ANNEX IV. WG’s annual summary (6)

WG D36/001/06 Annual report Project title: Redox activity of host-guest, organometallic and molecular structures at electrode interfaces. II. Scientific report The joint research of host-guest complexes included the synthesis of several derivatives, in which the permethylated cyclodextrins were attached covalently to fullerene. The fullerene moiety was attached to the primary and also to the secondary cyclodextrin rings. Solubility of these compounds in water enabled us investigation of redox reactions of C60 in protic medium. The objective was the distinction of an intramolecular complexation from interactions C60-cyclodextrin between two molecules by electrochemical methods. Results were jointly published in Carbon. The redox activity of pesticides containing the nitroaromatic group is significantly increased by cationic catalysis. The joint research included very low frequency electrochemical impedance measurements combined with the modeling. We proved that under certain conditions the catalyzed electron transfer gives rise to the negative differential resistance. Such heterogeneous redox system yields spontaneous electric oscillations. Hence it is a suitable model system for natural periodic reactions. Results were jointly published in Electrochemica Acta. A series of new spiral-shaped organic dications was synthesized. The structure– properties relationships were sought in a series of [5]helquats having different number of methyl substitutents in several positons of aromatic rings. This study proved possible tuning of redox properties for applications of helquats as redox transfer mediators. Furthermore, these compounds were thoroughly investigated by EPR and electrochemical techniques seeking distinction between the formation of a charge transfer complexe and a complete electron transfer. The publication was accepted to Phys. Chem. Chem. Phys. journal The application of in-situ spectroelectrochemical methods involves a close cooperation with D35 action. Both partner laboratories achieved numerous results in the field

1 of interfacial organometallic redox chemistry. This yielded a review article in a high-impact journal. The combination of the reaction-oriented electrochemistry with the species-focussed spectroscopy in spectroelectrochemistry (SEC) allows a more complete analysis of electron transfer processes and redox reactions in general. Selected examples involving UV-VIS-NIR and IR absorption spectroscopy as well as electron paramagnetic resonance (EPR) illustrate the potential and the applicability of this technique. Original results obtained this year are described below. Research of the electron transfer in new organometallic compounds included phosphorescent cyclometalated heteroleptic iridium(III) phenylpyridinato (ppy) complexes containing luminescent 1-pyridylimidazo [1,5-α]pyridine (pip) ligands. Excitation of + [[Ir(ppy)2 (pip)] in acetonitrile solutions at room temperature results in a dual luminescence, strongly quenched by O2. Four complexes show, in absence of O2, a high-energy emission (assigned to a 3MLLCT transition) with two maxima in the blue region of the visible spectra, and a second structured emission (assigned largely to a 3LC π–π* transition.

New tris(ferrocenylcopper) compounds {(µ3-dqp)[Cu(dppf)]3}(BF4)3, dppf = 1,1’- bis(diphenylphosphinoferrocene), dqp = hexamethyl-, hexachloro- and un-substituted diquinoxalino[2,3-a:2’,3’-c]phenazine = hexaazatrinaphthylene (HATN), undergo at least two differently separated reversible one-electron reductions and three very closely spaced one- electron oxidations. While the latter are attributed to the stepwise ferrocene→ferrocenium conversions, the first electron addition occurs in the ligand bridge to yield EPR detectable radical complexes. Reversible steps reveal very low energy transitions for the reduced forms in agreement with the frontier MO arrangement. Our WG published 7 papers and 9 congress presentations with abstracts. Two STSM were granted. Seven other exchange visits were financed from other local sources.

Publications:

1. L. Pospíšil, M. Hromadová, M. Gál, J. Bulíčková, R. Sokolová, S. Filippone, J. Yang, Z. Guan, A. Rassat, Y. Zhang Redox Potentials and Binding Enhancement of Fullerene and Fullerene-Cyclodextrin Systems in Water and Dimethylsulfoxide. Carbon, 48 (2010) 153. 2. M. Hromadová, L. Pospíšil, R. Sokolová, N. Fanelli New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions. Electrochim. Acta, 54 (2009), 4991

2 3. L. Adriaenssens, L. Severa, T. Šálová, I. Císařová, R. Pohl, D. Šaman, S. V. Rocha, N. S. Finney, L. Pospíšil, P. Slavíček, F. Teplý Helquats: A Facile, Modular, Scalable Route to Novel Helical Dications Chemistry Eur. J., 15 (2009) 1072. 4. L. Pospíšil, M. Hromadová, M. Gál, M. Valášek, N. Fanelli, V. Kolivoška Irregular Polarographic Currents Obey Feigenbaum Universality Route from Order to Chaos Coll. Czechoslovak Chem. Commun, DOI: 10.1135/cccc2009120 5. G. Volpi, C. Garino, L. Salassa, J. Fiedler, K. I. Hardcastle, R. Gobetto, C. Nervi Cationic Heteroleptic Cyclometalated Iridium Complexes with 1-Pyridylimidazo [1,5- α]Pyridine Ligands: Exploitation of an Efficient Intersystem Crossing Chem. Eur. J, 15 (2009), 6415. 6. S. Roy, B. Sarkar, C. Duboc, J. Fiedler, O. Sarper, F. Lissner, S. M. Mobin, G. K. Lahiri, W. Kaim Heterohexanuclear (Cu3Fe3) Complexes of Substituted Hexaazatrinaphthylene - (HATN) Ligands: Twofold BF4 Association in the Solid and Stepwise Oxidation (3 e) or Reduction (2 e) to Spectroelectrochemically Characterized Species Chem. Eur. J. 15 (2009), 6932 7. W. Kaim, J. Fiedler Spectroelectrochemistry: the best of two worlds Chem. Soc. Rev. 38 (2009), 3373

Congress presentations and abstracts:

1. R. Sokolová, M. Hromadová, J. Ludvík, L. Pospíšil, S. Giannarelli: “ The Autoprotolysis in Reduction Mechanism of Substituted Benzonitriles“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 8. 2. L. Pospíšil, M. Gál, , M. Hromadová, R. Sokolová, J. Bulíčková, Y. Zhang , A. Rassat, S. Filippone, J. Yang, Z. Guan: ”Water-Soluble Fullerene Compounds Facilitate Nitrogen Fixation“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 29. 3. M. Hromadová, L. Pospíšil, R. Sokolová, S. Giannarelli, M. Gál: “ Focus on the Fate of Bifenox Anion Radical in the Presence of Cyclodextrin Cavities“ in The 60th Annual Meeting of the International Society of Electrochemistry, Symposium S10 – Molecular Electrochemistry: In its own right and in service to related research areas, Cd of Abstracts, Beijing, China, August 16 – 21, 2009, p 42. 4. R. Sokolová, I. Degano, M. Valášek, J. Fiedler, M. Hromadová, L. Pospíšil, J. Bulíčková, M. Gál, M. P. Colombini: „The Oxidation of Natural Dye Quercetin“ in International Symposium on Frontiers of Electrochemical Science and Technology, Book of Abstracts, Xi’an, August 12 – 15, 2009, O08. 5. V. Kolivoška, M. Valášek, L. Pospíšil, R. Sokolová, M. Hromadová: „On the Adsorption of Extended Viologens at the Mercury-Solution Interface.“ in International Symposium on Frontiers of Electrochemical Science and Technology, Book of Abstracts, Xi’an, China, August 12 – 15, 2009, O14. 6. L. Pospíšil, F. Teplý, M. Gál, L. Adriaenssens, M. Horáček, L. Severa, ElectronTransfer in Helical Polyaromatics in International Symposium on Frontiers of Electrochemical

3 Science and Technology, Book of Abstracts, Xi’an, China, August 12 – 15, 2009, O06. 7. L. Pospíšil, M. Gál, M. Horáček, F. Teplý, L. Adriaenssens, L. Severa, Structure- Reactivity Relationships in Electron Transfers of Helical Polyaromatic Dications, COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.123. 8 Z. Guan, J. Yang, Y. Wang, F. Moussa, L. Pospíšil, Y. Zhang, Synthesis of novel 2:1 permethyulated-cyclodextrin-fullerene conjugates, COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.141. 9. G. Volpi, J. Fiedler, L. Pospíšil, M. Sandroni, C. Garino, R. Gobetto, G. Viscardi, C. Nervi, Electrochemical functionalization of glassy carbon electrode surfaces by organometallic moieties. COST Chemistry D36 Workshop, Structural-performance relationships at the surface of functional materials, Book of Abstracts, Benahavis, Malaga, Spain, 21.-23.10.2009, p.143

II A Innovative networking Participating laboratories gained a certaindegree of an innovative knowledge from sharing expertize in different fields. One example is the publication [1]. Previous research by a laboratory specialized in synthesis could not resolve a problem of supramolecular protection of reactive forms of fullerene. A joint experiments brought results by performing high sensitivity low-frequency impedance measurements, which could discriminate subtle effects of intramolecular interactions. It is expected that those derivatives may find application on pharmacology and other fields. The COST action promoted launching national and bilateral projects involving several institutes participating in this D36 project. At present four national projects were approved and granted. One international project for the cooperation France-Czechia was awarded. Another international project between Italy and Czechia is now under evaluation.

