst in conversion of lignin derivatives.

Biography

Yu-Chuan Lin was born in Taipei, Taiwan. He obtained his BS (2000) and MS (2002) degrees in Chemical Engineering from National Cheng Kung University (Taiwan). He received his PhD in Chemical Engineering from Kansas State University (2006). He did a postdoctoral stay at University of Massachusetts-Amherst (2008-2009). He is currently an Assistant Professor of Department of Chemical Engineering at National Cheng Kung University. He published about forty papers with an h-index of 18. He serves as an editorial board member of an open access journal, Catalysts, and is a reviewer for various catalysis and chemical engineering-related journals.

Supported 12-Tungstophosphoric Acid as Heterogeneous Catalysts for Polycondensation of D, L-Lactic Acid

Liana S. Chafran1*, Jonas M. C. Campos2, Sílvia C. L. Dias2 and José A. Dias2 1Union of the Central Plateau, Brazil 2University of Brasilia, Brazil

Abstract

Poly (lactic acid) (PLA) is an important polymer because of its significant biocompatibility and biodegradability properties.

Supported H3PW12O40 (H3PW) on activated carbon (C) at different loadings was utilized in the catalytic polymerization of D, L-lactic acid to form PLA.The stability of the polymer chain was monitored by thermogravimetric analysis (TG) using the temperature of the maximum velocity degradation (TD) to determine the optimal production conditions. The obtained polymer was characterized by gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FT-IR), 1H/ 13C nuclear magnetic resonance (NMR) spectroscopy, specific optical rotation ([α] D 25), powder X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The average molar mass of the polymer was 17,400 g mol-1. A stereo specific isomer, poly(L-lactic acid) (PLLA), was obtained with approximately 85% selectivity, probably by a mechanism of cationic polymerization.The comparative analysis of the catalyst before and after three reutilizations by SEM showed good dispersion of the spherical particles of H3PW and the presence of the polymer after the use of the catalyst, which might act as a crystalline seed for the growth of new chains in each new reaction cycle.Using 1H and 13C NMR spectroscopy, it was possible to prove the formation of PLA polymeric structure, which was also observed by XRD patterns of the crystalline material.

Biography

Liana Chafran was graduated in Chemistry from the UnB in 2010. She received her Master in 2012 and Doctor degree in 2016. At present, she is professor at the FACIPLAC and a post-Doc at the National Institute of Science and Technology of Nanobiotechnology – EMBRAPA. With experience in supported heterogeneous catalysts, she deposited a patent in 2012, for developing a cheaper way to synthesize PLA blends with high PLLA content through the use of D,L-lactic acid. Currently, she develops projects aiming the synthesis of functionalized biomaterials for application in sustained release systems as well as polymer matrix for bioprinting-3D.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 95 Towards Cleaner Environment and Sustainable Production – The Role of Catalysis

Riitta L. Keiski*, Satu Ojala, Satu Pitkäaho, Tiina M. Pääkkönen, Prem Kumar Seelam, Piia Juholin,Zouhair El Assal, Bouchra Darif, Niina Koivikko, Marja Kärkkäinen, Tiina Laitinen, Anass Mouammine, Tuomas Nevanperä, Buddhika Rathnayake, Felipe Lopes da Silva, Esa Turpeinen, Anna Valtanen and Mika Huuhtanen University of Oulu, Finland

Abstract

Air and water pollutants originating from mobile and stationary sources are in the core of causing health and environmental problems. The need of more efficient catalytic technologies to overcome these problems e.g. to achieve cleaner environment and improved air quality, is urgent. In addition, utilization of emissions present in flue gases and industrial side streams, i.e. converting them to valuable compounds such as fuels and other compounds, enhances sustainable development. Sustainable production of renewable fuels and chemicals, e.g. hydrogen, methane, methanol, by reforming, photocatalysis, and catalytic membrane technologies is under active development. Another major issue is the increasing need of clean potable water and the development of energy and cost efficient methods for water purification. The organic load in aqueous streams, such as drugs and pesticides, can be mineralized or converted to new products by hybrid photocatalytic/catalytic technologies. Catalysis offers among other technologies sustainable routes to mitigate pollutants.

The aim is to provide a general overview on the recent research topics and innovations in the field of environmental catalysis. Catalysis plays a major role in emissions abatement and utilization, both by enhancing primary and secondary methods in emission abatement, and in providing ways to use the emission compounds as resources and enablers in e.g. fuels, chemicals and materials production. It also gives paths to combine compounds in emission streams to e.g. biomass streams and thus enhances both bio- and circular economies. The use of catalysis fosters materials and energy efficiencies in industry and societies, and sustainable development.

Biography

Riitta L. Keiski, is a Professor, Dean of the Faculty of Technology at the University of Oulu, has a long experience in catalysis, sustainability, nanomaterials, and separation processes research. She is Adj.Prof. in Chemical process engineering, heterogeneous catalysis and environmental engineering; Dr. h.c. at Corvinus University of Budapest and National University of Engineering in Lima. Keiski has supervised 25 doctoral theses, supervises 20 doctoral students, and has over 230 publications, 400 other scientific contributions, one patent. She is a member of the Board of the Academy of Finland, has several other national and international academic responsibilities, and has coordinated tens of research projects.

Nanostructuring Catalysts for Solar and Electrolytic Water Splitting

Salvador Eslava1*, Dominic Walsh1, Katherine Fielden2, Tom Russell2 and Chris Bannister1 1University of Bath, UK 2Advanced Fuel Technologies, UK

Abstract

Facile, effective and greener approaches for the synthesis of nanostructured materials are a key in the development of photoelectrodes and electrocatalysts for artificial photosynthesis. Here I will present the recent developments we have achieved in the preparation of nanostructured photocatalysts, photoelectrodes, and electrocatalysts for on-board hydrogen devices. We put emphasis not only on tuning their final morphology to maximize their surface area but also on finding greener approaches that will be more sustainable and easier to commercialize. For example, exploiting the amphiphilic properties of graphene oxide and its oxygen functional groups, we have successfully imparted two-dimensionality features to TiO2 and LaFeO3photocatalysts and photoelectrodes, boosting their final performance. We have also successfully found greener approaches using naturally occurring acids to anodize tungsten foil and prepare WO3photoanodes, avoiding the frequent but dangerous use of HF acid. We have also found a greener and a more sustainable deep eutectic solvent based on food additives and fertilisers for the microwave synthesis of hematite Fe2O3 nanoparticles that can be doctor bladed for successful hematite photoanodes. Finally, we have also

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 96 recently developed MoS2 and Mo-Ti electrocatalysts for water splitting using oxoalkoxo clusters and graphene oxide templating. The final applications of these electrocatalysts are in on-board vehicle hydrogen devices to enrich diesel fuel with hydrogen. In a nutshell, this presentation will cover the recent advances in my group in tailoring the nanostructure of photoelectrodes and electrocatalysts for water splitting, together with the characterization that relates their properties to their activity.

Biography

Salvador Eslava is a Lecturer in Chemical Engineering at the University of Bath (UK). Before this, he was a postdoctoral research associate in the Materials Department at Imperial College London (2011-2014) and in the Chemistry Department at The University of Cambridge (2009-2011). He conducted his PhD work at the Centre for Surface Chemistry and Catalysis (COK) in Katholieke Universiteit Leuven and IMEC, Belgium. Dr Eslava currently leads a group on novel synthetic approaches for catalytic materials, including transition metal oxides, halide perovskites, oxide perovskites, and their application on energy generation and storage.

Copper Oxide Nanoparticles Prepared Under Ultrasonic Irradiation for the Removal of 2,4, Dichlorophenol Under Sun Light

Mohammadreza Kamali*, Maria Elisabete V. Costa and Isabel Capela University of Aveiro, Portugal

Abstract

Engineered nanomaterials have been widely studied in the last decade for the removal and degradation of various environmental contaminants. Within this context, copper oxide nanomaterials (nCuO) have drawn a particular attention due to their unique chemical, electrical, optical and thermal properties [1]. Recently, their functionality as photocatalytic materials has been reported for the efficient and economic treatment of a wide range of contaminates [2]. However, there is still a need to enhance the efficiency of these materials and also to master the parameters involved in real environmental conditions. In this research a fast and green route for the synthesis of nCuO was adopted. The performance of the synthesized nanomaterials towards the removal of a contaminant (2,4-dichlorophenol) from polluted waters was also studied. A direct photometric assay was used for the detection of the contaminant concentration. A circulating batch reactor with a number of advantages over simple batch reactors was developed and tested under various experimental conditions including i.e. pH, reaction time, nanomaterials dosage, flow rate, and the light irradiation. A L-9 Taguchi experimental design was employed to optimize the removal process and to identify the relative importance of the experimental parameters. Optimum conditions for the removal of 2,4-dichlorophenol were identified, being found that under 180 min of reaction time, 1 g/L of nanomaterials, pH 4, a circulating flow rate of 30 mL/min and sun light irradiation, 78% removal of the pollutant could be achieved without the assistance of any other oxidizing agents. The reaction time and pH were identified as the most critical parameters.

References: 1. S. P. Meshram, P. V Adhyapak, U. P. Mulik, and D. P. Amalnerkar, Chem. Eng. J., vol. 204–206, pp. 158–168, 2012. 2. A. J. Barik and P. R. Gogate, Ultrason. - Sonochemistry, vol. 36, pp. 517–526, 2017.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 97 Gliding Arc Plasma, an Easy but Powerful Approach to Prepare Oxide Catalysts and Boost their

Performance in Wastewater Treatment: The Specific Case of MnO2

F.W. Boyom Tatchemo1,2*, A. Tiya Djowe2, E. Acayanka2, S. Laminsi2 and E.M. Gaigneaux1 1Université catholique de Louvain, Belgium 2University of Yaounde I, Cameroon

Abstract

Recently, a great interest in fundamental and applicative research was focused on the synthesis and utilization of metal oxides nanoparticles. The synthesis of organized mesoporous materials with a transition-metal oxide framework has stimulated many researches. Among them, MnO2 is interesting for its low cost, environmental friendliness and its various applications including in photocatalysis, and plasma catalysis [1-3]. Several methods allow preparing MnO2 as sol-gel, thermal decomposition, and hydrothermal. Here, we report on an alternative plasma chemical procedure to produce MnO2 at ambient conditions. It rests on a gliding arc plasma; it is easy but very powerful. To our knowledge, the synthesis of MnO2 by such route technology not been reported previously. α Here, we show the variety of MnO2 nanostructures that we synthesized following this route. Mesoporous -MnO2nanorods, γ 2 and -MnO2nanospheres, with specific areas of 98 and 48 m /g were respectively obtained by plasma chemical reduction of · · KMnO4 and oxidation of Mn(CH3COO)3.2H2O at high voltage. The corresponding chemistry proceeds via NO and HO radicals generated in the plasma. Working at low voltage, we recorded a change in the nature of the polymorph formed with α an increase of the specific area. Impact of the temporal post-discharges species (H2O2, HNOONO) on the -MnO2 nanorods obtained after plasma chemical reduction of KMnO4 will also be addressed. Such post-discharge treatment induces indeed changes the physicochemical properties of the recovered material. Catalytic performances of the materials prepared will be reportedin the bleaching of the Tartrazin Yellow (TY) namely a dye representative of polluted wastewaters.

