Dean‘s Letter
Welcome to the Qatar Fertilizer Company – Texas A&M at Qatar Conference 2014.
On behalf of Texas A&M at Qatar, I am honored to host this seventh annual conference, and the sixth presented in collaboration with Qatar Fertilizer Company (QAFCO). This event is a perfect illustration of the essential importance of industry and academic partnerships in the role of development and in creating scientific solutions that directly impact the world around us.
This year’s focus, nanotechnology and energy, is fundamental to the further evolution of enhanced energy efficiency and the development of new technologies that can be applied across diverse branches of industry and leveragable conventional and renewable energy sources. The topic is vital to scientific advances in the energy and engineering sectors, and will come to play an ever more decisive role in the use – and conservation – of energy.
QAFCO has been a steadfast and dynamic partner to the University in these collaborations and I thank QAFCO for its unwavering belief in the strength of the University’s academic and research programs, faculty, students and its graduates.
Thank you for sharing your expertise with the professionals participating in this influential gathering of industry practitioners and scholars.
Best wishes for a very productive conference and thank you to QAFCO for their partnership in this influential meeting of international experts.
Best regards,
Dr. Mark H. Weichold Dean and CEO, Texas A&M University at Qatar
Nanotechnology and Energy 1 Chair and Co-Chairman‘s Letter
On behalf of the Science and Chemical Engineering programs at Texas A&M University at Qatar, we are pleased to welcome you to the annual QAFCO-Texas A&M at Qatar Conference 2014.
We are very proud of our partnership with QAFCO which has generously supported us in hosting a successful series of chemistry conferences for five years (2008 - 2013). This series attracted an impressive list of world renowned scientists over the years (52 invited speakers from 12 countries). The speakers list included two Nobel Laureates, Dr. Robert H. Grubbs and Dr. Ei-Chi Negishi. We are thankful to QAFCO for agreeing to expand the scope of the conference to include chemistry and chemical engineering and to support the event for the coming five years. This is a clear indication of their unwavering support of higher education and research activities in Qatar. This goes in parallel with the unprecedented industrial and economic development that the country has been witnessing in the last ten years.
We are glad to have Dr. Paul Alivisatos, Director of the Lawrence Berkeley National Laboratory, as keynote speaker of the 2014 edition of the conference, in addition to our invited speakers.
We hope this conference will be an outlet for the exchange of scientific knowledge, sharing ideas, and for discussing future collaborations. Your presence at this conference affirms our pursuits of cutting-edge chemistry and chemical engineering research in Qatar and the region.
Best regards,
Hassan S. Bazzi Chair, QAFCO - Texas A&M at Qatar Conference 2014 Chair, Science Program Ioannis Economou Co-Chair, QAFCO - Texas A&M at Qatar Conference 2014 Professor, Chemical Engineering Program
2 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 3 Schedule of Events time CHEMISTRY (LH 144)
Session II (Chair: Dr. Dave Seapy) Time Activity 8 a.m. Registration Open and Light Breakfast Dr. Tobin J. Marks 9 a.m. Welcome Session 10:30 – 11 a.m. Northwestern University, USA “Interface Science of Organic Photovoltaics” 9:10 a.m. Session I Dr. Spiros H. Anastasiadis 10:10 a.m. Coffee Break University of Crete, Greece 11 – 11:30 a.m. 10:30 a.m. Session II “Structure and Dynamics in Polymer/Layered-Silicate Nanocomposites” 12 p.m. Lunch Dr. F. Dean Toste 1:30 p.m. Session III University of California, Berkeley, USA 11:30 a.m. – 12 p.m. 3 p.m. Coffee Break “The Power of Catalysis: Homogeneous, Heterogeneous and In Between” 3:30 p.m. Session IV Session III (Chair: Dr. Ashfaq Bengali)
Dr. Hong-Cai Zhou Scientific Program 1:30 – 2 p.m. Texas A&M University, College Station, USA “Metal-Organic Frameworks through Cavity Design” Dr. Edward Hartley Sargent time Welcome Session University of Toronto, Canada 2 – 2:30 p.m. Dr. Hassan S. Bazzi, “The Application of Nanostructured Materials in 9 a.m. Chair, Science Program, Texas A&M University at Qatar Energy Conversion, Light Detection, and Biosensing” Dr. Mark H. Weichold, 9:05 a.m. Dean & CEO, Texas A&M University at Qatar Session IV (Chair: Dr. Ed. Brothers) Mr. Khalifa Al-Sowaidi, 9:10 a.m. Vice Chairman & CEO, Qatar Fertiliser Company Dr. Abdelkrim Chemseddine Institute for Solar Fuels, Germany Session I (Chair: Dr. Hassan S. Bazzi) LH 238 3 – 3:30 p.m. “Bottom-Up Approaches Using New Real Building Keynote Speaker Units and the Processing of Nanostructured Energy Materials” Dr. Paul Alivisatos Director, Lawrence Berkeley National Laboratory 9:10 – 10:10 a.m. Professor, Department of Chemistry, Dr. Fadwa El Mellouhi Science Program, Texas A&M University at Qatar University of California, Berkeley, USA 3:30 – 4 p.m. “Multi-Component Nanocrystals for Solar Energy and “Nano-Particulated Photochemical Water Splitting Catalysis Applications” Investigated with Electronic Structure Calculations”