II.B. Inter-disciplinary networking The application of in-situ methods involves a close cooperation within the project participants and with one D35 project. Partner laboratories achieved numerous results in the field of interfacial organometallic redox chemistry and in mechanistic studies of new organic compounds. An inter-disciplinary level of research proved to be a pre-requisite for identification of decomposition pathways of certain pollutants. A study of pesticides serves as one of the examples.

4 II.C. New networking Two additional members joint this project: (1) Atılım University, Facult of Engineering, Chemistry Group, Kızılcaşar Köyü, İncek, Gölbaşı TR-06836 Ankara, Turkey (Dr. A.Cihaner) (2) Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Rep., Flemingovo 2, 16610 Prague , The Czech Republic (prof. I. Stibor)

The total number of researchers is 23, females participate by 39 %. The Early Stage Researchers represent 43% of total participants. Early Stage Researchers participated in two STSM. One researcher participated in a training course in Ulm. Two Early Stage Researchers participated in a bilateral workshop ‘Dresden- Prague’. The number of publications is 7 and 9 congress communication with abstracts. The estimated amount of research funds raised by participants is at least 105 000 euro.

5 WG D36/003/06 2009 Scientific report

Interfacial functionalization of (bi)-metallic nanoparticles to prepare highly active and selective catalysts: understanding synergy and/or promotion effectInnovative networking

IIA. Innovative knowledge resulting from COST networking through the Action. (Specific examples of Results vs. Objectives The objectives of the working groups were essentially the following: 1. Understanding the relationship structure-activity/selectivity of supported (carbon, oxide) metal catalysts; (Au, Au-Me) 2. Developing highly selective catalysts for environmental processes:  Removal of pollutants (direct action)  Search of non polluting sources of energy (hydrotreatment, CH4, H2) (indirect action)

With respect to the first point, the group lead by Prof. Kruse in Belgium has studied the interaction CO-H2O over gold-palladium systems using an innovative approach based on the combination of FIM with time-of- flight mass spectrometry. Such method allowed a local chemical determination of the surface during the ongoing phenomenon and revealed drastic changes in the surface composition before and after the travelling of gases on the probed area. Moreover, contrary to thermodynamics forecasts Au enrichment, Pd segregation was observed in the presence of NO gas and was attributed to the chemical pumping effect by Oad species following NO dissociation.

In collaboration with the Palermo group, and more related to the objective no. 2, quite interesting results have been obtained on the reaction of the total oxidation of CH4 over Pd supported supported on TiO2 doped SiO2. Very active and selective catalysts were obtained. Moreover it was demonstrated for the first time (breakthrogh result) that SO2 treated TiO2 –doped Pd/SiO2 catalysts could be reactivated by CH4. TPD studies indicated that two forms of sulphate species exist. The first one, responsible for catalytic deactivation can be

removed by selective reduction in methane at 350°C.

The second one, rather stable and possibly removed at temperature higher than 700°, is associating with acidic sites polarizing the C-H bond in CH4, therefore as a promoter of the reaction. As a joint study between the two groups (Belgium/Hungary), model gold and silver catalysts were prepared by evaporation of gold onto native SiO2 covered Si(100) wafers producing gold films of different thickness. Creation of interface of gold films and gold nanoparticles over different oxides such as TiO2, FeOx and CeO2 deposited by pulsed laser deposition (PLD) changed drastically the catalytic activity of the oxide overlayers of the samples in the CO oxidation, demonstrating the importance of the interface effects. As collaboration between Sweden and Italy, synthesis of nanocrystalline CeO2 nanoparticles was achieved by a novel oil-in water microemulsion reaction method developed in Sweden. A series of nano- cerias were obtained by varying the microemulsion composition and the reaction conditions. The characterization studies demonstrate that nanocrystalline cubic ceria was obtained at room temperature with a specific surface area of 180 to 250 m2/g. As a very important result this material maintained the structural feature and the stability even after calcining at 400 °C.

In the figure on the right the XRD patterns of the calcined and uncalcined ceria are shown. In the left side figure the TEM image of the ceria nanoparticles before calcinations are shown. Adopting the microemulsion method, gold catalysts over different supports, TiO2, CeO2, and CeO2/ZrO2, were prepared and tested in the oxidation of CO. Due to the low temperature at which crystallized ceria was obtained the particular synthesis method may have a strong impact on practical application and is considered for technology transfer. Modeling of gas transport in a microporous solid using an innovative slice selection procedure and applied to the diffusion of benzene in zeolites was carried out by the French group lead by Prof. Jacques Fraissard. This research involved researchers from outside the COST countries, particulary involved people from Ternopil, Ukraine. Moreover they used 129Xe spectroscopy of adsorbed Xenon for exploring microporous carbon materials. The joint studies between Italy/Bulgaria has focused on the synthesis and investigation of gold catalysts supported on ceria modified by rare earth metals. Two preparation methods were considered, mechanochemical activation and coprecipitation. The catalysts were tested in the PROX reaction and also in the deNOx by CO and hydrocarbon. Concerning the PROX, the addition of yttrium to ceria was beneficial and the use of co-precipitation yielded the most active catalysts. The catalytic behavior in the NOx +CO reaction, analysed with a flow system in the laboratory of the ISMN in Palermo was evaluated under different experimental conditions and with different reaction mixtures. In particular we wanted to study the effect of the water. Combining the data of activity obtained with the IR and UV detector of the different reagent and product gases, with the mass quadrupole data, we observed that in the presence of water the selectivity to N2 is improved and there is no formation of ammonia. Such results makes these type of materials appealing for application in catalytic converters.

The recent involvement of the Turkish partner (Prof. Kantcheva from Bilkent University) has contributed to the understanding of the reaction mechanism between NO and CO using the Infrared Spectroscopy. The Kantcheva team performed in situ FT-IR spectroscopic investigation in order (i) to obtain information about the role of the components of the catalytic system in the reduction of NO by CO and (ii) to clarify the effect of H2 on the enhancement of the reduction process by gaining insights into the NO+CO reaction mechanism. 0 The NO+CO+H2 reaction in the 150-350 C range leads to formation of NCO species on all of the samples (peak at 2170 cm-1). Surface isocyanates are produced by a process involving the dissociation of NO on the oxygen vacancies of CeO2 and CeO2-Al2O3, followed by the reaction between N atoms lying on the surface and CO molecules. The results of this investigation clearly show that the CeO2-Al2O3 phase in the Au/CeO2- Al2O3 catalyst participates directly in the catalytic reduction of NO with CO. The role of gold is the modification of ceria with appearance of Ce3+ ions and oxygen vacancies and in the lowering of the reduction temperature of CeO and CeO -Al O , FT-IR spectra of the activated AuCe and AuCeCeAl20 2 2 2 3 whereas H keeps the surface reduced during the samples (a) and FT-IR spectra collected during 2 course of the reaction. exposure of the samples for 15 min to a (5 mbar NO + 0 0 10 mbar CO + 3 mbar H2) mixture at 150 C (b), 200 C (c), 2500C (d), 3000C (e), 3500C (f) and 4000C (g). Quite important, the collaboration between the three groups (Italy/Bulgaria and Turky) produced a spin off for a NATO Collaborative Project Grant expired in 2009 (CLG). Moreover Common project between the CNR and the BAS national institution were started. Concerning the activity on catalyst and reaction modeling the group in Romania has given an important contribution in the understanding of reactivity of small gold clusters deposited on the MgO(001) surface through a semiempirical study. The developed procedure allowed the investigation of deposition of clusters on surfaces, providing the configurations of the most stable clusters and information about the cluster reactivity. They applied the MOPAC semiempirical code. Their model predicted that neutral clusters of up to about nine gold atoms should be planar, an example being the D6h Au7 cluster, in which the Au-Au distance is predicted to be 2.71 Å (2.24). Clusters of up to 12 gold atoms are also predicted to be stable, provided the cluster has a single negative charge. The group lead by prof. Josef Korecki in Krakow, has studied in details the behavior of Au-based catalysts by comparing model and real system. Their objective within the COST action group consists in the understanding of the material gap between the ultrathin film catalysts and the real systems. Bi-metalic Au-Fe nanoclusters deposited at ultrahigh vacuum conditions on a single crystalline rutile TiO2(110) substrate were studied using STM and XPS, in view of the influence of the deposition sequence (Au,Fe or Fe,Au) on the cluster morphology and electronic properties. The most interesting and innovative result demonstrating the impact of the deposition conditions on the cluster assembly is shown in the figure on the right. The diameter (and height) of these bimetallic clusters could be tuned by annealing temperature and preparation recipe, which will be used for modeling Fig. 1. Height distribution of the bimetallic gold- real catalysts. iron clusters as a function of the deposition sequence and annealing temperature.