References: 1. M. Zheng, H. Zhiang, X. Gong, R. Xu, Y. Xiao, H. Dong, X. Liu, Y. Liu, Nano.Res.Let. 2013, 8:166. 2. W.H. Ry, D.W. Han, W.K. Kim, H.S. Kwon, J.Nanopart.Res. 2011, 13:10, 4777-4784. 3. F.W.Boyom-Tatchemo, S. Nzali, G. Kamgang-Youbi, A. Tiya-Djowe, D. Kuete-Saa, E. Acayanka, S. Laminsi, E.M. Gaigneaux, Top.Catal. 2017, 11244-017-0761-9.

Advanced Catalytic Membrane Reactor for Environmental Applications

Habiba Shehu*, Edward Gobina, Edidiong Okon and Ifeyinwa Orakwe Robert Gordon University, UK Abstract

The separation characteristics and dynamic behavior of two binary mixtures, CO2/CH4 (50:50, vol%) and C3H8/CH4 (50:50, vol%), on an alumina/zeolite membrane were studied experimentally. The permeation of the binary mixtures was compared with that of pure CO2, CH4, and C3H8 at 323–473 K and 10 - 100 kPa. The permeation flux of pure CH4 which has the strong adsorption affinity, was much higher than that of 2CO and C3H8. However, the permeation flux of the CO2/CH4 mixture was hindered by CO2 with large kinetic diameter. The molecular interactions, adsorption affinity, and kinetic diameter and structure of each component was studied and the transport mechanism of CH4 through the zeolite pores was investigated. The transient permeation and separation behavior of the gases through the zeolite membrane membranes was successfully predicted by Fick’s first law which assumes that the transport diffusivity of gases through the zeolite membrane is dependent on the operating temperature. Physical properties of the membrane were investigated by SEM micrographs. Results confirmed the deposition of the zeolite on the alumina support. The catalytic action of the Y-type zeolite on an alpha alumina membrane was observed with the low temperature of 293 K conversion of methane to C2+ compounds. Biography

Habiba Shehu is currently undergoing her PhD programme at the Robert Gordon University Aberdeen and is a research assistant at the Centre for Process Integration & Membrane Technology at Robert Gordon University Aberdeen. She has over 10 journal publications and written 5 book chapters. She is a member of the Royal Society of Chemist, the International

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 98 Association of engineers and the European Membrane Society (EMS).

Optimal Operating Condition for the Oxidation of Volatile Organic Compounds Using Plasma- Coupled Catalysis

Sang Hyeok Ko*, Jin Oh Jo, Sang Baek Lee and Young Sun Mok Jeju National University, South Korea

Abstract

The removal of volatile organic compounds (VOCs) using plasma-coupled catalysis over various metal oxides was investigated. The present plasma-coupled catalytic reactor was made up of two tubular electrodes wrapping around a quartz tube in which catalyst pellets were packed. The model VOC compounds were propane and butane. The simulated contaminated gas consisted of nitrogen 90% (v/v), oxygen 10%(v/v), and propane 200 ppm (or butane 200 ppm). The flow rate of each gas was precisely controlled by a mass flow controller, and the total flow rate was 2 L/min. Most of the experiments were conducted γ at room temperature. The catalyst prepared by impregnating -Al2O3 with aqueous metal precursor solutions. The metal compounds explored included Ag, Pd, Cu, Mn and Zn. The VOC removal efficiency mainly depended on the discharge power delivered to the reactor and the type of catalyst. The removal efficiencies of the model VOCs were both higher in the plasma- catalyst combined process than the plasma alone or the catalyst alone. In order to determine the best operating condition, the effects of the parameters on the removal efficiency and the byproducts distribution were examined. Temperature-programmed oxidation (TPO) was performed in the presence and in the absence of plasma discharge to understand the mechanisms for the removal of VOCs when plasma is combined.

Acknowledgment: This work was financially supported by The Project Management Center Cultivating Smart Grid & Clean Energy Manpowers, Jeju National University.

Biography

SanghyeokKo was born in 1994. He is majoring in Chemical Engineering at Jeju National University. His main research interest is the treatment of volatile organic compounds with plasma and plasma-activated catalysis.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 99 Deactivation of Nickel-based Catalysts during Steam Reforming of Naphthalene in the Presence of Hydrogen Chloride

Andrei Veksha1*, Wen-Da Oh1, Apostolos Giannis1, Victor W.-C. Chang2, Grzegorz Lisak1 and Teik-Thye Lim1 1Nanyang Technological University, Singapore 2Monash University, Australia

Abstract

Hydrogen chloride is commonly present in syngas produced from municipal solid waste and biomass gasification. The influence of HCl on the activity of nickel-based catalysts during catalytic reforming of naphthalene (one of the main tar compounds) was investigated. Two commercial alumina catalysts containing nickel and two catalysts prepared by impregnation of alumina support and limestone with a nickel salt were tested at 790 °C in the absence and presence of HCl (500-2000 ppmv).

Regardless of HCl presence, alumina supported catalysts converted ~90-100% of naphthalene into a mixture of H2, CO and

CO2. Limestone catalyst had the lower conversion efficiency in the absence of HCl (~80%), which remained stable during the testing period. However, in the presence of HCl, the catalyst rapidly deactivated due to the reaction of support with HCl as revealed by SEM/EDX. Although the conversion of naphthalene over alumina catalysts was stable for 5 h in the presence of HCl, the composition of product gas has changed during this period. Specifically, the production of CO increased while the concentration of CO2 decreased due to the loss of water-gas shift activity of nickel in the presence of HCl. The spent alumina supported catalysts were characterized using N2 adsorption, FESEM/EDS, XRD and TEM after the reforming in the absence and presence of HCl, and a possible deactivation mechanism was proposed.

Biography

Andrei Veksha is a postdoctoral research fellow in the Residues and Resource Reclamation Centre at Nanyang Environment and Water Research Institute (Singapore). Dr. Veksha received his Ph.D. degree in Environmental Science from Okayama University ( Japan). Before joining Nanyang Environment and Water Research Institute, he has been working as a postdoctoral research fellow at the University of Calgary (Canada). His areas of research include chemical reaction engineering, heterogeneous catalysis and material science. His current research work is focused on solid waste gasification and development of catalysts and sorbents for syngas upgrading.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 100 Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 101 Poster Presentations

Innovative Hydrocarbons Recovery and Utilization Technology Using Reactor-Separation Membranes for Off-Gases Emission

Edward Gobina1, Habiba Shehu*, Edidiong Okon and Ifeyinwa Orakwe Robert Gordon University, UK

Abstract

The separation characteristics and dynamic behavior of two binary mixtures, CO2/CH4 (50:50, vol%) and C3H8/CH4 (50:50, vol%), on an alumina/zeolite membrane were studied experimentally. The permeation of the binary mixtures was compared with that of pure CO2, CH4, and C3H8 at 323–473 K and 10 - 100 kPa. The permeation flux of pure CH4 which has the strong adsorption affinity, was much higher than that of 2CO and C3H8. However, the permeation flux of the CO2/CH4 mixture was hindered by CO2 with large kinetic diameter. The molecular interactions, adsorption affinity, and kinetic diameter and structure of each component was studied and the transport mechanism of CH4 through the zeolite pores was investigated. The transient permeation and separation behavior of the gases through the zeolite membrane membranes was successfully predicted by Fick’s first law which assumes that the transport diffusivity of gases through the zeolite membrane is dependent on the operating temperature. Physical properties of the membrane were investigated by SEM micrographs. Results confirmed the deposition of the zeolite on the alumina support. The catalytic action of the Y-type zeolite on an alpha alumina membrane was observed with the low temperature of 293 K conversion of methane to C2+ compounds.

Biography

Habiba Shehu is currently undergoing her PhD programme at the Robert Gordon University Aberdeen and is a research assistant at the Centre for Process Integration & Membrane Technology at Robert Gordon University Aberdeen. She has over 10 journal publications and written 5 book chapters. She is a member of the Royal Society of Chemist, the International Association of engineers and the European Membrane Society (EMS).

A Support Structure Effect of Ni-Cu and Ru-Rh Based Catalysts on Hydrogen Production by Methanol Steam Reforming

Aleksandra Lytkina*, Natalia Orekhova, Margarita Ermilova and Andrey Yaroslavtsev A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Russia

Abstract

Hydrogen production for PEM fuel cells presents an suitable alternative to internal combustion engines. Methanol steam reforming (MSR) is a promising way to produce pure hydrogen from biomass prepared source. Metal oxide-stabilized zirconia supports (MxZr1-xO2-d) with different dopants (M = Y, La, Ce) were prepared by coprecipitation method. Bimetallic Cu-Ni and Ru-Rh catalysts supported on MxZr1-xO2-d were prepared by the impregnation method for MSR. The effect of nature and quantity of dopant (M = Y, La, Ce) on the catalytic performance bimetallic catalysts was investigated. The activity of Ni-Cu/

YxZrO2-x (x=0.1–0.3) samples increases with increase in yttria concentration due to oxygen vacancy formation. The dependence of the catalytic activity on the ceria concentration was not monotonous. The sample containing 10% of cerium oxide showed the highest activity. The catalyst based on Ru–Rh alloy differed with higher activity and lower selectivity as compared with Ni–Cu samples. The selectivity of the process was not less than 99.5% even at high temperatures for all catalysts. But the improved activity of the catalyst also results in an increase in carbon monoxide formation and the hydrogen selectivity decreases. The optimal characteristics, such as rather high hydrogen yield, good selectivity and stability were shown by the catalyst with

Zr0.9Ce0.1O2-d support.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 102 Biography

Aleksandra Lytkina graduated from Voronezh State University in 2013 and was taken to a position of PhD student in the A.V. Topchiev Institute of Petrochemical Synthesis. She carrying out my research for four years under the guidance of Prof. Andrey Yaroslavtsev and Doc. Natalia Orekhova. Her research is devoted to hydrogen production via methanol steam reforming with the use of membrane catalysis technology. She has 26 publications, including 7 articles in scientific journals and 19 abstracts in the abstract books of Russian and international conferences. Currently she is preparing her thesis for the further defense. γ The Effect of Preparation Method on the Redox Properties of CeO2-promoted Cu/ -Al2O3 Catalysts for Water Gas Shift Reaction

Dae-Woon Jeong Changwon National University, South Korea

Abstract γ The purpose of this study was to investigate the effect of the preparation method on CeO2-promoted Cu/ -Al2O3 catalysts for the high temperature shift reaction using simulated waste-derived syngas (H2 + CO). To investigate the effect of preparation γ γ γ method on the CeO2-promoted Cu/ -Al2O3 catalyst, we compared catalytic performance over Ce/Cu/ -Al2O3, Ce-Cu/ - γ Al2O3, Cu/Ce/Al2O3, and Cu/ -Al2O3 catalysts, and tried to explain the differences in catalytic performance with various characterization methods. The physico-chemical properties of the CeO2-promoted catalysts were characterized using surface spectroscopies such as BET, XRD, TPR, XPS, Raman spectroscopy, photoluminescence spectroscopy, and N2O-chemisorption. The catalyst characterizations were correlated with activity results in the high temperature shift reaction.