4 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 5 CHEMICAL ENGINEERING (LH 143) Session II (Chair: Dr. Ioannis G. Economou) Dr. Doros N.Theodorou 10:30 – 11 a.m. National Technical University of Athens, Greece “Multiscale Modeling of Nanostructured Materials” Dr. Andreas Froba Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany 11 – 11:30 a.m. “Simultaneous Determination of Mutual and Thermal Diffusivity in Liquids with Dissolved Gases by Dynamic Light Scattering (DLS)” Dr. Peter Curran Stair Northwestern University, USA 11:30 a.m. – 12 p.m. “Synthesis of New Catalytic Systems by Atomic Layer Deposition” Session III (Chair: Dr. Marcelo Castier) Dr. Athanasios G. Konstandopoulos Aristotle University, Greece 1:30 – 2 p.m. “Aerosol Based Nanotechnology for Sustainable Mobility and Energy Production” Dr. Sharon Glotzer University of Michigan, USA 2 – 2:30 p.m. “Design Principles for Colloidal Crystals from Nanoparticles” Dr. J. Ilja Siepmann University of Minnesota, Minneapolis, USA 2:30 – 3 p.m. “Molecular-Level Insights for the Design of Extraction and Sorption Processes: Separation of Ethanol and Other Oxygenates from Aqueous Solutions” Session IV (Chair: Dr. Konstantinos Kakosimos) Dr. Vasilis Gregoriou National Hellenic Research Foundation, Greece 3:30 – 4 p.m. “New Dithienogermole-Based Conjugated Polymers for High Performance Organic Photovoltaics” Dr. Hae-Kwon Jeong Texas A&M University, College Station, USA 4 – 4:30 p.m. “High Performance Metal-Organic Framework Membranes for Energy-Efficient Olefin/Paraffin Separations”
6 QAFCO – Texas A&M at Qatar Conference 2014 Biography Multi-Component Nanocrystals for Solar Dr. Paul Alivisatos is director of the Lawrence Berkeley National Laboratory (Berkeley Energy and Catalysis Applications Lab) and is the University of California (UC) Berkeley’s Samsung Distinguished Professor of Nanoscience and Nanotechnology. He also directs the Kavli Energy Nanosciences Institute (ENSI), and holds professorships in UC Berkeley’s departments of materials science and chemistry. In addition, he is a founder of two prominent nanotechnology companies, Nanosys and Quantum Dot Corp, now a part of Invitrogen. Keynote Speaker Groundbreaking contributions to the fundamental physical chemistry of nanocrystals are the hallmarks of Dr. Alivisatos’s distinguished career. His research breakthroughs Dr. A. Paul Alivisatos include the synthesis of size- and shape-controlled nanoscrystals, and forefront studies of nanocrystal properties, including optical, electrical, structural and thermodynamic. In his Director, Lawrence Berkeley National Laboratory research, he has demonstrated key applications of nanocrystals in biological imaging and Professor, Department of Chemistry, renewable energy. He played a critical role in the establishment of the Molecular Foundry, University of California, Berkeley, CA 94720-1460, USA a U.S. Department of Energy’s Nanoscale Science Research Center; and was the facility’s founding director. Dr. Alivisatos has been recognized for his accomplishments, with awards such as the Linus Pauling Medal, the Ernest Orlando Lawrence Award, the Eni Italgas Prize for Energy Abstract and Environment, the Rank Prize for Optoelectronics, the Wilson Prize, the Coblentz Award for Advances in Molecular Spectroscopy, the American Chemical Society Award for Today it is possible to design complex solar cells with 30% power efficiency. In the Colloid and Surface Science, the Von Hippel Award of the Materials Research Society, the nanocrystals with multiple components second, a new type of inorganic nanocrystal Wolf Prize in Chemistry, the 2012 Niki Award, awarded by Athens Information Technology, that act together towards a particular micelle structure is designed to perform and most recently, the 2014 ACS Materials Chemistry Award. He is a member of the function. Two examples will be described multi-electron catalytic transformations. National Academy of Sciences and the American Academy of Arts and Sciences. here. In the first, nanocrystals are used Dr. Alivisatos received a Bachelor’s degree in Chemistry in 1981 from the University of in a luminescent solar concentrator, with Chicago and Ph.D. in Chemistry from UC Berkeley in 1986. He began his career with UC the goal of providing a low cost route to Berkeley in 1988 and with Berkeley Lab in 1991.