Concerning real catalysts they prepare three type of Au-Ni supported systems investigated in catalytic CO oxidation; a) Au-Ni nanoalloys supported on titania (Ni-Au/TiO2) ; b) Au nanoparticles deposited on Ni clusters or films and next supported on titania (Au/NiTiO3Ti) c) iii. Au and Ni nanoparticles subsequently deposited on titania (Au/Ni/TiO2). The activity of the synthesized catalysts was tested in the CO oxidation. It was shown that the lower the oxidation state of nickel, the lower was the catalytic activity.

Spin off of new EC RTD Framework Programme proposals/projects. (List) Project of the Foundation for Polish Science Team Programme co-financed by the EU European Regional Development Fund. 2009 – 2013. “Atomic and molecular level devising of functional nanostructures for magnetic and catalytic applications”

Spin off of new National Programme proposals/projects. (List) Bilateral CNR/BAS (2007-2009) “ Gold supported catalysts on ceria modified by different metal oxides for NOx removal” NATO CLG (2007-2009) “NOx reduction by CO over gold-ceria catalysts: activity and mechanism”

IIB. Interdisciplinary networking. As described above, the working group is formed by chemists, physicists, theoreticians and also chemical engineering. This partnership makes the research interdisciplinary and for sure should favor the solution of problems tackling them from different aspects.

II.C. New networking

Additional new members joining the Action during its life. Turkey has recently joined the WG.

Total number of individual participants involved in the Action work. (Number of participants. Give % of female and of Early Stage Researcher participants)

Italy: 5 participants, 80% Female Hungary: 3 participants 66% female. France: 4 participants 25% female. Bulgaria: 3 participants, 66% female Romania: 2 participants, 0% female Belgium: 4 participants: 0% female Sweden: 6 participants; 33% female. Poland: 6 participants; 33% female. Turkey: 1 participant; 100% female.

Total participants: 34, 41% female.

Involvement of Early Stage Researchers in the Action, in particular with respect to STSMs, networking activities, and Training Schools.

The following STSM have been granted in 2009.

1. STSM granted to Mr. Gerome Melaet, Universitè Libre de Bruxelles (Kruse) for the period of 3 weeks from 9/03/2009 in Palermo (Venezia). 2. STSM granted to Dr. Gabriella Di Carlo from ISMN-CNR, Palermo (Venezia) for a period of three months from 09/09/ 2009 at the Department of Chemical Engineering and Technology, Chemical Technology,Stockholm, (Boutonnet) 3. STSM granted to Dr. Ivan Bogoev Ivanov from Institute of Catalysis (Andreeva) for a period of four weeks from 14/04/2009 in Palermo at the ISMN-CNR (Venezia). 4. STSM granted to Ms. Timea Benko from Institute of Chemistry (Guczi) for a period of 2 weeks from 24/05/2008 in Palermo at the ISMN-CNR (Venezia)

Advancement and promotion of scientific knowledge through publications and other outreach activities. (Number of publications and other outreach activities that resulted from COST networking through the Action. Complete list should be given in an annex)

See the annex

Activities and projects with COST network colleagues.

• 3rd WG meeting, 23-26 October 2008, Nice. • 4th WG meeting, 15-16 May 2009, Palermo

Inter WG activity: A researcher from our WG was an Invited lecturer at the school Electrocatalysis at the Nanoscale: Theory and Modeling organised by the working group (D36/005/06- Structure-Reactivity Relationships of Pt and Pd Nanoarrays)

List of Publication Abstract in Congresses 1) K.Frey, G.Petö,V. Iablokov, N. Kruse, L. Guczi : "Au and Ag based catalysts for the abatement of environmental harmful gases" oral Europacat IX , 30th August-4th September 2009 , Salamanca 2) G. Melaet, K. Frey, R. Szukiewicz, S. Chenakin, N. Kruse: "Reactivation of TiO2-doped Pd/SiO2 catalysts for complete methane oxidation" oral Europacat IX , 30th August-4th September 2009 , Salamanca 3) V. Iablokov*, K. Frey*, O. Geszti*and N. Kruse: "Active Mn3O4 prepared via oxalate precipitation in low-temperature CO oxidation reaction" poster, Europacat IX , 30th August-4th September 2009 , Salamanca 4) T. Benkó, A. M. Venezia, L. F. Liotta, G. Pantaleo, A. Beck, L. Guczi, Z. Schay: Propene total oxidation over gold catalysts: Influence of TiO2 and CeO2 decoration on Au/mesoporous SBA-15, CLEAR „Catalysis Lectures for Environmental Applications & Renewables” Summer School in Catalysis 2009, May 24-29, Porto Carras, Chalkidiki, Greece 5) L. Ilieva, G. Pantaleo, I. Ivanov, R. Zanella, A. M. Venezia, D. Andreeva, “A comparative study of gold catalysts supported on modified by rare earths ceria, prepared by mechanochemical activation or coprecipitation, for preferential oxidation of CO “ Europacat IX, 30th August-4th September, 2009, Salamanca , Spain.

6) Lyuba Ilieva, Giuseppe Pantaleo, Ivan Ivanov, Rodolfo Zanella, Anna Maria Venezia, Donka Andreeva, “Gold catalysts supported on ceria, modified by rear earths for the preferential CO oxidation”. Gold 2009 - The 5th International Conference on Gold Science, Technology and Its Applications, 26-29 July, 2009, Heidelberg. Germany.

7) M. Kantcheva, O.Samarskayam L.Ilieva, G. Pantaleo, A.M.Venezia, D. Andreeva, Mechanism of the reduction of NO with CO over Au/CeO2-Al2O3 catalyst in the presence and absence of H2: in situ FT-IR spectroscopic investigation. Europacat IX, 30th August-4th September, 2009, Salamanca , Spain.

Invited lectures. 1) J. Fraissard, The search for lost illusions Plenary lecture, International congress “XEMAT 2009” Ruka, Finland, 7-10/06/2009 2) J. Fraissard, Modeling of gas transport in a microporous solid using a slice selection procedure: Application to the diffusion of benzene in ZSM5. Key note lecture VIIIJInternational Conference ” Mechanisms of Catalytic Reactions”Novosibirsk, 29 June- 2 July 2009 . 3) A.M.Venezia” Supported Bimetallic Catalysts: electronic and geometric effects” COST Workshop, 4-8 Oct. 2009, Reisensburg Castle, Ulm 4) J. Fraissard, … COST WORKSHOP