Biography

Dae-Woon Jeong was born in Korea, in 1980. He received the B.E. degree in Environmental Engineering from the Yonsei University, Korea in 2007, and his Ph.D. degree in Energy & Environmental Engineering. from the Yonsei University, Korea, in 2013. In 2015, He joined the department of Chemical Engineering and Applied Chemistry, University of Toronto, as postdoctoral fellow. Since March 2016, he has been with the school of civil, environmental, and chemical engineering, Changwon

National University, where he was an assistant professor. His current research interests include waste/biomass to energy, H2 production based on catalytic reaction. He is co-author of about 50 scientific papers on various topics in environmental-friendly energy production.

Palladium Complexes of (C‾, N, E) Pincer and Bidentate (N, E) Ligands (E = S or Se) based on Naphthalene Core in Catalysis of C-C Coupling via In Situ Formed Nanoparticles

Renu Bhaskar* and Ajai K. Singh Indian Institute of Technology Delhi,India.

Abstract The reaction of 1-naphthaldehyde with 2-(phenylthio/seleno)ethylamine gives air and moisture insensitive Schiff base ligands, L1 and L2. These ligandson treatment with NaOAc and Li2PdCl4 give palladacycle[Pd(L1-H/L2-H)Cl] (1/2) at room temperature, in which L1/L2 behaves as an unsymmetric (C‾, N, E = S/Se) pincer. The reduction of >C=N bond ofL1 and L2 with sodium borohydride gives L3 and L4 respectively. The reaction ofL3 /L4 at room temperature similar to those of L1/L2 results in complex [Pd(L3/L4)Cl2] (3 / 4) in which the ligand coordinates in a bidentate (N, E) mode. The 1-4 and L1 were authenticated with single crystal X-ray diffraction. Palladium adopts distorted square planar geometry in all the complexes. The Pd−S bond distances in 1 and 3 are 2.4255(13) and 2.259(3) Å respectively whereas Pd−Se bond lengths (Å) are: 2.5225(13) (2) and 2.3687(10) (4). The catalytic activity of complexes 1-4 was explored for copper and amine free Sonogashira coupling and Suzuki-Miyaura coupling (SMC) of aryl halides under aerobic conditions. The amount of catalyst required for achieving good conversion is 0.01 mol% (SMC) and 0.05 mol% (Sonogashira coupling). The generation of palladium containing nanoparticles (NPs) during both coupling reactions was observed. They were isolated and HR-TEM revealed their size as ~2-7 nm. For Sonogashira coupling formation and role of such Pd based NPs under aerobic conditions are observed for the first time. The catalysts have recycling potential as in eighth cycle conversion drops by 20 %. Palladacycles (1/2) were more efficient than3 and 4.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 103 Biography

Renu Bhaskar born in 1990, in Rajasthan, India. She did her B.Sc from Rajasthan University, Jaipur and M.Sc from Banasthali University. Currently she is pursuing research on “Palladium Catalysts for C–C coupling reactions” for a Ph.D. degree at the Chemistry Department, Indian Institute of Technology Delhi, under the mentorship of Prof. A. K. Singh.

Elucidation of the Catalytic Reduction Mechanism on Noble Metal Nanoparticles

Alina Sermiagin* and Tomer Zidki Ariel University, Israel

Abstract

Nowadays, hydrogenations are widely used reactions in the chemical industry. As these reactions are very important generally, a wide range of industrial catalytic hydrogenations involve an extensive usage of metals, especially in the solid-state catalysis. Many cases have revealed surfaces poisoning, decrease in catalytic activity and more different phenomena which are created during catalytic reactions under extreme conditions. The consequences of these phenomena originate a widespread impact on the environmental pollution.

One way to address the environmental factor is to use nanoparticles (NPs) based catalysts, in order to decrease the amount of metals in the catalytic processes. NPs are known for their high catalytic efficiency in mild conditions and thus are extensively investigated due to some unique properties like their surface to volume ratio.

Catalytic hydrogen evolution is among the hot topics in current scientific world. Thus, we have chosen to study the catalytic water reduction mechanism. We used sodium borohydride as the reducing agent and noble metal NPs catalysts (mostly silver, gold and platinum NPs) for the investigation. The experiments were carried out with sodium borodeuteride (NaBD4) as an isotopic marker and mass spectrometer analysis. We have elucidated, for the first time, the catalytic reduction mechanism of water reduction on noble metals NPs. A major question is whether the reduction proceeds via an H atom transfer, a hydride transfer or an electron transfer will be discussed. The results indicate that the water reduction mechanism is highly dependent on the reducing agent concentration.

Biography

Alina Sermiagin was born in Tashkent, Uzbekistan in 1990. Her family relocated to Israel in 1995. Alina got her B.Sc. in chemistry from the Hebrew university, Israel. She also got an education diploma in science teaching. During her military service, she served as a teacher for 5 years. After her discharge, she started her M.Sc. in chemistry under the supervision of Dr. Tomer Zidki in Ariel University, Israel. Right now Alina is finishing her M.Sc. and is planning to start her PhD.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 104 Palladium(II) Complexes of (Benzoimidazol-2-ylmethyl)Amine Ligands as Catalysts for the Methoxycarbonylation of Olefins

Thandeka A. Tshabalala* and Stephen O. Ojwach University of KwaZulu-Natal, South Africa

Abstract

Methoxycarbonylation of olefins is an important reaction in organic transformation since the resulting esters can be converted to alcohols, acids, and used for the preparation of detergents [1]. Palladium based catalysts have attracted considerable interest in recent years in the methoxycarbonylation reactions [2]. In this contribution, reactions of N-(1H-benzoimidazol-2-ylmethyl)- 2-methoxy aniline (L1) and N-(1H-benzoimidazol-2-ylmethyl)-2-bromo aniline (L2) with [PdClMe(COD)] afforded the neutral palladium complexes, [PdClMe(L1)] (1) and [PdClMe(L2] (2), respectively. Treatment of 1 and 2 with one equivalent of PPh3 in the presence of NaBAr4 (Ar = 3,5-(CF3)2C6H3) produced the corresponding cationic species, [PdMe(L1)]BAr4 (3) and [PdMe(L2)]BAr4 (4). All the palladium complexes formed active catalysts in the methoxycarbonylation of internal and terminal olefins. The effects of reaction conditions such as catalyst structure, acid promoter, nature of the phosphine deriatives and olefin chain length have been investigated and are herein discussed.

References: 1. Olah, G. A and Molnah, A., Hydrocarbon Chemistry, Wiley-Interscience, New York. (1995) 421. 2. Aguirre, P. A., Lagos, C. A., Moya, S. A., Zuniga. C., Vera-Oyarce, C., Sola, E., Peris, G and Bayon, J. C., Dalton Trans, (2007) 5466.

Biography

Thandeka Tshabalala has completed her MSc in 2014 at the age of 24 years from University of KwaZulu-Natal. She is currently pursuing her doctoral degree under the supervision of Assoc Prof Stephen. O. Ojwach at the University of KwaZulu- Natal on the design and development of palladium complexes as catalysts for the methoxycarbonylation of olefins. She has published 2 papers in reputed journal.

Synthesis of C2-Symmetric Diphosphormonoamidites and Their Use as Ligands in Rh-Catalyzed Hydroformylation

Galina Morales Torres1*, Stephan Behrens1, Dirk Michalik1, Detlef Selent1, Anke Spannenberg1, Susan Lühr2, Katrin Marie Dyballa3, Robert Franke3,4 and Armin Börner1 1Leibniz-Institut für Katalyse, an der Universität Rostock e.V., Germany 2Universidad de Santiago de Chile, Chile 3Evonik Performance Materials GmbH, Germany 4Ruhr-Universität Bochum, Germany

Abstract

A series of diphosphoramidites has been synthetized with a piperazine, homopiperazine, and an acyclic 1,2-diamine unit in the backbone. New compounds were tested alongside related N-acyl phosphoramidites as ligands in the Rh-catalyzed hydroformylation of n-octenes to investigate their influence on the activity and regioselectivity. A subsequent study of their hydrolysis stability revealed that the most stable ligands induced the highest activity in the catalytic reaction.

Biography

Galina Morales Torres studied chemistry at the University Oriente, Cuba. After working for a period as a research assistant in the University of Granma, Cuba in 2004 she joined the group of Prof. Dr. Christian Vogel, Rostock, Germany and completed a PhD on the synthesis of carbohydrates in 2007. Between 2007 and 2014 she has worked as research assistant and professor for organic chemistry in the University of Granma. At present she is part of Prof Dr. Armin Börner’s group in the Leibniz-Institute for Catalysis (LIKAT), Germany. Her research focuses on applied homogeneous catalysis and natural products.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 105 Removal Photocatalytic of Different Pesticides in Agro-waste Water at Pilot Plant Scale under Natural Sunlight

José Fenoll1*, Isabel Garrido1, Aliaksandr Kushniarou2, Pilar Flores1, Pilar Hellín1, Nuria Vela3 and Simón Navarro2 1Instituto Murciano de Investigación y Desarrollo Agrario y Alimentario, Spain 2Universidad de Murcia, Spain 3Universidad Católica de Murcia, Spain

Abstract

In recent years there has been growing interest in the use of Advanced Oxidation Processes (AOPs) to remove pesticide residues in water as alternative to methods that are more conventional because they allow the abatement of them by mineralization. Among AOPs, heterogeneous photocatalysis using different semiconductor oxides has been extensively reviewed in the recent literature due to its efficiency in the removal of pollutants at ambient temperatures and pressures, without the formation of harmful by-products. A pilot facility for decontamination of wastewater with residues of pesticides produced in farms by remnants in containers and tanks of plant protection products from treatment equipment has been developed. Natural sunlight and titanium dioxide (TiO2) as photocatalyst in tandem with an oxidant (Na2S2O8) used as electron acceptor has been employed to degrade different pesticide, commonly used on different vegetables and fruit crops in the Region of Murcia (SE of Spain), in these wastewaters. Ultrafiltration membrane has been used to remove TiO2 solid from the water. The reusability of the TiO2 solid has been also evaluated several times. Therefore, the assayed systems (equipment and procedures) were a viable alternative for decontamination of water with residues of pesticides from washing of containers and phytosanitary treatments equipment.

The authors acknowledge financial support received from the EU through the LIFE Program (LIFE 13 ENV/ES/000488). In addition, the authors are grateful to H. Jiménez, I. Garrido, J. Cava and M. V. Molina for technical assistance.