8 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 9 Interface Science of Organic Photovoltaics Structure and Dynamics in Polymer/ Layered-Silicate Nanocomposites
Tobin J. Marks Spiros H. Anastasiadis Institute of Electronic Structure and Laser, Foundation for Research Department of Chemistry, Materials Research Center, and Technology-Hellas, Crete, Greece Argonne-Northwestern Solar Research Center Department of Chemistry, University of Crete, Crete, Greece Northwestern University, Evanston IL, USA
Abstract Abstract
The ability to fabricate molecularly 1. Controlling charge transport across Polymer/layered silicate nanocomposites Severe confinement influences significantly tailored interfaces with nanoscale precision hard matter (electrode)-soft matter are of particular interest among different the structure of the polymer: the PEO chains offers means to selectively modulate interfaces in organic photovoltaic cells. nanohybrids because of their anticipated intercalated within the inorganic galleries charge transport, molecular assembly, 2. Controlling charge transport by superior properties. Mixing polymers as well as those in close proximity to the and exciton dynamics at hard matter-soft specific active layer orientational with layered inorganic materials can outside walls are purely amorphous; it is matter and soft-soft matter interfaces. organization at electrodes. lead to three different types of structure, only when there is large amount of excess Such interfaces can facilitate transport 3. Controlling exciton dynamics and depending on the specific interactions polymer outside the completely filled of the “correct charges” while blocking carrier generation at donor-acceptor between the constituents: phase separated, galleries that the bulk polymer crystallinity transport of the “incorrect charges” at interfaces in the active layer. intercalated and exfoliated. Intercalated is abruptly recovered. The dynamics of the the electrode-active layer interfaces of 4. Designing transparent conducting hybrids are also model systems for the polymers confined within the galleries is organic photovoltaic cells. This interfacial electrodes with improved properties. study of the static and dynamic properties probed by quasi-elastic neutron scattering tailoring can also suppress carrier-trapping It will be seen that such rational of macromolecules in nano-confinement. and dielectric spectroscopy. The very local defect densities at interfaces and stabilize interface engineering along with We describe our recent efforts to dynamics of the confined chains show them with respect to physical/thermal improved bulk-heterojunction polymer elucidate the effects of severe confinement similarities with those in bulk, whereas decohesion. For soft matter-soft matter structures guided by theoretical/ utilizing hydrophilic nanohybrids of PEO or the segmental dynamics, probed at interfaces, interfacial tailoring can also computational analysis affords solar hyperbranched polymers mixed with temperatures above the bulk Tg , depend facilitate exciton scission and photocurrent power conversion efficiencies greater Na+-MMT. Intercalated hybrids with mono-, very strongly on the polymer/inorganic generation in such cells. In this lecture, than 9% along with far greater cell bi- and tri-layers of chains are obtained interactions varying from much faster to challenges and opportunities in organic durability. for all compositions covering the complete much slower or even frozen dynamics as the photovoltaic interface science are range from pure polymer to pure clay. strength of the interactions increases. illustrated for four specific and interrelated areas of research: Acknowledgments
This work has been performed in collaboration with K. Chrissopoulou, S. Fotiadou, S. Bollas, K. Andrikopoulos, G. A. Voyiatzis, I. Tanis, K. Karatasos, B. Frick, K. Androulaki, M. Labardi, D. Prevosto. This research has been co-financed by the European Union (European Social Fund – ESF) and Greek national funds (Program: THALES - Investing in knowledge society through the European Social Fund, MIS 377278).