Publication

1) L. Ilieva, G. Pantaleo, I. Ivanov, R. Nedyalkova, A.M. Venezia, D. Andreeva, “NO reduction by CO over gold based on ceria, doped by rear earth metals”, Catal. Today, 139 (2008) 168-173. 2) L. Ilieva-Gencheva, G. Pantaleo, N. Mintcheva, I. Ivanov, A. M. Venezia, D. Andreeva, “Nanostructured Gold Catalysts Supported on CeO2 and CeO2-Al2O3 for NOx reduction by CO: Effect of Catalysts pretreatment and Feed Composition”, J. Nanoscience & Nanotechnology, 8 (2008) 867. 3) K. Frey, V. Iablokov, G. Melaet, L. Guczi, N. Kruse: CO oxidation activity of Ag/TiO2 catalysts prepared via oxalate co-precipitation, Catal. Lett. 124 (2008) 74 4) Michael Petryk, Sebastien Leclerc, Daniel Canet and J. Fraissard, Modeling of gas transport in a microporous solid using a slice selection procedure. Application to the diffusion of benzene in ZSM5, Catalysis Today, 139 (2008) 234-240 5) Kancheva, O. Samarskaya, L. Ilieva, G. Pantaleo, A.M. Venezia, D. Andreeva, “In situ FT-IR investigation of the reduction of NO with CO over Au/CeO2-Al2O3 catalysts in the presence and absence of H2”, Appl. Catal. B: Environ., 88 (2009) 113-126. 6) L. Ilieva, G. Pantaleo, R. Nedyalkova, J.W. Sobczak, W. Lisowski, M. Kantcheva, A.M. Venezia, D. Andreeva, “NO reduction by CO over gold catalysts based on ceria supports, prepared by mechanochemical activation, modified by Me3+ (Me = Al or lanthanides): Effect of water in the feed gas”, Appl. Catal. B: Environ., 90 (2009) 286- 294. 7) L. Ilieva, G. Munteanu, P. Petrova, D. Andreeva, “Nanostructured gold catalysts supported on ceria modified by rare earths: TPR and kinetic parameters of reduction”, Nanoscience and Nanotechnology (Eds. E. Balabanova, I. Dragieva), 9 (2009) 189-192. 8) L. Ilieva, G. Pantaleo, I. Ivanov, R. Zanella, A.M. Venezia, D. Andreeva, “A comparative study of differently prepared rare earths modified ceria-supported gold catalysts for preferential oxidation of CO”, Int. J. Hydrogen Energy, 34 (2009) 6505- 6515. 9) L. Guczi, A. Beck, K. Frey: Role of promoting oxide morphology dictating the activity of Au/SiO2 catalyst in CO oxidation, Gold Bulletine 42 (2009) 5 10) A. Beck, A. Horváth, G. Stefler, M. S. Scurrell, L. Guczi: Role of preparation techniques in the activity of Au/TiO2 nanostructures stabilised on SiO2: CO and preferential CO oxidation, Topics in Catalysis 52 (2009) 912 11) A.M. Venezia, G. Di Carlo, G. Pantaleo, L. F. Liotta, G. Melaet, N. Kruse, Oxidation of CH4 over Pd supported on TiO2-doped SiO2: Effect of Ti(IV) loading and influence os SO2, Appl. Catal. B: 88 (2009) 430-437. 12) K.V. Romanenko, O.B. Lapina, X. Py and J. Fraissard 129Xe spectroscopy of adsorbed Xenon. Possibilities of exploration of microporous carbon materials, Russian Journal of General Chemistry, 2009, Vol. 78, N°11, pp. 2171-2181 13) K.V. Romanenko, O.B. Lapina, V.L. Kuznetsov and J. Fraissard “Potential of 129Xe NMR spectroscopy of adsorbed Xenon for testing the chemical state of the surface of mesoporous carbon materials illustrated by the example of aggregates of diamond and oniono –like carbon nanoparticles, Kinetics and Catalysis, 2009, Vol. 50, N° 1, pp. 26- 30.

WG D36/005/06 2009 Annual Report

Structure Reactivity Relationships of Pt and Pd Nanoarrays Activity Report

Workgroup members

1. Dr. Alvaro Colina, University of Burgos (UBU), Spain 2. Prof. Robert Dryfe, University of Manchester (UMAN), UK 3. Dr. David J. Fermín, University of Bristol (UBRI), UK 4. Prof. Marc Koper, University of Leiden (ULEI), Holland 5. Prof. Julie Macpherson, University of Warwick (UWAR), UK 6. Dr. Virginia Ruiz, Helsinki University of Technology (HUT), Finland 7. Dr. Elizabeth Santos, University of Ulm (ULM), Germany 8. Prof. Wolfgang Schmickler, University of Ulm (ULM), Germany 9. Prof. Patrick Unwin, University of Warwick (UWAR), UK

II.A. Innovative networking

II.A.1. Innovative knowledge/scientific breakthrough resulting from COST networking. The research activities of the working group have covered fundamental aspects linked to the reactivity of Pd and Pt nanostructures at carbon based materials, molecular interfaces and polymer films. Significant progress has also been achieved on theoretical aspects of electrocatalysis at metal nanostructures, in particular on hydrogen evolution reaction. The D36/005/06 has not only delivered the key scientific objectives set out in the original research programme, but also established new partnerships with groups in the heterogeneous catalysis field as a result of the highly successful training schools. The specific activities, results and collaborating institutions for each workpackage are summarized below.

WP1. Wet Chemical Synthesis of Nanostructures and Self-Assembly at Solid Supports (UBRI, UWAR, UBU, HUT). The key objectives of WP1 have already been completed, including: a- Synthesis of Pd and Au-Pd core-shell nanostructures with various shell thickness by colloidal methods (publications in progress) b- Characterisation of the nanostructures by high resolution TEM, electron diffraction and XRD c- Electrostatic assembly of 2 and 3D arrays of the nanostructures at electrode surfaces [1,2].

1 d- Generation of Pt-polyaniline and Pt-PEDOT nanocomposites employing layer-by-layer methods [3].

WP2. Electrodeposition of nanoparticles arrays on CNTs (UWAR, UBU, HUT) UWAR has developed its carbon nanotube growth protocols to allow the growth of single-walled carbon nanotube (SWNT) networks with a wide range of surface densities, from relatively sparse 2D networks to essentially fully-covered surfaces [4]. The mechanisms of SWNT growth on various surfaces have also been intensely studied [5]. These materials show impressively low background currents for the amperometric detection of analytes including those of biological significance [4]. High and low SWNT arrays are also being explored as supports for the formation of metal nanoparticles via electrodeposition. Hitherto, UWAR has looked at Au, Pt and Ni (work/papers in progress). Initial work suggests these materials have impressive electrocatalytic properties for reactions such as the oxidation of hydrazine (Au-SWNTs) and methanol (Pt-SWNTs). In the coming year we plan to use similar protocols to deposit semiconductor nanoparticles and nanowires in conjunction with UBRI. The intrinsic electrochemical activity of SWNTs is a matter of considerable debate and controversy and UWAR have recently provided a comprehensive summary that identifies issues to be addressed to progress in this area [6]. UWAR has also investigated the deposition of metal nanoparticles on other surfaces, including conducting diamond [7], graphite and indium tin oxide [8]. In the former case, it has been demonstrated that ultra-small particles can be formed by simple electrodeposition methods. These particles can be used to detection oxygen by electro-reduction. In the latter case, potential cycling of various types of electrodes was used to control the density of pre- formed chemically-functionalised nanoparticles at electrode surfaces. HUT and UBU have jointly investigated milder and more efficient methods to remove undesired metal catalysts remaining in carbon nanotubes after their synthesis. CNT purity is critical for their application as electrocatalyst supports because the presence of metallic impurities even at trace level can dominate the electrochemical response of the CNTs, leading to misplaced claims about their superior intrinsic electrocatalytic properties of CNTs. On the other hand, too harsh washing conditions can be detrimental for the CNT properties. The work has focused on comparing different purification methods for SWCNTs. Among them, electrochemical purification proved to be more the most advantageous as it is faster, more efficient and less destructive for the CNTs than other conventional methods [9]. HUT is also exploring different large-scale methods (gram scale) to deposit of Pt nanoparticles on various types of carbon nanotubes and nanofibers. A comprehensive study is underway to try to establish the influence of both the carbon support functionalisation and catalyst deposition method on the catalyst size/dispersion, catalytic activity and stability.

2

(a) (b) (c)

Figure 1. TEM images of Pt nanoparticles on different carbon nanomaterials: (a) single-walled CNTs, (b) few-walled CNTs and (c) carbon nanofibers.

WP3. Electrochemical Nucleation of metallic clusters at membrane supported liquid/liquid interfaces (UMAN, UBU, HUT) The generation and stabilisation of Pd nanostructures at polarisable liquid/liquid interfaces was investigated. We have strong evidence that catalytic hydrogen evolution occurs on the Pd deposits, however a key problem is the uncontrolled aggregation of the particles formed at the polarisable liquid/liquid interface. The conventional route to avoid this problem, for nanoparticles in bulk solution, is to stabilise the particles by addition of an appropriate ligand. A number of possible ligands were explored, with promising results obtained for Pd particles stabilised with tetra-octylammonium cations: work in this area is ongoing. The UBU and HUT groups developed a new device to perform spectroelectrochemistry at L/L interfaces. The new design allows monitoring process taking place at both sides of the interface by a mobile slit. This precise micropositioning of the slit further facilitates the alignment of the incoming light beam at the interface.