Impact of Hydrophilic Surface Modification of TiO2 on the Photo-catalytic Activity for Methylene Blue and Phenol Oxidation

Byeong Jun Cha1*, Tae Gyun Woo1, Eun Ji Park1, 2, Il Hee Kim1, Jung Eun An1, Hyun Ook Seo3 and Young Dok Kim1 1Sungkyunkwan University, South Korea 2Korea Basic Science Institute, South Korea 3Sangmyung University, South Korea

Abstract

We modified surface of P-25 TiO2 nanoparticles into hydrophilic via thermal deposition of polydimethylsiloxane (PDMS) followed by vacuum annealing at 800oC. This procedure produced a thin layer composed of hydrophilic organic functional groups

(e.g., carbonyl group) as well as SiOx structures on the surface of TiO2. The surface modified TiO2 showed a higher adsorption capacity and photo-catalytic decomposition rate toward methylene blue. However, for the photo-catalytic decomposition of phenol, total mineralization of phenol was more complete when bare TiO2 was used, whereas partial oxidation of phenol was more dominant and total oxidation of phenol was restrained when surface modified TiO2 was used. Overall, one cannot simply conclude that hydrophilic modification of TiO2 leads to a higher affinity to H2O molecules with a higher yield of strong oxidizing agents (OH radicals) to promote the photo-catalysis in aqueous solutions. Our results imply that a balance of the adsorption energy or rates among H2O, reactants, and reaction intermediates can be an important factor for determining the photo-catalytic decomposition rates. Different types of photo-catalyst surface modification can be beneficial or detrimental depending on the reaction. It is highlighted that one should scrutinize and evaluate the overall photo-catalytic decomposition rates of assorted catalysts, as opposed to simply using a few dye-decomposition experiments.

Biography

Byeong Jun Cha is a M.S. candidate at department of chemistry, SungKyunKwan University where his study mainly about photo-catalyst with background of surface physical chemistry. Byeong Jun Cha graduated from the SungKyunKwan University with B.S. degree in chemistry and started master course this year. He has a great interest in surface chemistry of catalysts, kinetics of catalysis, spectroscopy.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 106 Electrocatalytic Activity of Electrodeposited Pd/Ni Alloys: Effect of Composition and Structure

J.Georgieva*, M.Monev and N. Dimitrova Bulgarian Academy of Sciences, Bulgaria

Abstract

Pd-based electrocatalyst are intensively investigated as an alternative to replace platinum as electrodes for low temperature fuel cells (PEMFCs, DMFCs, AMFCs). Various forms of Pd/Ni system, obtained by different techniques (direct melting, galvanic displacement, electrodeposition, sputtering, chemical precipitation, impregnation) were studied as electrodes for hydrogen oxidation and oxygen reduction reactions, electrooxidation of glycerol, methanol, ethanol, formic acid, as well as for other purposes – preparation of switchable mirrors with better optical switching durability, sugar analysis.

The present study describes the effect of the nickel content in electrodeposited Pd/Ni alloy coatings on the rate of hydrogen and oxygen reactions in acidic and alkaline media, respectively. Catalytic activity of the electrodeposited layers towards methanol oxidation was investigated by cyclic voltammetry. The surface morphology and composition of the samples were characterized by Scanning Electron Microscopy (SEM) and energy-dispersive spectrometry (EDS). The crystal structure of the Pd/Ni alloys was examined by X-ray diffraction (XRD). The existence of a concentration range with respect to the Ni content was shown, wherein the electrocatalytic activity of the Pd/Ni alloy is higher than that of pure Pd. It was found that the occurring structural changes in the alloys have also a contribution to the catalytic activity.

Biography

Jenia Georgieva has more than 20 years of experience in materials science and electrochemistry and has been working on photoelectrochemistry for the past 10 years (40 journal publications). She received her MS in Electrochemistry and corrosion from the University of Chemical Technology and Metallurgy, Sofia, Bulgaria in 1993. She then joined the Institute of Physical Chemistry of the Bulgarian Academy of Sciences (BAS) as a Research Associate where she received her PhD in Electrochemistry in 2008 and was appointed Assistant Professor. Since 2010 she has been an Associate Professor in the same Institute. She has participated in 6 Bulgarian or International Research Projects.

An Alternative Method for Preparation of Ir/TiO2 and Ir/TiO2/graphene Composites

Nina Dimitrova1*, J. Georgieva1, S. Sotiropoulos2, E. Valova1 and S. Armyanov1 1Bulgarian Academy of Sciences, Bulgaria 2Aristotle University of Thessaloniki, Greece

Abstract

A facile, alternative method was developed to combine the photocatalytic activity of TiO2 with the electrocatalytic activity of IrO2 towards oxygen evolution. Ir was deposited on the surface of TiO2 powder by UV photodeposition from appropriate Ir salt aqueous solutions. In order to increase the conductivity of TiO2 and its sensitivity towards visible light, the semiconductor was modified with reduced graphene oxide. The resulting Ir-TiO2 and Ir/TiO2/graphene composites have been characterized by transmission electron microscopy (TEM), energy-dispersive spectrometry (EDS) and X- ray photoelectron spectroscopy (XPS). A non-homogeneous Ir particle size distribution was observed, ranging from small, separated and very well dispersed crystallites to aggregates of different sizes. Depending on preparation conditions, both metallic and oxide forms of IrO2 were detected. The electrochemical characterization of the resulting Ir-TiO2 material was carried out by cyclic voltammetry (to identify the surface electrochemistry of the catalyst) and linear sweep voltammetry/photovoltammetry to test oxygen evolution/ water splitting activity.

Biography

Nina Dimitrova is a PhD student in the Institute of Physical Chemistry, BAS, Sofia, Bulgaria, since 2016.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 107 Manganese Oxides – Catalysts for Methylene Blue Removal in the Presence and Absence of H2O2

Borjana Donkova1*, Miroslava Nedylkova1 and Georgi Avdeev 2 1University of Sofia, Bulgaria 2Bulgarian Academy of Science, Bulgaria

Abstract

Many kinds of Mn oxide-based materials have been studied for the degradation of water-soluble commercial colorants and present good wastewater treatment ability. The latter is enhanced by the application of advanced oxidation processes. However, the exact role of manganese oxides (adsorbent, catalyst and/or oxidizer) has seldom been clearly distinguished in the process of contaminant removal.

In the present study, the efficiency of the manganese oxides rods for Methylene blue (MB) removal is investigated. The effect of H2O2 assistance on the mechanism of MB removal and on the activity of the samples is tested also. The mixtures of manganese oxides with different Mn(II):Mn(III):Mn(IV) ratio are obtained by thermal decomposition of manganese oxalate at different annealing temperatures. The phase contents (Mn2O3, Mn3O4, and Mn5O8) and physicochemical characteristics of the products obtained are determined by XRD, SEM, FT-IR, UV-Vis, and nitrogen adsorption. The activity of the samples for MB removal is studied under natural conditions. The results show the dependence of the efficiency and removal mechanism on the chemical composition. The percent of MB removal decreases with decreasing of Mn(IV) content in the sample. The absence of Mn(IV) leads to the bleaching of MB solution by adsorption mechanism, while the presence of Mn(IV) leads to

N-demethylated degradation of the contaminant. In the presence of H2O2, the activity of the samples increases up to twice and the changes in the mechanism of MB removal are established

Acknowledgement: M.Nedyalkova and B.Donkova are gratefully acknowledged for the financial support from the Bulgarian Science Fund (project DCOST-01/18).

Biography

Borjana Donkova works at Department of Inorganic chemistry, Faculty of Chemistry and Pharmacy, University of Sofia “St. Kliment Ohridsky”; Ph. D. in Inorganic Chemistry (University of Sofia). Her research interests includesCrystallization and co- crystallization processes at moderately and sparingly soluble compounds; Thermal decomposition; Catalysis and photocatalysis; Nanoscale materials and composites.

Diffusion with Chemical Reaction in a Single Catalyst Pellet: Cobalt Catalyzed Fischer-Tropsch Synthesis

Dragomir Bukur 1,2*, Milos Mandic1, Branislav Todic1 and Nikola Nikacevic3 1Texas A&M University at Qatar, Qatar 2Texas A&M University, USA 3University of Belgrade, Serbia

Abstract

Fischer-Tropsch synthesis (FTS) is a heterogeneous reaction used to convert synthesis gas into a range of hydrocarbon products. This reaction is a key step in gas-to-liquid (GTL) process in which natural gas is converted into liquid fuels and value-added chemicals. Low temperature FTS is often conducted commercially in multi-tubular fixed bed reactors, where the overall design goal is to maximize productivity and selectivity to desired products (low methane and high selectivity to liquid hydrocarbons) while minimizing pressure drop and costs. These requirements lead to intraparticle diffusional limitations resulting in lower catalyst effectiveness and decrease in selectivity to liquid hydrocarbons.

In this study we investigate effects of particle shape (sphere, slab, solid and hollow cylinder), size (i.e. diffusion length), catalyst distribution (uniform vs. eggshell type distribution for a spherical particle) and process conditions (temperature, pressure, syngas composition and conversion level) on catalyst effectiveness factor and methane selectivity inside a particle using mathematical modeling. Based on an extensive number of simulations we conclude that the use of small spherical particles

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 108 (0.2 – 0.5 mm) or eggshell distribution with a larger spherical particle (dp = 2 mm) with catalyst layer thickness less than approximately 0.13 mm at base case conditions (473 K, 25 bar, H2/CO = 2 and low CO conversion) is needed to avoid negative impact of diffusional limitations on CH4 selectivity for a highly active catalyst.

Biography

Dragomir B. Bukur is a Research Professor at Texas A&M University at Qatar, and Professor Emeritus at Texas A&M University in College Station. His research interests are in catalysis, kinetic modeling and reactor design aspects of coal-to- liquids (CTL) and gas-to-liquids (GTL) processes, H2 production via chemical looping steam methane reforming. He has served as a consultant to several major oil and chemical companies in the USA. He was elected a Fellow of American Institute of Chemical Engineers (2000) for his contributions to chemical engineering profession through research, service and education.

Solar Fuel Production: Opportunities for Nanostructures

Zhigang Zou* and Yingfang Yao Nanjing University, China

Abstract

The photocatalytic and photoelectrochemical reduction of water or CO2 is an intriguing approach to producing sustainable solar fuels, and has attracted growing and intense interest. Nanostructuring of photocatalysts and photoelectrodes has been proven to be a strong strategy to dramatically improve overall solar-to-fuel conversion efficiencies. Another technological barrier for the practical implementation of solar fuel production is long-term material durability, which has recently been well addressed by using conformal coatings of protective layers onto the narrow band-gap semiconductors that are suitable for efficient solar-to-fuel conversions but photoelectrochemically unstable. These significant progresses may lead us to the practical implementation of solar fuel production. We focused on the exciting progresses achieved by using nanostructuring strategies, specifically regarding how the nanostructure influences the charge transport and separation. Special attention was paid to how a nanoscale coating (overlayer) passivates the surface states, thereby reducing the surface electron hole recombination, and how a nanoscale coating (protective layer) prevents the photo-corrosion or photo-passivation of the semiconductors with optimal band gaps. We hope that the design strategies using these nanostructures will offer new and greater opportunities for efficient solar fuel production to existing photocatalytic and photoelectrochemical systems.