10 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 11 The Power of Catalysis: Homogeneous, Metal-Organic Frameworks Through Heterogeneous and In Between Cavity Design
F. Dean Toste Hong-Cai Zhou, Jian-Rong Li, Daqiang Yuan, Dawei Feng, Weigang Lu, and Tian-Fu Liu Department of Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley National Department of Chemistry, Texas A&M University Laboratory, Berkeley, CA, USA College Station, TX, USA
Abstract Abstract
The past decade has witnessed reactions catalyzed by cationic transition Metal-Organic Frameworks (MOFs) “bridging angle” of a ligand determines the remarkable development in the use of metal complexes. For example, cationic have attracted worldwide research efforts geometry of the cavity.3 I will demonstrate cationic gold(I) complexes as homogenous phosphinegold(I) complexes encapsulated by because of their fascinating structures that bridging-lig and substitution reaction catalysts for the transformation of carbon- an anionic Ga4L6 tetrahedral demonstrated and intriguing potential applications in can be generally applied in both MOP and carbon π-bonds.1 Several years ago, we higher turnover numbers, rate acceleration4 clean energy, especially in gas storage MOF preparation.4 From there, I’ll show demonstrated that the reactivity of and/or produced different products5 and carbon capture.1 Synthetically, a that single cavities can be assembled into these complexes could be controlled by compared to the unencapsulated catalysts. one-pot reaction between a metal salt chains5 and 2D or 3D networks of cavities modification of the counter anion to these More recently, we found that cationic and an organic linker has dominated either by step-wise assembly6 or ligand 2 7 cationic transition metal complexes. The catalysts encapulated in Ga4L6 tetrahedral the field. This approach appears simple design and extension. These synthetic use of these ionic interactions to control supramolecular clusters were well-tolerated but the reactions happened during the methods have lead to novel MOFs such as selectivity of cationic species has generally by the enzymes and in some cases show procedure are complicated. To study the “single-molecule traps”8 and “elastic single- relied on small molecular anions.3 As improved reactivity and selectivity relative mechanism of MOF assembly and to molecule traps”9 for carbon capture. MOFs an extension of this concept, we have to the free cationic guest.6 Ultimately, we gain more control in MOF synthesis, we with unusual stability will also be presented. been exploring the use of supramolecular envision that these concepts can be applied to launched a cavity-by-cavity approach.2 In At the end, a biomimetic MOF built assemblies as the anionic component in the design of integrated catalyst networks.7 this presentation, I will start with a single from 1D cavities (channels) that exhibits cavity (the enclosure of a Metal-Organic enzymatic functions will be discussed.10 Polyhedron or MOP), and show that the References
1. D. J. Gorin, F. D. Toste, Nature 2007, 446, 395-403. 2. G. A. Hamilton, E. J. Kang, M. M. Blázquez, F. D. Toste, Science 2007, 317, 496-499. 3. R. J. Phipps, G. L. Hamilton, F. D. Toste, Nature Chem. 2012, 4, 603-614. 4. Z. J. Wang, C. J. Brown, R. G. Bergman, K. N. Raymond, F. D. Toste, J. Am. Chem. Soc. 2011, 133, 7358-7360. 5. W. M. Hart-Cooper, K. N. Clary, F. D. Toste, R. G. Bergman, K. N. Raymond, J. Am. Chem. Soc. 2012, 134, 17873-17876. 6. Z. J. Wang, K. N. Clary, R. G. Bergman, K. N. Raymond, F. D. Toste, Nature Chem. 2013, 5, 100-103. 7. P. Anbarasan, Z. C. Baer, S. Sreekumar, E. Gross, J. B. Binder, H. W. Blanch, D. G. Clark, F. D. Toste, Nature 2012, 491, 235-239.
12 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 13 The Application of Nanostructured Materials in Energy Conversion, Light Detection and Biosensing
Edward Hartley Sargent University of Toronto, Department of Electrical and Computer Engineering, Toronto, Canada
Abstract
The chemical synthesis and physical understanding of nanostructured materials such as colloidal quantum dots has improved vastly in the past two decades. This has created the opportunity for materials scientists and device physicists to build engineered solid-state materials that Fig. 1 A MOF constructed from three types of cavities. leverage the low cost, size-tunability and tunable morphology of this powerful class of materials. Keywords: I will discuss advances in creating ultrasensitive light detectors based on MOF; porosity; carbon capture; biomimetic catalysis; gas storage. colloidal quantum dots; and on achieving efficient energy harvesting via photovoltaic conversion of the sun’s broad spectrum References: into electrical power with the aid of size- tuned tandem solar cells. I will also discuss 1. Zhou, H.-C., Long, J.; Yaghi, O. Chem. Rev. 2012, 112, 673. the application of bottom-up-grown, top- 2. Zhao, D.; Timmons, D. J.; Yuan, D. Q.; Zhou, H. C. Accounts Chem. Res. 2010, 44, 123. down-templated, nanostructured materials 3. Li, J.-R.; Yakovenko, A.; Lu, W.; Timmons, D. J.; Zhuang, W.; Yuan, D.; Zhou, H.-C. J. Am. Chem. Soc. 2010, 132, 17599. in biomolecular detection for infectious 4. Li, J.-R.; Zhou, H.-C. Nature Chem. 2010, 2, 893. disease and cancer diagnosis. 5. Liu, T.-F.; Chen, Y.-P.; Yakovenko, A. A.; Zhou, H.-C. J. Am. Chem. Soc. 2012, 134 (42), 17358. 6. Li, J.-R.; Timmons, D. J.; Zhou, H.-C. J. Am. Chem. Soc. 2009, 131, 6368. 7. Yuan, D.; Zhao, D.; Sun, D.; Zhou, H.-C. Angew. Chem. Int. Ed. 2010, 49, 5357. 8. Li, J.-R.; Yu, J.; Lu, W.; Sculley, J.; Balbuena, P. B.; Zhou, H.-C. Nature Commun. 2013, 4, 1538. 9. Wriedt, M.; Sculley, J.; Yakovenko, A.; Ma, Y.; Halder, G.; Balbuena, P.; Zhou, H.-C. Angew. Chem. Int. Ed. 2012,51, 9804. 10. Feng, D.; Gu, Z.-Y.; Li, J.-R.; Jiang, H.-L.; Wei, Z.; Zhou, H.-C. Angew. Chem. Int. Ed. 2012, 51, 10307.