WP4. Electrocatalytic Activity of the Nanostructured Surfaces (ULEI, UBRI, UMAN, UBU, HUT) The ULEI group has uncovered interesting properties of defect sites in nanostructured surfaces on the CO electro-oxidation [10]. Defect sites appear to have a dual reactivity towards carbon monoxide: CO sitting close to the defect, but not on it, reacts rapidly with OH in the defect or step. However, CO sitting on the step or defect reacts only slowly with OH on a terrace site. The UBRI group has made significant progress on rationalising the interactions between hydrogen and ultrathin Pd shells at Au nanostructures. The electrochemical responses associated with hydrogen loading into the Pd domains in 3D nanostructured assemblies were investigated in acid solutions. Responses arising from the electrochemical H adsorption and absorption were effectively deconvoluted in the potential scale. As expected, the charge originating from H absorption increases as the thickness (volume) of the Pd shell increases. However, detailed analysis of the hydrogen loading charges vs. Pd thickness revealed high

3 H/Pd ratios which have not been previously reported for either nanostructured or extended surfaces. These developments have recently been submitted for publication. The UMAN and ULEI groups investigated the oxidation of dimethylamine borane at single crystal gold electrodes employing in-situ IR spectroscopy. The mechanism of the (irreversible) oxidation of this widely used reducing agent is not clear and a number of conflicting articles have appeared in recent literature. The process is catalysed by noble metals, Au most efficiently, and the adsorption of borane on Au has been previously suggested. Voltammetric studies revealed a strong influence of the crystallographic plane orientation on the oxidation kinetics. Furthermore, evidences of reversibility (reduction process) were obtained for the first time at a particular crystal orientation. The analysis of the voltammetric and in situ spectroscopy is currently ongoing. UWAR collaborated with UBU and HUT to study the electrodeposition of platinum nanoparticles on highly oriented pyrolytic graphite (HOPG) and on HOPG modified with a conducting polymer. They have shown that ultrathin films of poly(3,4-ethylenedioxythiophene) enhanced the rate of electro-oxidation of formic acid compared to similarly-sized platinum nanoparticles on native carbon. This suggests that chemically-functionalised interfaces may be attractive supports for noble metal electrocatalysts for various organic transformations. The UBU and HUT teams developed a new cell for Raman spectroelectrochemistry compatible with conventional Raman spectrometers as well as confocal micro-Raman spectrometers. This technique allows obtaining in-situ spectroscopic information about the reaction products generated during the electrocatalytic reactions. The technique has been used to characterise the SWCNT electrodes used to support Pt nanoparticles. In collaboration with the UBRI group, these spectroelectrochemical approaches will be used to investigate the electro-oxidation of methanol and formic acid on the Au-Pd core-shell nanostructures.

WP6. Theoretical Modelling of Nanostructure Reactivity (ULM) The Ulm group have made significant progress on the theoretical aspects of electrocatalytic reactions at nanostructures [11-16]. Particularly, hydrogen oxidation and evolution have been investigated at ultrathin Pd films deposited on various metal substrates. A good agreement with experimental data reported in the literature has been obtained. The analysis showed that lattice strain associated with the distances to nearest neighbour plays an important role on the reactivity of the Pd overlayers, although it is not the only key parameter. Chemical interactions with the substrate also produce modifications in the electronic properties and in consequence in the catalytic activity. Of the investigated systems, Pd on Au(111) exhibits the best catalytic effects, while monolayers on Cu(111) are less active than bare surfaces of Pd(111) in accordance with experimental results. The reactivity of Pd sub-monolayer on Au(111) with a coverage degree of 0.33 was also investigated. A cluster of three Pd atoms was analysed on two different structures, (i)

4 embedded in the surface of Au(111) replacing Au atoms in the lattice and (ii) deposited as an overlayer on the hollow sites of the Au(111) surfaces. The density of states of the d band of Pd as well as the electrocatalytic properties were found highly sensitive to the structure of the cluster. For instance, the hydrogen oxidation process was found seven times faster on the Pd overlayer than in the sub-monolayer.

II.A.2. Spin off of new EC RTD Framework Programme projects. Recent research projects involving group members of the D36/005/06 include:

i. Surface Electrochemical Reactivity in Electrocatalysis: A Combined Theoretical and Experimental Approach” (ELCAT): multisite Initial Training Network within the EU Seventh Framework Programme involving ULEI and ULM.

II.A.3. Spin off of new National Programme projects. Recent research projects involving group members of the D36/005/06 include: i. Study of the formation of Pd nanoparticles at L/L interfaces using a new mobile slit spectroelectrochemical cell: project funded by the Junta de Castilla y Leon involving UBU, HUT and UMAN. ii. Development of Optically Transparent Electrodes based on Single Walled Carbon Nanotubes: project funded by the Junta de Castilla y Leon involving UBU and HUT. ii. Novel carbon nanomaterial networks as ultrasensitive/efficient platforms for analysis and electrocatalysis: project funded by the Research Council for Natural Sciences and Engineering of the Academy of Finland involving HUT.

II.B. Inter-disciplinary networking

II.B.1. Collaboration with other working groups within COST. Strong collaboration has recently been established with the D36/006/06 (Understanding the Chemical Reactivity of Alcohols over Catalytic Materials: From Probe Molecules to Practical Applications), certainly increasing the level of inter-disciplinarity within the Action. Dr. Monica Calatayud, Dr. Frederik Tielens are working in collaboration with Dr. Elizabeth Santos and Prof. Wolfgang Schmickler on theoretical aspects associated with the formation of alkylthiol self-assembled monolayers at Au surfaces. In addition, Dr. Guido Mul and Prof. Marc Koper have initiated a joint research activity on nanoscale photo-electrocatalytic reduction of CO2.

II.C. New networking

II.C.1. Structure of the workgroup. A total of 34 researchers have been involved in the D36/005/06 group, from which over 32% are female and over 75% are Early Stage Researchers (ESR).

5 II.C.2. Involvement of Early Stage Researchers in the Action. Three Short-term Scientific Missions (STSM) were developed in the current reporting period:

i. Ms. Daniela Plana (UMAN): In-situ Spectroscopic Investigation of the Electrocatalytic Oxidation of Dimethylamine Borane, Leiden University (Prof. Marc Koper), June 8th to July 17th 2009

ii. Mr. Markus Vogelsang (ULM): Electrocatalytic activity of particles deposited at liquid/liquid interface, University of Manchester (Prof. R. Dryfe), March 1st to April 30th 2009.

iii. Dr. Elisabeth Santos (ULM): Investigation of the adsorption mechanism of alkyl thiols on Au(111) surfaces, using ab-initio methods. Université Pierre et Marie Curie (Dr. Monica Calatayud), September 14th to 23rd 2009

Some STSMs scheduled for 2010 include:

1- Ms. María Guadalupe Montes de Oca Yehma (UBRI) to ULEI. This STSM will focus on the electrocatalytic oxidation of CO at Pd@Au nanoarrays. The oxidation of CO at multilayer assemblies of Pd@Au nanostructures as reported in WP1 will be investigated in CO saturated solution. An important aspect to be addressed is the effect of the Pd layer thickness on the rate of the process. The possibility of combining electrochemical measurements with on-line mass spectrometry will be considered.

2- Ms. María Guadalupe Montes de Oca Yehma (UBRI) to UWAR. This mission will extend preliminary studies on the kinetics of hydrogen evolution at the Pd@Au nanostructures employing scanning electrochemical microscopy. These studies involve measurement and simulation of SECM approach curves as a function of the particle number density at insulating substrates following the method recently developed by the UWAR group. 3- Mr Petr Dudin (UWAR) to ULEI. This mission will focus on the investigation of electrocatalytic processes at the level of a single metal nanoparticle. The work will build on UWARs recent studies of metal nanoparticles supported on carbon nanotubes and combine this with the expertise of ULEI in the investigation of small scale systems. 4- Mr Andrey Koverga (ULEI) to ULM. This mission will investigate the stability of water on small Pt and/or Pd nanoparticles using first-principles DFT calculations, as well as the binding energies of the relevant intermediates. These data can also serve as input for the calculation of the electrocatalytic properties of such particles using the model developed in Ulm.

II.C.3.Publications (see last section, references)

II.C.4. Activities with COST network colleagues. A second Training School on Heterogeneous Catalysis and Electrocatalysis at the Nanoscale was organised in Reisensburg Castle near Ulm from 4th to 8th October 2009. This School was devoted to theory and computer modelling of interfacial reactions with strong emphasis on the relationships

6 between heterogeneous catalysis and electrocatalysis. Theoretical surface science has experienced tremendous progress in the last decades. The great improvement on computing power and the development of efficient algorithms has opened the possibility of modelling surface structures and reactions in terms of electronic interactions obtained from first principles. Electrocatalysis and heterogeneous catalysis are strongly interrelated, although the former is rather sensitive to the properties of the solvent and the dynamics of electron exchange between electrode and electrolyte which are integral aspects of every electrochemical reaction. The incorporation of these two aspects in theoretical modelling has been extremely challenging, although significant progress have been made in recent years. Techniques such as density functional theory (DFT), Monte Carlo, and molecular dynamics simulations, both classical and quantum, are increasingly being applied to electrochemical systems and electrocatalysis. One of the key contributions of the workgroup D36/005/06 is the development of a generalised theory for electrocatalytic reactions (WP6) that has provided valuable insights into the dynamics of hydrogen evolution and oxidation at nanostructured surfaces. As part of the key deliverables of D36/005/06, the Ulm group led the organisation of a Training School devoted to methods and models relevant to electrocatalysis and heterogeneous catalysis. A panel of twenty experts delivered lectures on: • Electron transfer theories: from Marcus theory to theories of electrocatalysis • Simulation methods: Monte Carlo and Molecular dynamics, both classical and quantum versions. • Quantum chemical methods • Relation between electrocatalysis and heterogeneous catalysis. Over 30 participants from the whole of the Action D36 took part on the 4 day event and the feedbacks received were overwhelmingly positive.