Biography

Engaging long-term in the fundamental and application research of energy and environmental materials, Prof. Zou is a member of Chinese Academy of Science, the chief scientist of Chinese “973” project, and the chairman of Chinese National Committee of Photochemistry and Photocatalysis. He has made systematic and original contributions to the academic fields of the new-generation energy and environmental materials, including superconductive, photocatalytic materials, etc. by developing the design theories, critical syntheses, and application fundamentals. He has published over 500 research articles, SCI cited for 20,000 times, with an H index of 69. He achieved over 30 Chinese, 1 US, and 2 Japanese patents. And He also won the International Centre for Diffraction Data Certificate Award twice in 1999 and 2003, the first prize of Jiangsu Science and Technology Award twice, and the second prize of Chinese National Science Award as the first contributor.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 109 A Ru-cyclam Based Electrocatalyst for the Oxygen Reduction Reaction

I. L. Vera-Estrada1*, O. Jiménez-Sandoval1 and J. Uribe-Godínez2 1Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, México 2Centro Nacional de Metrología, México

Abstract

The search for achieving a better performance in proton exchange membrane fuel cells (PEMFC) has heavily relied on the improvement of the catalyst activity. In this regard N4-macrocyclic complexes have had special attention due to their similarity with enzymes and because their catalytic activity can be modified by changing the central atom as well as the peripheral ligand. This work presents the synthesis, structural characterization (FT-IR, micro-Raman, EDS, 1H-NMR and mass spectrometry) and electrocatalytic activity for the oxygen reduction reaction (ORR) of a Ru-cyclam (1,4,8,11-tetraazacyclotetradecane) complex, evaluated by the rotating disk electrode (RDE) technique.

This compound, in contrast with most of the complexes with 4N -macrocyclic ligands (phthalocyanines, porphyrins, etc.) studied to date for the ORR, has a much smaller and simpler (in terms of chemical bonds) macrocyclic structure; moreover, it does not have to be thermally treated (as other known complexes do) to function as an efficient ORR catalyst, even in the presence of methanol. Such properties render this complex a potential candidate to be evaluated as a lower cost cathode in hydrogen and methanol PEM fuel cells.

Biography

Lucía Vera-Estrada is a graduate student at Cinvestav (Center for Research and Advanced Studies of the National Polytechnic Institute, Mexico). She has worked with several kinds of electrocatalysts for the reactions taking place in PEM fuel cells, including mono- and bi-metallic carbonyl complexes and metal compounds with macrocyclic ligands, using hydrogen as well as organic fuels.

Novel N5-Macrocyclic Complexes as Methanol Resistant Electrocatalysts for Oxygen Reduction

I. L. Vera-Estrada1*, O. Jiménez-Sandoval1 and J. Uribe-Godínez2 1Unidad Querétaro. México 2Centro Nacional de Metrología, México

Abstract

Proton exchange membrane fuel cells (PEMFC) are a versatile source of alternative energy, however, the search for an adequate and affordable catalyst to perform the reactions taking place in them is still a challenge. A group of catalysts known as N4-macrocyclic complexes, especially those of Fe and Co, has been widely investigated. The catalytic activity of these compounds for the oxygen reduction reaction (ORR) is favored by the presence of nitrogen; nevertheless, most of them need a heat treatment to improve their activity and stability.

This work presents two novel catalysts based on N5-macrocyclic ligands (Figure 1). These compounds were structurally characterized by FT-IR, micro-Raman, EDS, 1H-NMR and mass spectrometry; their electrocatalytic activity for the ORR in an acid medium was evaluated by the rotating disk electrode (RDE) technique.

These compounds were synthesized from 2,6-diacetylpyridine and triethylentetramine. A first N5-macrocyclic ligand was obtained (Pydiene-N5, Fig. 1a) as its Mn(II) complex and was used as a precursor for a second N5-macrocycle (Pyane-N5, Fig. 1b), by reducing the two imino bonds. The catalysts were obtained by direct reaction of each of these ligands with a ruthenium and a rhodium salt, respectively, and neither of them received any further heat treatment.

These materials exhibit a good behavior as electrocatalysts for the ORR, even in the presence of methanol, thus being interesting novel candidates to be evaluated as cathodes in PEMFC.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 110 a b ) )

Figure 1. (a) Pydiene-N5 (b) Pyane-N5

Biography

Lucía Vera-Estrada is a graduate student at Cinvestav (Center for Research and Advanced Studies of the National Polytechnic Institute, Mexico). She has worked with several kinds of electrocatalysts for the reactions taking place in PEM fuel cells, including mono- and bi-metallic carbonyl complexes and metal compounds with macrocyclic ligands, using hydrogen as well as organic fuels.

Biodiesel Production Using Cr Deposited on Animal-bone Photocatalyst and Solar Radiation as Energy Source

María Griselda Corro Hernández1*, Nallely Sánchez1, Umapada Pal1 and José Luis García Fierro2 1Benemérita Universidad Autónoma de Puebla, México 2Instituto de Catálisis y Petroleoquímica, Spain

Abstract

The production of biodiesel from waste frying oil (WFO) by a two-step process was investigated. In the first step, the free fatty acids (FFAs) present in the oil were esterified with methanol by a photocatalytic process using Cr/Animal-bone (cow-bone) and solar irradiation as light source. The catalytic performances of Cr/Animal-bone calcined at different temperatures (500- 1000°C) were investigated in FFAs photo-esterification process. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), and nitrogen physisorption. Characterization results revealed the presence of Cr6+ in the samples calcined at temperatures between 500-600°C. However, a mixture of Cr6+ and Cr3+ was detected in the samples calcined at higher temperatures (700-1000°C). The catalysts calcined between 700- 1000°C showed a very high activity for FFAs photo-esterificaton. A mechanism is proposed to explain this high photoactivity, 6+ 3+ + . assuming a synergetic electronic interaction between Cr and Cr during photo-irradiation, which generates H , CH3O and R-COOH. radicals in high concentration at the photocatalyst surface.

The second step consisted in the triglycerides transesterification with methanol through thermal activation using solar irradiation as heating source and catalyzed by NaOH. Produced biodiesel by this process, fulfills all the international requirements for its utilization as a fuel.

Biography

Grisel Corrowas born in Puebla, a sunny city in Mexico, in front of Popocatepetl, a big volcano always showing its presence. Grisel obtained a PhD in Poitiers, France in Physical Sciences. Grisel research deals with Catalysis for pollution abatement and for renewable energy generation. Popocatepetl has influenced me catalytically in my research choice.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 111 γ Hydrothermal Stability Improvement on Pt/Ni/ -Al2O3 Catalysts for Aqueous Phase Reforming of Glycerol/water Mixture

M.El Doukkali1,2, A.Iriondo2, J.F.Cambra2 and P.L.Arias2 1University of Sultan Moulay Slimane, Morocco 2University of the Basque Country(UPV/EHU), Spain

Abstract

The 2H massive utilization as an energy vector makes necessary to develop its production from clean and renewable sources with low costs. There are different reforming processes of biomass-derived by-products, among them the catalytic aqueous-phase reforming (APR) established, in 2002 by Dumesic and their collaborators, that shows potential advantages γ over conventional reforming process of these derived. Recently stable hydrothermal catalyst of Pt/Ni–based -Al2O3 has been developed in ours Moroccan and Spanish laboratories with a good catalytic performance for H2 production by aqueous phase reforming of glycerol/water mixture. These developments based on the study of the catalysts properties, their influence in the catalytic activity and selectivity, as well as the deactivation mechanisms, was having allowed improving its catalytic performance in term of hydrothermal stability in APR process of glycerol and its H2 productivity. These works have led to set new strategies γ related to the hydrothermal stability enhancement and to the reduction of the deactivation causes of Pt/Ni– based -Al2O3 catalysts, lengthening even more its lifecycle in the APR reaction of glycerol.

Biography

Mohamed El Doukkali received his PhD in Chemical Engineering & Materials Sciences from the University of the Basque Country (Spain, 2012), during which, he also benefited of mobility for the Lille-IUniversity (France). He was Post- doc researcher at the Higher Technical School of Engineering (Spain,2013). Dr. El Doukkali currently works as Full Professor at the University of Soultan Moulay Slimane (Morocco), where he is teaching Catalysis/Kinetic, Thermodynamic, and Physicochemical of Surfaces/interfaces. He is, also, member of several research projects dealing with the development of sustainable materials and technologies for biomass valorization, and publishing various papers in international Journals with high-impact.

Thermal Analysis of Polyvinylpyrrolidone Assisted NiO Nanoparticle Reduction Process

Jaeho Shin1*, Daeho Lee2 and Seung Hwan Ko1 1Seoul National University, South Korea 2Gachon University, South Korea

Abstract

Reductive sintering process is one of promising candidates for the fabrication of flexible electronic circuits. Especially, compared to the sintering process of metal nanoparticles, in situ reduction and sintering of metal oxide nanoparticles enables far simple fabrication process because oxidation prevention of nanoparticles is not required. The microscopic mechanism of the reductive sintering process however, has not yet been elucidated, and only speculation has been suggested that thermal decomposition of the solvent or other additives of the nanoparticle ink may be involved. In this study, TG-DTA analysis of NiO nanoparticle ink was conducted. As a result, it was experimentally confirmed that thermal decomposition of polyvinylpyrrolidone (PVP) which is originally added for dispersion into the nanoparticle ink plays an important role in reduction of NiO nanoparticle.

Biography

Shin is in his doctoral course of Mechanical Engineering in Seoul National University, Korea. He received his BS in Physics from Seoul National University in 2010. After graduation, he joined Samsung Electronics Company, and conducted research on solar cells and organic light emitting diodes. In 2015, he joined the Applied Nano and Thermal Science Laboratory. His research interests focus on laser processing of various materials. He is currently working on flexible electronics fabrication through laser digital pattering and silicone laser machining.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 112 Comparative Study of Ni-Mg-Al ,Ni-Co-Mg-Al and Ni-Ce-Mg-Al Catalysts Obtained via Hydrotalcites for the Dry Reforming of Methane

Ali Zaz1,2*, V.M.Gonzalez-delaCruz3,D Halliche1, J. P.Holgado3, A.Caballero3, K.Bachari4, A.Saadi1, S.Tezkratt2 and O.Cherifi1 1USTHB, Algerie 2UMMTO, Algerie 3University of Seville, Spain 4Centre de Recherches Scientifiques (CRAPC), Algeria

Abstract

Production of the synthesis gas and the hydrogen represents one stakes major in the chemical industry in the world. Synthetic Mg–Al layered double hydroxide materials have found many applications due to their unique physicochemical properties. We Are Interested in the Methane Dry Reforming Reaction for Its Positive Effect on the Environment: it consumes both CO2 and CH4 greenhouse gases. The Catalysts materials Ni-Mg-Al, Ni-Co-Mg-Al and Ni-Ce-Mg-Al were synthetized by classical method of co-precipitation at basic PH. We investigated the effect of the method of preparing the nickel catalyst by hydrotalcites way and the effect promoter of cobalt and cerium on nickel catalyst, for the dry reforming of methane reaction. A number of technical physicochemical characterized the catalysts: XRD, ICP, TPR, BET and SEM.