14 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 15 Bottom-Up Approaches Using New Real Nano-Particulated Photochemical Water Building Units and the Processing Splitting Investigated with Electronic of Nanostructured Energy Materials Structure Calculations
M. Albornoz1, Fadwa El Mellouhi2, G. Ramos-Sanchez1 Abdelkrim Chemseddine O. Bouhali2, P. B. Balbuena1 1 Chemical Engineering Dept., Texas A&M University, Institute for Solar Fuels (E-IF), Helmholtz-Zentrum Berlin für College Station Texas, USA. Materialien und Energie, Berlin, Germany 2 Physics Department, Texas A&M University at Qatar, Texas A&M Engineering Building, Education City, Doha, Qatar
Abstract Abstract
This talk will address two approaches properties relevant to applications in Solar-driven hydrogen generation the stability against degradation and to control the growth and formation of the area of energy, photocatalysis and has been recognized as a green and dissolution. In this work, we will present nanostructured oxide films. The first is environment. The second approach is promising way to produce clean energy the electronic properties of nanowires based on the concept of generating a key based on controlling thermally activated and solve the fossil fuel shortage problems. coated with organic molecules focusing cluster as intermediate building unit to growth of nanostructures on substrates. The conversion of sun energy into a the conservation of the photochemical be used as a single source to grow oxides Photoluminescence spectroscopy shows the usable carrier is possible by using nano- water splitting properties and possible nanocrystals, nanostructured films or advantage of both methods in overcoming particulated photochemical water splitting charge transfer. We will show that nanopowders. Due to their atomic packing the formation of defects and therefore the systems. We present electronic structure functionalization of the Zn3P2 nanowires and their propensity to condense and self- recombination of photo-excited carriers. investigation of the properties of promising with organic molecules not only improve assemble into the desired bulk oxide, these These approaches will be shown in the case nanowires whose electronic band structure stability but can serve as a way to transfer soluble clusters are called real building of titania, titanates, zinc oxide tungsten is appropriate for water splitting with electrons to a transition metal site where units (RBU). This wet chemistry allows oxide and in more complex oxide such as visible sunlight. Due to the nanowires poor catalysis of the hydrogen evolution reaction the processing of highly homogeneous BiVO4. Applications of these materials in stability, functionalization using organic could be done more easily. and transparent films, free of pinholes water photosplitting, solar cells and in self- molecules has been proposed to enhance and cracks and with physicochemical cleaning windows will be shown.
+0.1000 +0.1900 +0.2800 +0.3700 +0.4600 +0.5500 +0.6400 +0.7300 +0.8200 +0.9100 TiO Ti2O10(TAA)2H10 WO W3O6(OH)6(H2O)3 +1.0000
16 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 17 Multiscale Modeling of Nanostructured Materials
Doros N.Theodorou
School of Chemical Engineering, National Technical University of Athens, Athens, Greece
Abstract
Nanostructured materials play an Theory-inspired Monte Carlo simulations. increasingly important role in solving Each level of representation invokes problems related to health, energy, parameters that can be extracted from telecommunications, and the protection the previous (more detailed) level, such of the environment. Computer modeling that all calculations are ultimately based can relate the properties of such materials on an atomistic force field. We will explore to their chemical constitution and thereby how the segmental dynamics and glass support efficient and cost-effective design. transition temperature of the polymer are The extremely broad spectra of length affected by the presence of nanoparticles and time scales governing structure and and how conformations in the corona of molecular motion in nanostructured grafted chains change with chain length materials pose a great challenge for and grafting density. predictive modeling, however. Only The second example concerns transport hierarchical approaches operating at many of aromatic hydrocarbons in the nanopores interconnected levels, from the atomic to of zeolites, a problem important in the macroscopic, can meet this challenge. industrial separations and shape-selective We will discuss two examples of catalysis. Here we invoke umbrella hierarchical modeling and computer sampling to compute the free energy of simulation of nanostructured materials. a sorbate molecule as a function of its The first example concerns the structure center of mass position along the pores. and dynamics of nanocomposites consisting Infrequent event analysis based on the free of nanoparticles of spherical shape, either energy profiles yields rate constants for bare or carrying surface-grafted polymer jumps executed by the molecule between chains, dispersed within amorphous sorption sites in the zeolite crystal. From polymer matrices. The modeling strategy the network of sites and the transition rate encompasses atomistic molecular dynamics, constants between them, the diffusivity is coarse-grained Monte Carlo, and Field obtained via a new analytical approach.