II.C.5. Raising of research funds. The large proportion of ESR demonstrates the capacity of the group members to obtain funding for COST related activities. Organisations that have supported the D36/005/06 group includes the Engineering and Physical Science Research Council (UK), Consejo Nacional de Ciencias y Tecnología (Mexico), The Swiss National Science Foundation (CH), the International Society of Electrochemistry, the Lorentz Center

Leiden (NL), National Physical Laboratory (UK), Birmingham Science City: Innovative Uses for Advanced Materials in the Modern World (West Midlands Centre for Advanced Materials Project 2; AM2 and Hydrogen-Energy (both Advantage West Midlands supported projects, with AM2 also part-funded by the European Regional Development Fund).

References [1] F. Li, I. Ciani, P. Bertoncello, P.R. Unwin, J. Zhao, C.R. Bradbury and D.J. Fermin, J. Phys. Chem. C 112 (2008) 9686.

7 [2] C.R. Bradbury, C. Bünzli, J. Zhao, M. Carrara, G.P. Kissling, E. Aslan-Guerel and D. J. Fermín, CHIMIA, 62 (2008) 841. [3] S. Palmero, A. Colina, E. Muñoz, A. Heras, V. Ruiz, and J. López-Palacios, Electrochem. Commun. 11 (2009) 122. [4] I. Dumitrescu, J. P. Edgeworth, P. R. Unwin, and J. V. Macpherson, Adv. Mater. 21 (2009) 3105. [5] A. Rutkowska, D. Walker, S. Gorfman, P. A. Thomas and J. V. Macpherson, J. Phys. Chem. C 113 (2009) 17087. [6] I. Dumitrescu, P. R. Unwin and J. V. Macpherson, Chem. Commun. 45 (2009) 6866. [7] L. Hutton, M. E. Newton, P. R. Unwin and J. V. Macpherson, Anal. Chem. 81 (2009) 1023. [8] M. Peruffo, P. Contreras-Carballada, P. Bertoncello, R. M. Williams, L. De Cola and P. R. Unwin, Electrochem. Commun. 11 (2009) 1885. [9] A. Heras, A. Colina, J. López-Palacios, P. Ayala, J. Sainio, V.Ruiz and E. I. Kauppinen, Electrochem. Commun. 11 (2009) 1535. [10] G. Garcia, M.T.M. Koper, J. Am. Chem. Soc. 131 (2009) 5384 [11] E. Santos, A. Lundin, K. Pötting, P. Quaino and W. Schmickler. J. Solid State Electrochem. 13 (2009) 1101. [12] E. Santos, P. Quaino and W. Schmickler, J. Chem. Sci. 121 (2009) 575. [13] E. Santos, A. Lundin, K. Pötting, P. Quaino and W. Schmickler, Phys. Rev. B 79 (2009) 235436. [14] E. Santos, A. Lundin, K. Pötting, P. Quaino and W. Schmickler, ChemPhysChem (in press). [15] E. Santos, P. Quaino and W. Schmickler, Electrochim. Acta, (in press). [16] E. Santos, G. Soldano, P. Quaino and W. Schmickler, Electrochem. Commun. 11 (2009) 1388.

8 WG D36/006/06 2009 Annual Report ANNEX

SCIENTIFIC REPORT – Period 1-1-2009 – 31-12-2009

The research activities of this action have been directed at the development of catalysts for alcohol conversion through oxidative processes in general, and glycerol conversion in particular, through a rational design approach based on operando spectroscopic data in combination with molecular modeling. Many STSM activities have been carried out in 2009. Intensive interactions between the modeling group in Paris, and the experimental groups in Madrid, Poznan, and Delft have been established. The involvement of the groups in Helsinki, München, and Utrecht have been less intensive the past year, due to changes in personnel (Maternity leave and leaving Post-Docs). One working group meeting was held in Paris, in addition to the meeting of the whole action in Benahavis, Spain. In the following, first the members of the group are indicated, the various STSM’s briefly presented, and specific details concerning the networking issues identified. Finally, an overview is given of the various papers that have been published in the framework of the topic of the present working group.

List of Participating groups

1. Sudchemie, Germany, (G. Mestl) 2. CSIC-Madrid, Spain (M. Banares, V. ) 3. Universite Paris, France (M. Calatayud, F. Tielens) 4. Mickiewicz University-Poznan, Poland (M. Ziolek, ) 5. Utrecht University, Netherlands (B.M. Weckhuysen, A.N. Parvulescu) 6. Delft University, Netherlands (G .Mul, A.R. Almeida) 7. Helsinki University of Technology, Finland (S. Airaksinen) 8. Bochum University, Germany (W. Grünert) 9. University of Malaga (O.

Working Group Meetings:

In the past year the second WGM of the project D36/006/2009 “Molecular structure-performance relationships at the surface of functional materials” took place 29th and 30th May 2009, at the following location:

Université Pierre et Marie Curie Place Jussieu, 4 75252 Paris – France

The second meeting was part of the D-36 meeting, and was held in Benahavis, Spain. See for information on this meeting the web-site that has recently been established: http://www.uma.es/costd36/board.html

II.A. Innovative networking

Innovative knowledge resulting from COST networking through the Action.

Significant scientific breakthroughs as part of the COST Action.

CaO catalyzed Glycerol Conversion

It was found that the presence of both strong basic sites and Lewis acid sites are necessary for the etherification of glycerol. The more basic the character of the oxide, the more exothermic is the adsorption and the higher the dissociation extent. Thus, the dissociation of glycerol increases in the series: MgO (not dissociated) < CaO < SrO < BaO (completely dissociated). The dissociation of glycerol forms surface hydroxyl groups that interact by hydrogen bonds with the molecule. The geometry of adsorption is determined by the topology of the surface, i.e. the lattice parameters and the basicity, together with the interaction with the surface hydroxyl groups. The M-O_glycerol distances correlate with the crystal lattice parameter. Regarding the adsorption modes, MgO shows a preference for top adsorption sites, while CaO, SrO and BaO stabilize bridging modes between two surface metal sites, due

to the larger M-Olatt distances. Overall, the modeling results nicely correspond to our experimental data and confirm our earlier observation that the strength of basic sites on the oxide surface is the main factor deciding the activity of the material in glycerol etherification. The differences in the reaction rate between different CaO materials during the activation period, when the oxide surface structure is still stable, also might be possibly connected with Lewis acidity. The aforementioned most Lewis-acidic CaO material also exhibits the highest rate of glycerol etherification during that activation period.

Synthesis and characterization of novel functionalized mesoporous materials

The group of Poznan important progress has been made in the synthesis and characterization of novel mesoporous materials functionalized by various transition metal oxides and noble metal particles relevant for the desired conversions of alcohols. Characterization has been performed in cooperation with the group of Miguel Banares in Madrid. Reactions with these materials have been attempted. Alcohol conversion (gas phase reaction) has been performed in the Poznan labs (see list of publications), and liquid phase oxidation of glycerol in aqueous media in Delft (see STSM reports Sobczak and Machej). The project is also progressing very well in the area of modeling. Satu Korhonen has completed two successful STSM’s and discussed in the meeting both some background on the activities in the field of glycerol oxidation, as well as her exciting results obtained in Paris. Monica Calatayud and Fred Thielens also presented exciting novel data on the structures and modeling of transition metal oxides (vanadia/titania) and zeolitic framework stability, respectively.

Silica-based materials doped by metals for glycerol conversion

Experimental (M. Trejda, Poznan) and theoretical (F. Tielens, Paris) investigations confirm that group 5 metals V, Nb, Ta were incorporated in the zeolite framework. Niobium samples showed the best incorporation affinity. Characterization is done by XRD, UV-vis and TEM, combined with DFT calculations on sodalite model. S. Dzwigaj (Paris) discussed the incorporation of Ti(IV) into BEA zeolites. The zeolites were synthesized and characterized using FTIR, 29Si-NMR, XRD, UV-vis and XPS. Different supports for gold used in glycerol oxidation to glyceric acid were characterized using XRD, UV-vis and TEM by M. Ziolek (Poznan). F. Tielens studied the results on the characterization of gold grafted silica materials with periodic DFT. An agreement between the experimental results and theoretical results was found on the form of the gold precursor as a function of the pH of the solution during grafting reaction. The groups of Madrid and Paris have exchanged samples for characterization by complementary experimental techniques.