The diffraction X-ray analysis showed HDL structure for all the catalysts before calcination. The catalytic tests on CH4 / CO reaction showed a good conversion of methane and Carbon dioxide and good stability of catalysts. The addition of cobalt or cerium improves the conversion of methane and carbon dioxide. Biography

Ali Zazi is a teacher and researcher in the Department of Chemistry of the Faculty of Sciences at the University Mouloud Mammeri of Tizi Ouzou (UMMTO) and Researcher in (Laboratoire de chimie du gaz naturel) at chemistry faculty of the University of Science and Technology Houari Boumedienne(USTHB) Algeria.

Hydrodynamic Characteristics and Heat Transfer at the Layer Inversion Point in Three-Phase Fluidized Beds with Binary Solid

Dong Hyun Lee Sungkyunkwan University, South Korea Abstract

Layer inversion in gas-liquid-solid fluidized beds with binary solids was examined in a semi-acrylic column of 1.8 m ρ height and 0.21 m inner diameter. Binary solid combinations were composed of polymer beads (PB, dp = 3.3 mm, s = 1,280 3 ρ 3 kg/m ) and glass beads (GB, dp = 0.385 mm, s = 2,500 kg/m ). Various volumetric ratios (PB:GB = 0.67:0.33, 0.6:0.4, 0.5:0.5,

0.4:0.6, 0.33:0.67) were used to examine superficial liquid velocities, Ul = 21.6 - 34.2 mm/s, and superficial gas velocities, Ug = 0 - 16.6 mm/s. Previous studies using a single mixing ratio found that the injection of gas into a liquid-fluidized bed decreased the superficial liquid velocity required for layer inversion. Bubble size, bed height, and superficial liquid velocity at the layer inversion point vary with the binary composition. Upon gas introduction into a liquid-solid fluidization column, the superficial liquid layer-inversion velocity increases if it occurs when there is initial bed contraction. On the other hand, the liquid layer inversion velocity decreases when there is initial bed expansion behavior. For all binary solid combinations showing initial bed expansion, liquid layer-inversion velocity decreases with increasing superficial gas velocity in three-phase fluidization, consistent with the gas-perturbed liquid model. Biography

Dong Hyun Lee received his undergraduate degree in chemical engineering in 1984 from Sungkyunkwan University. He received his Ph.D. from the KAIST in 1994. Prof. Lee was a senior research fellow at Hanwha Chemical R&D Center from 1986 to 1998. He was a postdoctoral fellow at University of British Columbia from 1999 to 2000. In 2002, he joined Sungkyunkwan University as an assistant professor. He was promoted to Full Professor in 2012. In 2017, Prof. Lee accepted the position of department head in Sungkyunkwan University. He is the author of more than 125 refereed publications, has more than 20 issued patents.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 113 Selective Production of 2,5-dimethylfuran From Sugars in a Continuous Flow Process, using Solid- Acid and Nickel-based Catalysts

Marius Bäumel*, Max Braun, Valerio Molinari and Markus Antonietti Max Planck Institute of Colloids and Interfaces, Germany

The extensive environmental and social impact of crude oil exploitation is a hot topic in science and society, raising interest in sustainable alternatives. In this spirit, the present work focuses on the catalytic conversion of carbohydrates originating from non-edible biomass as a regenerative source for the production of 2,5-dimethylfuran (DMF), a new generation biofuel of superior quality [1] and also a suitable platform molecule for the production of fine chemicals.

As catalytic advancements in industry are usually not achieved with catalyst powders, we developed supported Ni-based catalysts, in order to facilitate catalyst packing in flow reactors. For the prepa- ration of porous nitrogen-doped carbon (NDC) catalyst supports we employed unconventional but intuitive methods: Using an industrial pasta machine, precursor doughs are extruded in stable pasta shapes. In order to subtly tune the hierarchical porosity and the nitrogen content of the final car- bonic catalyst support, the contents of semolina (carbon precursor) and several templating agents in the dough are altered. This approach comprises well-established techniques s.a. hard-templating.

A main challenge of the kinetic engineering is to prevent the undesired reaction of the intermediate

5-hydroxymethylfurfural (HMF) towards the side product levulinic acid, which easily occurs in the acidic medium [2]. Therefore, it is paramount to instantaneously hydrogenate HMF to DMF. For this, a bicatalytic reactor is implemented, containing a mixture of a commercial sulfonated, highly cross linked polystyrene-divinylbenzene for the acidic dehydration of the fructose ring to HMF and the prepared Ni@NDC catalyst for the subsequent hydrogenation to DMF. This setup facilitates the conversion of sugar solutions in the liter sc with both high conversion and DMF selectivity.

References: 1. Y. Román-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic Nature 2007, 447, 82-985 2. M. Braun, M. Antonietti Green Chem., 2017, 19, 3813-3819

Biography

Marius Bäumel graduated in Chemical Engineering in 2016 at Karlsruhe Institute of Technology, Germany. In the same year, he began his current PhD studies at the Max Planck Institute of Colloids and Interfaces in Potsdam under the supervision of Markus Antonietti, focusing his research on the development of porous heterogeneous catalysts and reactor systems for biorefinery applications.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 114 Use of Agricultural Hybrid Bead for Treatment of Heavy Metal Ion from Aqueous Solution

Hee-Jeong Choi Catholic Kwandong University, South Korea

Abstract

The aim of this study was to investigate heavy metal removal using agricultural hybrid bead, corncob powder and chitosan, in an aqueous solution. Hybrid bead, which are biomaterials, have a large number of hydroxyl groups and are highly suitable for removal of heavy metals. Therefore, in this study, we investigated the possibility of removal of Pb(II), and Cd(II) in aqueous solution by using hybrid bead. The pseudo-second order model was a better fit to the heavy metal adsorption experiments using hybrid bead than the pseudo-first order model. The adsorption of Pb(II) and Cd(II) by hybrid bead was more suitable with the Langmuir isothermal adsorption and showed an ion exchange reaction which occurred in the uneven adsorption surface layer. The maximum adsorption capacity of Pb(II) and Cd(II) was determined to be 1.345 mmol/L and 0.782 mmol/L, respectively. In the thermodynamic experiment, ΔGo and ΔHo were a negative value, and ΔSo were positive values. It can be seen that the heavy metal adsorption process using hybrid bead was spontaneous in nature and was an exothermic process. This experiment, in which heavy metals are removed using the hybrid bead, is an eco-friendly new bio-adsorbent method because it can remove heavy metals without using chemicals while utilizing waste recycling.

Biography

Hee-Jeong Choi has received her PhD. at Technical University Berlin, Germany, on studies with biological wastewater treatment. After PhD. she returned to Korea and started hers research department of Health and Environment in Catholic Kwandong University, Korea. Nowadays, she hasexpanded research area as biochemistry, biotechnology of microalgae, and biological wastewater treatment. She has joined to increasing of research quality with Germany (Frauenhofer Institute and Technical University Berlin), India (Mizoram University) and China (Harbin University). Prof. Dr. Hee-Jong Choi has more than 100 publications and supervised dozens of students mostly on aspects related to biological wastewater treatment and biotechnology of microalgae.

Synergistically Strengthened Alginate/Silica Hybrid Aerogel Beads with Tunable Functional Surface for Removal Lead Ion from Water

Wei Wei1*, Zhifeng Jiang1,2 and Jimin Xie1 1Jiangsu University, China 2The Chinese University of Hong Kong, China

Abstract

To achieve high removal efficiency of lead ion pollutants and overcome recycling difficulty of aerogel powders, alginate/ silica hybrid aerogel beads with tunable functional surface were successfully prepared by the orifice-coagulation bath with ambient pressure drying method. The morphologies, porosity characteristics, and ion absorbencies of the aerogel beads were systematically investigated. The obtained aerogel beads are milky light spherical solid with large specific surface area (125.2 ~ 157.2 m2/g), low density (0.171 ~ 0.177 m2/g) and highly degree of sphericity. Results showed that obtained samples has good adsorption effect on Pb2+, the aerogel beads modified with silane coupling agent DB-590 have the experimental maximum adsorption capacity of Pb2 + 193.73 mg·g-1. These aerogel beads may be used as versatile sorbents for ion pollutants removal due to tunable functional surface.

Biography

Wei Wei is currently a Postdoctoral Fellow in the group of Prof. Jimin Xie in School of Chemistry and Chemical Engineering of Jiangsu University. He received his Ph.D. degree (environmental science) from Jiangsu University, China. His research interest focuses on design of hybrid aerogel composites for water remediation and evaluation the adsorption/catalysis mechanisms using surface science study.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 115 Carbon Nitride Modified with CdS-TiO2 Nanodots as 2D/0D Hybrid Material with High Hydrogen Evolution Efficiency

Zhifeng Jiang1,2*, Huaming Li,1 Shouqi Yuan1 and Po Keung Wong2 1Jiangsu University, China 2The Chinese University of Hong Kong, P.R. China

Abstract

Photocatalytic H2 evolution from water splitting requires an efficient photocatalyst with excellent charge separation ability and broad visible-light adsorption region. The as-synthesized ternary composite of CdS-TiO2@g-C3N4 exhibits enhanced visible-light-driven photocatalytic H2 evolution activity, as compared to the binary composites and their single components, which is about 6.7 and 11.2 times higher than those of single CdS and g-C3N4, respectively. Moreover, the as-obtained ternary composite has external quantum efficiency (EQE) of 11.9% at 420 nm, implying the high utilization efficiency of photo- induced charges. In addition, the superior photostability can be achieved by this coupling method. The enhanced photocatalytic activity was attributed to the efficient charge separation originated from the three-level electron transfer system, the matched energy level positions, the abundant adsorption sites and active sites (0D/2D structure) and the synergistic effect among CdS,

TiO2 and g-C3N4.

Biography

Zhifeng Jiang is currently a“Hong Kong Scholar” Postdoctoral Fellow in the group of Prof. Po Keung Wong in School of Life Sciences of The Chinese University of Hong Kong. He received his Ph.D. degree (environmental science) from Jiangsu University, China. His research interest focuses on design of semiconductor/biohybrid catalysts for energy production and evaluation the reaction mechanisms using surface science study.