18 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 19 Simultaneous Determination of Mutual and Synthesis Of New Catalytic Systems Thermal Diffusivity in Liquids with Dissolved By Atomic Layer Deposition Gases by Dynamic Light Scattering (DLS)
Andreas Heller,1 Thomas M. Koller,1 Michael H. Rausch,1,2 and Andreas P. Fröba 1,2 Peter Curran Stair 1 Erlangen Graduate School in Advanced Optical Technologies (SAOT), Department of Chemistry, Northwestern University, Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany Evanston, IL USA 2 Institute of Engineering Thermodynamics, Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany
Abstract Abstract
At present, increasing technical interest flow contributions. Atomic Layer Deposition (ALD) has synthesis of supported metal nanoparticles in liquids containing dissolved gases can be The present contribution demonstrates enormous potential for the synthesis of and developed a procedure in which the found in energy technology. For example, that Dynamic Light Scattering (DLS) can advanced heterogeneous catalysts with metal and support materials are grown ionic liquids (ILs) are potential solvents be applied for a reliable simultaneous control of composition and structure at the sequentially in each ALD cycle. This method for the separation of carbon dioxide from determination of mutual and thermal atomic scale. The ability of ALD to produce makes possible the synthesis of exceptionally flue gas due to their attractive properties. diffusivity of liquids containing dissolved conformal oxide coatings on porous, small particles, ca. 0.5 nm. Using additional Furthermore, the synthesis of hydrocarbons gases. The determination of both properties high-surface area materials can provide ALD support layers at the conclusion of the from hydrogen and carbon monoxide by by DLS is based on the temporal analysis of completely new types of catalyst supports. growth, a process we call overcoating, the the Fischer-Tropsch process is used for the microscopic fluctuations of concentration At the same time ALD can achieve highly metal particles can be stabilized against production of high-value fuels. The mutual and temperature present in a fluid mixture uniform catalytically active metal and sintering and leaching while still remaining diffusivity in corresponding mixtures in macroscopic thermodynamic equilibrium. oxide phases with (sub-) nanometer active under harsh conditions in both gas strongly affects the selectivity and kinetics, Measurement results are presented for dimensions. This lecture will provide and liquid phase reactions. Through proper e.g., in separation processes or catalytic mixtures of 1 alkyl-3-methylimidazolium- examples from our laboratory of ALD used annealing procedures the overcoating oxide reactions. Until now, however, hardly any based ILs having the anions to synthesize oxide supports, catalytic develops porosity, thus ALD becomes a binary diffusion coefficients can be found tetracyanoborate and tricyanomethanide oxide overlayers, metal nanoparticles, and method for introducing and controlling pore for mixtures of ILs with carbon dioxide as with carbon dioxide as well as of different new porous structures. These materials structures. Finally, with templated ALD it is well as liquid hydrocarbons with hydrogen liquid n-alkanes with carbon monoxide or have been characterized by SEM, XRF, ICP, possible to prepare surface cavities, which and/or carbon monoxide. This is caused hydrogen over a wide range of temperature UV-Vis absorption spectroscopy, Raman we call nanobowls. These structures exhibit by the limitations of available measuring and pressure or composition. Here, special spectroscopy and evaluated for catalysis size selectivity, where large molecules are methods. The Taylor dispersion technique attention is paid to the separation of signals of oxidative and non-oxidative alkane excluded from interacting with the catalyst can only be applied at low viscosities. For from concentration and temperature dehydrogenation, selective photo-oxidation, material. the Loschmidt-cell technique, the slow fluctuations, which match under certain and combustion. We have focused on the diffusion processes in liquid systems conditions. Results for the mutual diffusivity generally cause extensive measuring times. agree well with experimental data from Other methods based on the analysis of conventional techniques and data derived time-dependent absorption of gases in from molecular dynamics (MD) simulations. liquids are often affected by additional
20 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 21 Aerosol Based Nanotechnology for Sustainable Mobility and Energy Production
Athanasios G. Konstandopoulos Aerosol & Particle Technology Laboratory, CERTH/CPERI, Greece Department of Chemical Engineering, Aristotle University, Thessaloniki, Greece
Abstract
We review our progress in the area of to reduce nitrogen oxides (NOx). We show Sustainable Mobility and Energy Production how ABN can address these challenges that has been enabled exploiting advances and demonstrate a multifunctional reactor in Aerosol Based Nanotechnology for Diesel Emission Control that exhibits (ABN), including nanoparticle synthesis, significantly better performance with deposition and characterization. Highly respect to state of the art. An important compact, multifunctional ceramic reactors spin-off activity from this research is are developed initially for applications the concept of a functionalized solar in Automotive Emission Control and thermochemical reactor for the production the technology is further extended of Carbon-Neutral Fuels. These solar fuels