Methanol oxidation reactions on vanadia catalysts

Basic steps in methanol oxidation were studied from DFT calculations (P. Gonzalez, Paris) studied the molecular reaction mechanism for the oxidation of methanol on supported vanadium oxide catalysts. First, the dissociation of the molecule on V-OH or V-O-Ti takes place. Further steps (mainly the electron transfer) are found to proceed through vanadyl V=O groups via a two-state mechanism. The formation of different products, dihydrogen, water and formaldehyde, is analyzed by the accurate calculation of the corresponding energy barriers for the rate limiting step. Five-fold vanadium intermediates are found to be potentially interesting for reactivity, since the barrier for the oxidation step is considerably decreased. The molecular structure of vanadia catalysts was studied from experimental (A. Lewandowska, Madrid) and theoretical (M. Calatayud) methods for alkali-doped and hydrated materials. In both cases the vanadyl V=O bonds are found to stretch causing a red-shift of the corresponding band, in agreement with Raman spectra.

Cyclohexane photo-catalytic oxidation on anatase

The photocatalytic oxidation of cyclohexane to cyclohexanone on a commercial anatase catalyst has been investigated (A. R. Almeida, G. Mul, Delft). The selectivity is found to depend on the desorption rate, and several methods have been tested to improve such step, such as increasing temperature or blocking surface sites by hydrophobic groups. Periodic DFT calculations have been carried out to unravel the atomic structure of the catalyst as regards the most exposed planes, the hydration degree, the presence of Lewis and Bronsted sites.

Summary of STSM’s conducted

Tangible medium term socio-economic impacts achieved or expected.

Academic and Industrial Institutions are expected to benefit from the educational aspects of the STSM achievements. This is particularly so in view of the large participation of ‘Early Stage Researchers’ in the STSM program.

Spin off of new EC RTD Framework Programme proposals/projects.

Integrated processing of lignocellulosic materials to chemicals (LIGNOCELLUCHEM) N/A

Spin off of new National Programme proposals/projects. (List)

COST Domain Chemistry and Molecular Sciences and Technologies Proposal Reference oc-2009-1-4487 Title: Holistic Approach Towards Controlling Heterogeneous Catalysed Reactions

COST Domain Chemistry and Molecular Sciences and Technologies Proposal Reference oc-2009-1-4159 Title: Rational catalyst design through precise mechanistic and kinetic understanding Call identifier: FP7-2009-BIOREFINERY; ENV.2009.3.3.2.2 Sustainable Biorefineries

COLLABORATIVE PROJECT:

II.B. Inter-disciplinary networking

Additional knowledge obtained from working with other disciplines within the COST framework.

Evaluation of whether the level of inter-disciplinarity is sufficient to potentially provide scientific impacts.

Evaluation of whether the level of inter-disciplinarity is sufficient to potentially provide socio-economic impacts.

II.C. New networking

Total number of individual participants involved in the Action work

1. Miguel A. BAÑARES, Prof. Dr. (Spaniard) 2. Vanesa CALVINO-CASILDA, Dr. (Spaniard) 3. Anna E. LEWANDOWSKA, Dr.(Polish) 4. Olga GUERRERO-PEREZ, Dr. (Spaniard) .... moved to Universidad de Malaga 5. Ricardo LOPEZ-MEDINA, MSc. PhD student (Mexican) 6. Elizabeth ROJAS-GARCIA, MSc, PhD student (Mexican) 7. Ewelina Joanna MIKOLAJSKA, MSc, PhD student (Polish) 8. Manuel GARCIA-CASADO, PhD student (Spaniard) 9. María José VALERO-PEDRAZA, PhD student (Spaniard-French) 10. Bert M. Weckhuysen 11. Andrei Parvulescu 12. Gerhard Mestl 13. Inga 14. Prof. Maria Ziolek 15. Dr Izabela Sobczak 16. Dr Maciej Trejda 17. Hanna Golinska 18. Anna Wojtaszek

19. Witold Klimas 20. Monica Calatayud 21. Frederik Tielens 22. Christian Minot 23. Stanislaw Dwzigaj 24. Olga Syzgantseva 25. Patricio Gonzalez 26. Mazrahul M. Islam 27. Outi Krause 28. Sanna Airaksinen 29. Inkeri Kauppi 30. Wolfgang GRUENERT 31. Mr. Sascha Heikens (M. Sc.) 32. Ms. Olga Petrova (M. Sc.). 33. Mr. Patrick

STSMs carried out during the year

Involving WG6 groups

- Anna E. Lewandowska, ICP to UPMC, (20 Feb - 8 Mar 2009) Alkali doped vanadia catalysts

- Elizabeth Rojas Garcia, ICP to UPMC, (20 May – 20 July 2009) Ammoxidation reaction on VSbO4

- Ana Rita Almeida, TU Delft to UPMC (October –November 2009) Photooxidation of cyclohexane to cyclohexanone on Anatase TiO2

Involving several other COST actions/working groups

- M. Islam, UPMC to Milano (20 July-20 September 2009) Hydrogen diffusion in anatase. Involves COST actions D36 and D41.

- Elizabeth Santos, U. Ulm to UPMC (15 Sept- 22 Sept) Self assembled materials COST D36 WG5

- Noelia Luque, U. Ulm to UPMC (15 Oct- 15 Dec) Self assembled materials COST D36 WG5

Involvement of researchers from outside of COST Countries

Advancement and promotion of scientific knowledge through publications and other outreach activities

N/A

Activities and projects with COST network colleagues.

N/A

The capacity of the Action members to raise research funds

Banares Group

IN SITU/OPERANDO RAMAN AND UV-Vis FOR REAL TIME SPECTROSCOPIC CONTROL OF FIXED BED CATALYSTS (AutOPERANDO)” (CONTROL ESPECTROSCOPICO EN TIEMPO REAL DE CATALIZADORES DE LECHO FIJO USANDO RAMAN Y UV-VIS IN SITU/OPERANDO (AutOPERANDO)) Grant# CTQ2008-04261/PPQ;

Agency: MCINN, Spanish Ministry of Science and Innovation 100 000 €, 1 4-year fellowship IP: Miguel A. Bañares

CHAIRMANSHIP OF COST ACTION D36 (PRESIDENCIA ACCIÓN COST D36 ESF) Grant # ACI2008-0727, ACI-LIDERA (Acción Complementaria Internacional) - 73.500 €, 2009-2012 Agency: MCINN, Spanish

ANNEX – DETAILED LIST OF PUBLICATIONS

International Journals

M. Calatayud, A. M. Ruppert, B. M. Weckhuysen Theoretical Study on the Role of Surface Basicity and Lewis Acidity on the Etherification of Glycerol over Alkaline Earth Metal Oxides Chemistry: A European Journal 15 (2009) 10864

A. Wojtaszek, I. Sobczak, M. Ziolek, F. Tielens Gold Grafted to Mesoporous Silica Surfaces, a Molecular Picture J. Phys. Chem. C 113 (2009) 13855

M. Trejda, M. Ziolek, P. Decyk, D. Duczmal The radical species and impurities present in mesoporous silica as oxidation active centres”, Microp. Mesop. Mater., 120 (2009) 214 – 220

H. Golinska, P. Decyk, M. Ziolek, E. Filipek Sb-V-Ox catalysts - role of chemical composition of MCM-41 supports in physicochemical properties Catal. Today, 142 (2009) 175-180

Raman Spectroscopy for the Structural Characterization of Operating Catalysts”, M.A. BaÑares, G. Mestl, ADVANCES IN CATALYSIS, 52 (2009) Chapter 2, pages 43-128 REVIEW by invitation only

M. Ziolek, M. A. Bañares, I. E. Wachs (Guest Editors), Preface, Catalysis Today, 142 (2009) 91

V. Calvino-Casilda, M. O. Guerrero-Pérez, M. A. Bañares Efficient microwave-promoted acrylonitrile sustainable synthesis from glycerol Green Chemistry 11 (2009) 939-941

Elizabeth Rojas, M. Olga Guerrero-Pérez, Miguel A. Bañares Direct ammoxidation of ethane: an approach to tackle the worldwide shortage of acetonitrile, Catalysis Comm. 10 (2009) 1555-1557

I. Sobczak, M. Ziolek, N. Kieronczyk Gold-vanadium-niobium catalysts in environmental protection – adsorption and interaction of NO, C3H6 and O2 – FTIR study Adsorption, 15 (2009) 145–155