Photocatalytic CO2 reduction by Mg(OH)2/CuO Composite for CH3OH and HCOH Production

E. Luévano-Hipólito*, L. M. Torres-Martínez, D. Sánchez-Martínez and M. R. Alfaro Cruz Universidad Autónoma de Nuevo León, México

Abstract

Cu2O and CuO oxides have been applied as photocatalyst for H2 generation. The oxides were prepared by soft chemistry methods such as sonochemical and microwaves at low temperature (80°C). In particular, Cu2O oxide was prepared using different amounts of glucose (C6H12O6) as reducing agent. Glucose was choosing as reductant since its abundance in nature, 0 non-toxicity, and low cost. Higher loads of glucose during the preparation of Cu2O promoted the formation of Cu , which had an important role in the photocatalytic activity for H2 generation. Microwave method provided adequate physical and chemical properties to CuO and Cu2O to carry out an efficient H2 generation from water splitting, such as low and homogeneous particle size and a convenient potential of their conduction and valence band. The highest H2 generation using Cu2O under the aforementioned experimental conditions was 26 μmol g-1h-1. Additionally, glucose was added to the photocatalytic reactor to -1 -1 act as hole scavenger, and improve the charge separation in Cu2O, promoting a higher H2 production (133 μmol g h ). From -7 these data, it was possible to calculate the values of reaction rate and adsorption constant; k=8.7x10 mol/min and Kd=2.8/M.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 116 Effect of Ni on MCM-41 in the Adsorption of Nitrogen and Sulfur Compounds to Obtain Ultra-Low Sulfur Diesel

J. C.García-Martínez1*, H. A. González Uribe1, M. M.González-Brambila1, J. A. Colín-Luna1, N. G. Flores del Río2. A, Lopez-Gaona1 and L. Alvarado-Perea2 1Universidad Autónoma Metropolitana Azcapotzalco, México 2Universidad Autónoma de Zacatecas, Mexico

Abstract

In recent years, worldwide legislation on sulfur content of diesel fuel has become more stringent. Nitrogen content in diesel feedstocks to obtain fuel is very important because inhibit the active sites of the catalyst for the hydrodesulfurization reaction [1]. The production of ultra-low sulfur diesel (ULSD) (< 10 ppmw of sulfur) is motivated by the need for using new emission- control technologies of sulfur (EURO VI norm). In particular, basic nitrogen compounds like quinoline (Q), can be adsorbed strongly on the acidic sites of various catalysts used in the petroleum-refining processes, poisoning the active sites [1]. Adsorptive desulfuration and denitrogenation are methods that can be applied to obtain an ULSD previous to the hydrodesulfurization reaction. Materials that are being used are activated carbons [2], SBA-15 with nickel [3] and MCM-41 [4]. Thus, in this work the adsorption of Q and dibenzothiophene compounds using MCM-41 and Ni-MCM-41 as adsorbents was studied.

Adsorption experiments were performed in jacketed glass containers maintaining an atmospheric pressure at 313 K in batch mode (Adsorptive denitrogenation and desulfurization of model nitrogen and sulfur containing compounds in dodecane as solvent). The concentration of nitrogen and sulfur was set in the interval from 0 to 250 ppmw and always in the same ratio in each experiment. In each experiment, the mixture was stirred vigorously (400 rpm) until its complete homogenization. Simultaneously, 0.2 g of adsorbent was added and samples were collected periodically. Ni containing MCM-41 was effective to remove N and S compounds.

References: 1. García-Martínez J. C., Castillo-Araiza C. O., De los Reyes Heredia J. A., Trejo E., Montesinos A., Chemical Engineering J. 210 (2012) 53. 2. M. Almarri, X. Ma, C. Song, Energy Fuel 23 (2009) 3940. 3. S. Shariar, X. Han, H. Lin, Y. Zheng, Int. J. Chem. React. Eng. 14 (4) (2016) 823. 4. W. Li, Q. Liu, J. Xing, H. Gao, X. Xiong, Y. Li, X. Li, H. Liu, AIChE J. 53 (12) (2007) 3263.

Size Control of Pt, Pd and Ag Nanoparticles by Controlling the Surfactant Content

Park Dong Kook and LeeMan Sig Korea Institute of Industrial Technology, South Korea

Abstract

Researches on application to electronic devices, chemical sensors, biosensors and catalysts using metal nanoparticles have been actively carried out. In the case of fabricating a device using metal nanoparticles, it is possible to fabricate a device with high efficiency, which was difficult to realize with a bulk device made of conventional technology. In addition, metal nanoparticles can be used as catalysts for Suzuki, Heck and Sonogashira reactions and hydrogenation reaction of olefine in a considerably small amount because surface atoms have high activity and large surface area ratio. Since these properties are highly dependent on the size and distribution of nanoparticles, studies on methods and properties for efficiently producing metal nanoparticles having a uniform size should be preceded.

To date, much research has been done on the synthesis of silver, platinum and palladium nanoparticles. Generally, the method of synthesizing metal nanoparticles is well known such as sputter deposition, hydrogen reduction, thermal decomposition, electrodeposition, and liquid phase reduction. The liquid phase reduction method is advantageous in that the size and shape of the metal particles can be easily controlled because the metal ion is bottom-up method in which the metal ions are grown as metal particles by using a reducing solution. However, the size distribution of the metal nanoparticles synthesized by the liquid reduction method is wide. A method of synthesizing nanoparticles using a surfactant (surface stabilizer) is known in order to reduce the size of the metal nanoparticles and to stabilize the surface.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 117 In this study, to control the size of silver, platinum and palladium nanoparticles, nanoparticles were synthesized by varying the concentration of surfactant. The size and size distribution of synthesized nanoparticles were measured by TEM analysis. Therefore, we will present quantitative criteria for the use of surfactants to control the size of silver, platinum and palladium nanoparticles.

Biography

Dong Kook Park received his PhD from the Inorganic Chemistry group of Kookmin University (The South Korea) in 2016. His PhD research focused on the carbon capture catalyst research for carbon capture and storage. He currently works as a scientist at Korea Institute of Industrial Technology in Ulsan, South Korea.

Surface Modified LAP/BN Composites with PPS Matrix for High Mechanical and Thermal Conductive Laser Direct Structuring Applicable Composite Material

Kiho Kim*, Dabin Park and Jooheon Kim Chung-Ang University, South Korea

Abstract

The super engineering plastic (SEP) polyphenylene sulfide (PPS) based composite with laser-activated particle (LAP)/ boron nitride (BN) was fabricated via melt-mixing. The LAP and BN surfaces were modified using sodium hydroxide and silane coupling agents. The LAP and BN dramatically deteriorate the mechanical properties of PPS because of its low compatibility with the polymer. However, surface modification, especially via amino silane treatment, effectively prevented the degradation of mechanical properties upon adding fillers. Moreover, thermal conductivity also notably enhanced after particle surface modification due to the air voids between particle/matrix interfaces were removed which act as a heat insulating layer. Finally, thermally and mechanically enhanced LAP/BN/PPS composites were patterned via laser irradiation and formed a metal circuit via electroless plating for 3-D moulded interconnects device application.

Biography

Kiho Kim is doctoral student of Chung-Ang University, Department of chemical engineering & materials science in Seoul, Korea. Kiho Kim graduated from Chung-Ang University. He received a Master degree in Chemical Engineering.

The Impact of Hydrophilic Surface Modification TiO2 on its Photocatalytic Activity Towards Toluene Total Oxidation

Tae Gyun Woo*, Byeong Jun Cha and Young Dok Kim Sungkyunkwan University, South Korea

Abstract

The photocatalytic degradation of toluene by spin-casted TiO2 on SUS plate under UV light irradiation was studied with on-line gas chromatography equipped with flame ionization detector and a batch type reactor. We investigate poisoning of the catalyst surface as well as the reaction products during the photocatalytic reactions qualitatively and quantitatively. We compared behaviors of bare and hydrophilic TiO2 as photocatalysts. The hydrophilic modification of the surface of commercially available TiO2 powder (P25, Degussa) was achieved by coating thin film of PDMS (polydimethylsiloxane) on the surface of

TiO2 followed by vacuum annealing. The surface of bare TiO2 was easily poisoned by intermediates of photocatalytic toluene oxidation reaction, and the reaction intermediates responsible for the poisoning of photocatalysts are suggested to be most likely benzaldehyde or benzoic acid. The only reaction product of photocatalytic oxidation of toluene using bare TiO2 detected by GC was CO2. The presence of water molecule in the atmosphere facilitated regeneration of photocatalytic activity through more efficient combustion of the remaining reaction intermediates on the surface of bare TiO2. Using hydrophilic TiO2, we could find two different reaction paths, making CO2 and a second reaction product as a result of partial oxidation of toluene detectable using GC. Interestingly, the reaction path responsible for the production of a second reaction product (acetamide) did not show significant deactivation behavior with time. The origin of the deactivation-free behavior of the hydrophilic TiO2 regarding the second reaction path will be discussed more in detail.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 118 Biography

Tae Gyun Woograduated from Sungkyunkwan University with B.S. degree and started the master course this year at the same place. Tae Gyun Woo major physical chemistry and specifically, He is interested in unveiling mechanism of photocatalytic reactions together with enhancing photocatalytic activity by surface structure modification of photocatalyst.

Catalytic Reductions and Tandem Reactions of Nitro Compounds Using In Situ Prepared Nickel Boride Catalyst in Nanocellulose Solution

Kaniraj Jeya Prathap* and Peter Dinér KTH-Royal Institute of Technology, Sweden

Abstract

With the emergence and development of nanotechnology, nanocellulose attracts more attention as cheap, renewable, and biodegradable materials. The most developed approach has been to use nanocellulose as support for metal nanoparticles (NPs) and, for instance, hybrids materials made of cellulose supported silver, gold, cadmium, iron, and nickel nanoparticles [1]. However, the production of nickel-based nanoparticles supported on nanocellulose has been morescarce. Here we wish to present a mild, highly efficient, and practical chemical protocol for the reduction of nitro groups into amines using nanocellulose-supported nickel boride (Ni2B-NCF) using only water as a solvent and NaBH4 as mild reducing agent [2] (see scheme below).

The protocol is able to reduce a large number of nitro compounds at room temperature with low catalyst loading (0.25 α mol% of NiCl2) in high isolated yields. Similarly, we have developed a tandem reaction methodology to prepare a -amino alcohol by mixing of an epoxide and nitrobenzene in water under the developed reduction condition.

References: 1. Kaushik, M, Moores, A, Green Chem. 2016, 18, 622-637 2. Prathap, K. J, Qiong, W, Richard T. O, Peter D, Org. Lett., 2017, 19 , 4746-474.