and cross-fertilized in the area of Solar can be synthesized from hydrogen (H2) Thermochemical Reactors for the and carbon monoxide (CO) produced by production of Carbon-Neutral Fuels using solar thermochemical water (H2O) and
exclusively renewable/recyclable raw carbon dioxide (CO2) splitting respectively,
materials. opening the door to the treatment of CO2 Catalytically coated ceramic as a raw material, rather than as a waste monolithic reactors such as wall-flow to be disposed. In this way not only an
Diesel Particulate Filters (DPFs) are the alternative to CO2 underground storage is most complex component of today’s offered but also a solution to the problem
emission control systems as they need of storing and transporting H2 is obtained. to incorporate different and often Eventually the advent of solar conflicting functionalities such as high Carbon-Neutral Fuels along with efficient soot nanoparticle filtration efficiency, low Multifunctional Reactors for emission pressure drop behavior, direct catalytic soot control will make possible the transition oxidation activity, high oxidation activity for to a sustainable and clean future with carbon monoxide, (CO) hydrocarbons (HC) only minimal changes in the existing fuel and nitrogen oxide (NO), as well as ability infrastructure and automotive technology.
22 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 23 Design Principles for Colloidal Molecular-level Insights for the Design Crystals from Nanoparticles of Extraction and Sorption Processes: Separation of Ethanol and Other Oxygenates from Aqueous Solutions
J. Ilja Siepmann, Peng Bai, Samuel L. Keasler, Deeksha Jain, Jeffrey Sharon C. Glotzer Sung, and Mansi Shah University of Michigan, Department of Chemical Engineering, Ann Arbor, MI, USA University of Minnesota, Department of Chemistry and Chemical Theory Center, Minneapolis, USA
Abstract Abstract
Ordered assemblies formed structures, entropy stands apart as Efficient Monte Carlo algorithms and of hydrogen-bonded aggregates and spontaneously from colloidal building a statistical “force” that can drive accurate force fields are used to carry out influences separation selectivity and blocks of nanometer to micron size are systems toward both order and simulations in the Gibbs ensemble with the capacity. The zeolites investigated include highly desired for their potentially novel disorder. In the absence of any other aim to explore liquid-liquid extraction and MFI and FAU frameworks with Si/Al ratios properties. They are prevalent in natural, interactions, entropic forces that zeolite-based sorption processes for the of ∞ and 6 (with calcium cations), and biological, and synthetic systems, and emerge upon crowding due to steric separation of ethanol and other oxygenates the simulations provide molecular-level can exhibit great complexity, including a interactions can drive transitions to from aqueous solution (over a range of insights on how pore dimension and hierarchy of structures. Two inter-related highly ordered structures, including feedstock compositions and temperatures). Al substitution control sorbate-sorbent “holy grails” in materials design are: complex crystals and quasicrystals, The extraction solvents investigated include and sorbate-sorbate interactions and liquid crystals, and rotator crystals. primary, secondary, and tertiary C10 alcohols influence separation selectivity and capacity. 1. The prediction of crystal and other Entropic forces are of particular and their mixtures with 1-methoxynonane, Furthermore, simulation results will be ordered structures from knowledge of importance in colloidal assembly, and the simulations provide molecular-level presented for the competitive adsorption of the constituent building blocks where they can be as large as several insights on how the architecture of these complex hydrocarbon mixtures in zeolites 2. The inverse design of the optimal kT at the onset of ordering, competing solvent molecules controls the formation and metal-organic frameworks. building block for self assembly into a with van der Waals, electrostatic, and target structure. other interactions. Much progress has been made on 3. Through shape, these entropic this front by considering “anisotropy forces become directional, creating dimensions” for building blocks an entropic “valence” capable of that allow for the systematic study dictating bulk crystal structures. We of how the forces between building discuss the implications of emergent blocks dictate preferred structures. directional entropic forces for the self- Among the many forces responsible assembly of nano materials. for the formation of highly organized
24 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 25 New Dithienogermole-based Conjugated candidate for application in tandem solar reported for all the co-polymers containing cells configuration due to its high efficiency bridged bithiophenes with 5-member fused Polymers for High Performance Organic at very low band gaps (Eg opt = 1.32 rings in the central core and possessing an opt Photovoltaics eV). Finally, the 6.6% PCE is the highest Eg below 1.4 eV.
Dr. Vasilis Gregoriou National Hellenic Research Foundation, Athens, Greece
Abstract
Over the last couple of years, the (DFBT) and [1,2,5]thiadiazolo[3,4-c]pyridine global research community has been (PT) are reported. It is demonstrated how experiencing an Organic Photovoltaics the choice of the acceptor unit (BTz, DFBT, (OPV) boom, triggering a fast growing PT) influences the relative positions of the interest in industry in this young and energy levels, the intramolecular transition disruptive technology. In particular, OPV energy (ICT), the optical band gap (Eg opt), opens up new opportunities for design in and the structural conformation of the architecture, e.g. the integration of solar DTG-based co-polymers. Moreover, the cells into facades, overhead glazings or photovoltaic performance of poly[(4,4- windows. Major challenges associated bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b’] with bringing organic photovoltaics to dithiophen-2-yl)-([1,2,5]thiadiazolo[3,4-c] the market are increasing the power pyridine)] (PDTG-PT), poly[(4,4-bis(2- conversion efficiency, reducing the ethylhexyl)-4H-germolo[3,2-b:4,5-b’] production costs and increasing the dithiophen-2-yl)-(2-octyl-2H-benzo[d] material and device long-time stability. [1,2,3]triazole)] (PDTG-BTz), and poly[(4,4- In order to increase the power bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b’] conversion efficiency, our efforts have dithiophen-2-yl)-(5,6-difluorobenzo[c] been focused on the development of [1,2,5]thiadiazole)] (PDTG-DFBT) is studied a series of donor–acceptor (D–A) low in blends with [6,6]-phenyl-C70-butyric band gap conjugated polymers utilizing acid methyl ester (PC70BM). The highest 4,4-bis(2-ethylhexyl)-4H-germolo[3,2- power conversion efficiency (PCE) is b:4,5-b’]dithiophene (DTG) as the electron obtained by PDTG-PT (5.2%) in normal rich unit and three electron withdrawing architecture. The PCE of PDTG-PT is further units of varying strength, namely improved to 6.6% when the device 2-octyl-2H-benzo[d][1,2,3]triazole (BTz), architecture is modified from normal to 5,6-difluorobenzo[c][1,2,5]thiadiazole inverted. Therefore, PDTG-PT is an ideal
26 QAFCO – Texas A&M at Qatar Conference 2014 Nanotechnology and Energy 27 High Performance Metal-Organic Framework Membranes for Energy-Efficient Olefin/ Paraffin Separations
Dr. Hae-Kwon Jeong Artie McFerrin Department of Chemical Engineering and Materials Science and Engineering Program, Texas A&M University, College Station, TX, USA
Abstract
Membrane-based gas separations are of growth, are generally derived from those great interest due to their energy-efficiency developed for zeolite membranes. As a result, when compared with their conventional MOF membranes would eventually face similar counterparts such as distillation. Currently challenges that zeolite membranes have faced membrane-based gas separations are for their large-scale commercial applications. primarily limited to the separation of non- These challenges include reproducibility, condensable gases such as air separation. scalability and high manufacturing cost. While the separation of condensable In this talk, I would like to discuss gases such as hydrocarbon isomers and radically different strategies for large-scale olefin/paraffin (e.g., ethylene/ethane MOF membrane synthesis with high gas and propylene/propylene) is much bigger separation performance. Using the new market, there are no commercially available techniques, we were able to produce membranes for these gases. This is continuous well-intergrown membranes of primarily due to the challenges associated prototypical MOFs, HKUST-1 and ZIF-8 in with materials and processing technologies. relatively short period of time (tens of min). Metal-organic frameworks (MOFs) With a minimal consumption of precursors are crystalline organic/inorganic hybrid and a greatly simplified synthesis protocol, materials that are made of metal nodes our new technique provides potential for interconnected with organic linkers, continuous, scalable, reproducible and forming well-defined channels and cavities easily scalable routes for the rapid synthesis in the scale of molecules. Due to their of high separation performance MOF microporous channels with tunable pore membranes. In particular, ZIF-8 membranes shape, size and functionality, MOFs has show greatly improved propylene/propane attracted a significant research interest for separation performances as compared to gas separation membrane applications. those prepared by conventional solvothermal Conventional MOF membrane fabrication methods indicating improved membrane techniques, namely in situ and secondary microstructure.
28 QAFCO – Texas A&M at Qatar Conference 2014 Texas A&M Engineering Building, Education City PO Box 23874, Doha, Qatar tel. +974.4423.0010 fax +974.4423.0011 www.qatar.tamu.edu