Biography

Jeya Prathap Kaniraj is a Wenner-Gren fellow at KTH and working on nickel-based catalysts on nanocellulose. During his Ph. D. studies, he worked on enantioselective synthesis using different transition metal catalyst at the Central Salt & Marine Chemicals Research Institute (CSMCRI, India). He has also a post-doctoral experience from the TECHNION-Israel Institute of Technology in the group of Prof. Galiya Maayan.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 119 A Novel Synthetic Method for Mixed Monosilyl Acetals and Catalyst-Dependent Chemoselective Mukaiyama Aldol Reactions

Hye Sung Yang1* and Sun Min Kim1, Heesung Eum2, Hyun-Joon Ha2 and Jung Woon Yang1 1Sungkyunkwan University, South Korea 2Hankuk University of Foreign Studies, South Korea

Abstract

In general, acetals are used as protecting group for aldehydes, ketones or diols. In addition, O,O-Mixed acetals are well known as synthetic equivalents of aldehydes or esters and are widely used in diverse synthetic organic reactions, such as the Mukaiyama aldol, Diels-Alder, and radical cyclization reactions. So we develop a highly selective, direct, and simple synthetic method for the synthesis of monosilyl acetals from aldehydes. In particular, we success chemoselective Mukaiyama aldol reactions with mixed monosilyl acetals, relying on the discriminative activation of the alkoxy group on the acetal by different oxophilic catalyst. Furthermore, this study provided the existence of an oxonium ion intermediate and of its kinetically controlled reaction with the pre-equilibrated silyl enol ether obtained from (E)- and (Z)- isomerization.

O t OTMS NaO Bu, TMS-N3 + NaN3 R H benzene, RT, 1h R OtBu

Mixed monosilyl acetal

Chemoselective Mukaiyama aldol reaction

t OTMS OTMS O Bu O . Cu OTf TMSO O BF3 OEt2 + ( )2 t u e R O R O B OM HO O R O P PhO OPh

Biography

Hye Sung Yang graduated undergraduate school in Sungkyunkwan University. Presently studying combined master’s and doctorate program from 2014. Hye published with a topic of enantio-selective organocatalytic cyclopropanation in the Journal of Organic Chemistry and the experimental results of abstract is published at Chemistry A European Journal; also the paper is selected as frontispiece.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 120 Active Catalysts for Biodiesel Production: A Review

Videsha Bansal* and Mohd. Shahnawaz Khan JK Lakshmipat University, India

Abstract

The most promising fuel for vehicles after petroleum and diesel is biodiesel. Biodiesel being an excellent alternative for diesel is in demand nowadays. Various approaches have been done on its preparation. Different oils and alcohols (MeOH/ EtOH) are used to increase the yield of resultant biodiesel. But the major role in the production of biodiesel is of the catalyst used during the trans-esterification reaction. These catalysts only enhance the yield and quality of the product. This catalyst can be either homogeneous or heterogeneous in nature. Different studies are done on catalyst and its effect on the final product biodiesel. This review basically focuses on the types of catalyst used in the production of biodiesel and identify their various effects and catalytic activities to enhance the purity and yields of the final product i.e. Biodiesel.

Biography

Videsha Bansal is a student perusing Bachelor of Technology in Chemical Engineering (IInd year), JK Lakshmipat University, India.Dr. Mohd. Shahnawaz Khan is a professor in Department of Chemistry, JK Lakshmipat University, India. He did his Ph.D in Synthetic Organic & Medicinal Chemistry from St. John’s College, India.

Characteristics of Nitrogen Oxides Emission from Passenger Car using SCR or LNT on NEDC and WLTC

Jinyoung Jang*, Youngmin Woo, Ahyun Ko, Yongjin Jung, Oh Seuk Kwon and Young Jae Lee Korea Institute of Energy Research, South Korea

Abstract

Because of Volfswagen gate, diesel passenger cars need to meet the new and strengthened EURO-6 regulations. Until then, NEDC (New European Driving Cycle) was used to regulate emissions, but now it is regulated by WLTC (Worldwide harmonized Light vehicle Test Cycles) and RDE (Real Driving Emissions). Prior to the introduction of new test methods, diesel passenger cars meet regulations using the DPF-LNT after treatment system.

In this study, three different diesel passenger cars was used to compare the emission levels of nitrogen oxides including N2O. Two different vehicles have a DPF-LNT aftertreatment system and another vehicle has a DPF-SCR after treatment system. A chassis dynamometer was used to conduct the test according to the NEDC and WLTC. All the test vehicles met the NOx regulation of EURO-6 in NEDC mode. However, one of DPF-LNT vehicle did not meet the NOx regulation of EURO-6 in

WLTC. Since N2O has about 300 times the greenhouse effect of CO2, it should be reduced. All the test vehicles were emitting around 20 mg/km of N2O emissions.

(This research was supported by the CEFV(Center for Environmentally Friendly Vehicle) as Global-Top Project of KMOE(Ministry of Environment, South Korea)).

Biography

Jinyoung Jang is currently working as aprincipal research at KIER (Korea Institute ofEnergy Research) and his research fieldincludes combustion in the internal combustionengines and vehicles, especially withnew and renewable fuels to mitigate climatechanges and draw out both better energy efficiency and emissions.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 121 Expansion the Temperature Window of Catalytic Action via “Lattice Tuning” of Ceria

Gulyaev Roman1,2, Kardash Tatyana2, Slavinskaya Elena2, Malykhin Sergey2 and Alexandra Ivanova2 1NIOST LLC, Russia 2Boreskov Institute of catalysis, Russia

Abstract

The interaction of palladium and ceria with formation of ionic palladium species is considered to be a main reason of high activity of Pd/CeO2 catalysts in CO and methane oxidation at low-temperatures [1-3]. The formation of the solid solution PdxCe1-xO2-x-δ 2+ in Pd/CeO2 catalysts have been proposed in literature, and the near-square-planar local environment of Pd ion in ceria lattice 2+ was established experimentally in our work [4]. The bulk Pd ions, serving as a dopants, increase the O2- ions non-stoichiometry in parent ceria phase and decrease the size of ceria particles which results in thermostability enhancement [5].

Nickel which is analog of palladium is able to similar interaction with a ceria lattice with formation of the bulk NixCe1- 2+ xO2-x-δ solid solutions. The same near-square-planar environment of Ni in ceria was demonstrated using resonance Raman spectroscopy. Ni2+ incorporation in ceria lattice leads to it contraction in contrast with it expansion while Pd2+ is incorporated in ceria. We have shown that tuning of lattice period of ceria is possible via variation of Pd2+/Ni2+ ratio which results in substantial enhancement of the stability of such doped ceria to sintering. Obtained (PdNi)xCe1-xO2-x-δ catalyst show unique wide window of catalytic action: high activity at below-ambient temperatures (for CO) and below 300oC (for methane) and stability up to 900oC.

References: 1. M. S. Hegde et. al, Catalysis Today, 2015, 253, 40-50. 2. S. Colussi et. al, Angewandte Chemie International Edition, 2009, 48, 8481-8484. 3. P. Senftle et. al, ACS Catalysis, 2015, 5, 6187-6199. 4. R.V. Gulyaev, et.al, PCCP, 2014, 16, 13523-13539. 5. E.M. Slavinskaya, et.al, Applied Catalysis B: Environmental 166–167 (2015) 91–103.

Ag- GO- TiO2 Composite as Electrode Material for Photocatalysis and Photoelectrochemical System

Chabaiporn Junin2*, Attera Worrayingyong2, Chanchana Thnachayanont1 and Chanapa Kongmak2 1National Metal and Materials Technology Center (MTEC), National Science and Technology Development Agency (NSTDA), Pathumthani, 12120, Thailand 2Department of Materials Science, Faculty of Science, Kasetsart University, Thailand

Abstract

Ternary catalyst composite consisting of Ag nanoparticle, graphite oxide (GO) and titanium dioxide (TiO2) was synthesized to improve efficiency of powder materials for photocatalysis application and used as working electrode for a photoelectrochemical system. Ag nanoparticle was prepared by photoreduction and the graphite oxide was synthesized by the modified Hummer’s method in green synthesis. The weight percentages of Ag to TiO2 were 0.5 and 5% and of GO to TiO2 were 5 and 15%wt. Photocatalytic activity of the prepared composite was evaluated using Rhodamine B degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were tested and the photocatalytic performance was enhanced by photoelectrochemical system. X-ray diffraction (XRD), scanning electron microscope (SEM-EDX), transmission electron microscope (TEM) and Raman spectroscopy were used to confirm the crystal structure, morphology of the composite component. XRD, TEM and Raman results revealed that the composite composed of graphite oxide like a flake structure having diffraction pattern in plane (002), (101) and (110). SEM- EDX in backscattering mode showed Ag nanoparticle which was consistent with the TEM result. The photocatalytic activity test in rhodamine B degradation showed that 5%Ag15%GOTiO2 composite performed the highest photocatalytic activity (70.2%), which was chosen for fabricating as thin film electrode for photoelectrochemical system.

Biography

Chabaiporn Junin has worked as a research assistant at National Metal and Materials Technology Center since2006.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 122 Her experience related to synthesis and characterization of nanomaterials for many applications such as photocatalyst, solar cell, thermoelectric materials. She is now studying doctoral program in nanomaterials science, Kasetsart University. The research topic is “Photo-electrochemical catalysis of chemical waste destruction by graphene-based TiO2 and Ce- doped TiO2 electrodes”.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 123 About United Scientific Group

United Scientific Group (USG), an expert-driven initiative led by the editors association and the advisory board which includes academicians, researchers, and industry leaders across various fields of research. USG provides broad range of services in the fields of science and technology including publishing, conducting world class scientific events, and holding highly interactive and proficient world forums.

USG Editors Association

Founding President Founding Vice-President

Kenneth Blum, PhD, DHL Sayon Roy, PhD, FARVO University of Florida, USA Boston University, USA

The scientific industry involved in networking, organizing meetings and publishing scholarly journals is increasing constantly in order to meet the ever changing demands of emerging new concepts and subjects in different fields of science. Rigorous, meticulous policies and guidelines are essential to maintain the highest standards of scientific excellence. USG is fortunate to have the United Scientific Group Editors Association (USGEA) that serves this role. USGEA is an association of United Scientific Group Journals editors with diverse backgrounds and professional experience, who seek to foster cooperation and communication among editors, improve editorial standards, promotes the concept of self-criticism, self-regulation in scholarly publishing, and encourage research on the editorial principles and practices of publishing.

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 124 Founding Members

Ahmad Salehi, MD, PhD Rajendra Badgaiyan, MD Stanford Medical School Wright State University USA USA

Jin Jun Luo, MD, PhD Dawei Li, PhD Mun Yhung Jung, PhD Temple University Shanghai Jiao Tong Woosuk University USA University, China South Korea

Reza Hakkak, PhD University of Arkansas for Medical Sciences, USA

Catalysis and Chemical Engineering (CCE-2018) | Feb 19-21, 2018 | Paris, France 125 Scientific UNITED Group

# 8105, Rasor Blvd - Suite #112, PLANO, TX 75024, USA Ph: +1-408-426-4832, +1-408-426-4833 Toll Free: +1-844-395-4102; Fax: +1-408-426-4869 Email: [email protected] Web: www.unitedscientificgroup.com/conferences/catalysis