M. Trejda, A. Wojtaszek, M. Ziolek, J. Kujawa Various hexagonally ordered mesoporous silicas as supports for chromium species – the effect of support on surface properties Applied Catalysis A: General 365 (2009) 135–140

A. Wojtaszek, I. Sobczak, M. Ziolek, F. Tielens Gold Grafted to Mesoporous Silica Surfaces, a Molecular Picture J. Phys. Chem. C 113 (2009) 13855–13859

I. Sobczak

The role of niobium in MCM-41 supported with Pt and Au – a comparative study of physicochemical and catalytic properties Catal Today, 142 (2009) 258-266

H. Golinska, M. Ziolek, M.O. Guerrero-Perez, M.A. Banares Ammoxidation of propane on mesoporous materials containing SbVOx Studies in Micro-and Mesoporous Materials, 1 (2009) 151-158

A. Wojtaszek, A. Floch, M. Trejda M. Ziolek The possible location of V, Nb and Ta in the framework of faujasite type zeolite Studies in Micro-and Mesoporous Materials, 1 (2009) 115-120

J. Florek, P. Decyk, M. Ziółek Mesoporous SBA-3 materials containing Cu – physicochemical and catalytic properties Studies in Micro-and Mesoporous Materials, 1 (2009) 79-84

W. Klimas, P. Decyk, M. Trejda, M. Ziółek Amorphous vs crystalline niobium containing catalysts in liquid phase oxidation with hydrogen peroxide Studies in Micro-and Mesoporous Materials, 1 (2009) 177-182

Oral Communications

M. Calatayud, A. M. Ruppert and B. M. Weckhuysen Glycerol etherification over alkaline earth metal oxides: a periodic DFT study ABC-6 6th world congress on Catalysis by Acids and Bases, Genova, Italy, 10-14 May 2009

A.N. Parvulescu, P.C.A. Bruijnincx, P.J.C. Hausoul, M. Arias, R.J.M. Klein Gebbink, B.M. Weckhuysen Etherification of glycerol and other biomass-derived polyols: New routes to valuable bulk chemicals COST Chemistry D36 3rd Workshop and 5th Management Committee Meeting, Benahavís, Spain, 21-23 October, 2009

P. C. A. Bruijnincx, A. M. Ruppert, A. N. Parvulescu, M. Arias, P. J. C. Hausoul, M. Calatayud, R.J.M. Klein Gebbink, B. M. Weckhuysen Etherification of Glycerol and Other Biomass-Derived Polyols: New Routes to Valuable Bulk Chemicals AiCHE Annual Meeting, Nashville, USA, 8-13 November 2009

A.E. Lewandowska, M. Calatayud, C. Minot, M.A. Bañares Combination of theory and experiment to study the effect of alkali additives on the structure and reactivity of the vanadium catalytic system Operando III, Rostok, 19-23 April, 2009, Germany

Golinska, Hanna; Ziolek, Maria; Guerrero-Perez, M. Olga; Banares, Miguel A.; Calvino-Casilda, Vanesa New V-Sb oxide catalysts on MCM-41 supports for ammoxidation of propane and novel ammoxidation of glycerol;, EuropaCat IX, 30 Aug – 4 Sep., 2009, Salamanca, Spain

E. Rojas, R. Lopez-Medina, M. Ziolek, Miguel A. Bañares, M.O. Guerrero-Pérez, H. Golinskaa The effect of porosity of niobosilicate supports and VSbOx loading on the ammoxidation of propane”, 3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

R. López-Medina, H. Golinska, M. Ziolek, Miguel A. Bañares, M.O. Guerrero-Pérez Nanostructured MoVNbTeO Oxide Catalysts for Selective Oxidation Reactions 3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

J. Ewelina Mikolajska, Anna E. Lewandowska, Miguel A. Bañares Operando Studies of VPO catalysts in n-butane selective oxidation reaction. Activity, selectivity and structure transformations 3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

Elizabeth Rojas, Mónica Calatayud, M. Olga Guerrero-Pérez, Miguel A. Bañares Theoretical Investigation of the Ammonia Adsorption Process on (110)-VSbO4 Surface

3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

Ana R. Almeida, Guido Mul Adsorption of cyclohexanone on TiO2 surfaces: modelling and ATR_FTIR spectroscopy 3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

I. Sobczak, K. Jagodzinska, M. ZiolekGlycerol oxidation on gold catalysts supported on group five metal oxides – acomparative study with other metal oxide and carbon based catalysts 3rd Workshop and 5th Management Committee Meeting; 21-23 October 2009, Benahavis, Spain

Poster Communications

F. Tielens, E. Santos SH and AuS bond formation during the formation of alkylthiol SAMs on Au(111) studied with DFT COST Chemistry D36 3rd Workshop and 5th Management Committee Meeting, Benahavís, Spain

F. Tielens, A. Wojtaszek, I. Sobczak, M. Ziolek Gold clusters on mesoporous silica surfaces in the presence of chloride – periodic DFT calculations EuropaCat IX, Salamanca, Spain, 30th August- 4th September, 2009.

E. Rojas, M. Calatayud, O. Guerrero-Pérez, M. A. Bañares Theoretical Investigation of the Ammonia Adsorption Process on (110)-VSbO4 Surface. COST Chemistry D36 3rd Workshop and 5th Management Committee Meeting, Benahavís, Spain 21-23 October 2009

H. Golinska, E. Rojas, R. Lopez-Medina, M. Ziolek, M.A. Banares, M.O. Guerrero- Perez The effect of porosity of niobosilicate supports and VSbOx loading in ammoxidation of propane COST Chemistry D36 3rd Workshop and 5th Management Committee Meeting, Benahavis, Spain, 21-23 October 2009

Anna Wojtaszek, Anna Floch, Maciej Trejda, Maria Ziolek Zeolites of Y Type containing Nb, V Or Ta COST D36 Working Group meeting, Paris, 29-30th May 2009

Maciej Trejda, Anna Floch, Maria Ziolek Solid state interaction of vanadium and tantalum oxides with Y zeolites EUROPACAT IX, Salamanca, Spain, 2009

H. Golinska, M. Ziolek, M.O. Guerrero-Perez, M.A. Banares Ammoxidation of propane on mesoporous materials containing SbVOx Forum Zeolitowe, Skorzęcin, 2009

J. Florek, P. Decyk, M. Ziółek Mesoporous SBA-3 materials containing Cu – physicochemical and catalytic properties Forum Zeolitowe, Skorzęcin, 2009

W. Klimas, P. Decyk, M. Trejda, M. Ziółek Amorphous vs crystalline niobium containing catalysts in liquid phase oxidation with hydrogen peroxide Forum Zeolitowe, Skorzęcin, 2009

A. Wojtaszek, A. Floch, M. Trejda M. Ziolek The possible location of V, Nb and Ta in the framework of faujasite type zeolite Forum Zeolitowe, Skorzęcin, 2009

I. Sobczak, K. Jagodzinska, M. Ziolek Glycerol oxidation on gold catalysts supported on group five metal oxides – acomparative study with other metal oxide and carbon based catalysts COST D 36 3rd Workshop, Benahavis (Malaga), Spain, 21-23 2009

M. Trejda, A. Wojtaszek, A. Floch, M. Ziolek, R. Wojcieszak, E.M. Gaigneaux

New V, Nb, Ta – FAU zeolites – texture and surface properties COST D 36 3rd Workshop, Benahavis (Malaga), Spain, 21-23 November 2009

A. Wojtaszek, A. Floch, M. Trejda, M. Ziolek The possible location of V, Nb and Ta in the framework of faujasite type zeolite WG COST D 36 3rd Meeting, Benahavis (Malaga), Spain, 24 2009

WG D36/007/06 2009 Annual Report

Molecular Catalysis and Photocatalysis at Soft Interfaces: Towards Chemical Fuel Cells

Proposed Start Date: 01.01.2007

Report

The milestone of this project is to continue developing the idea of reactivity at the liquid– liquid interfaces. In particular, joint efforts have been directed towards the oxygen reduction reaction for fuel cell applications and more recently to hydrogen generation. Accordingly, a collaboration network has been set among five institutions: EPFL – Ecole Polytechnique Fédérale de Lausanne JHIPC – J. Heyrovský Institute of Physical Chemistry TKK – Helsinki University of Technology BUTE –Budapest University of Technology LIMSAG – Université de Bourgogne Selçuk University

The long-term objective is the design of a novel class of “chemical fuel cells” based on a soft interface. The followed strategy has been maintained unchanged and strongly relies on the combination of research groups from the six institutions aforementioned with expertise in the synthesis of molecular catalysts, theoretical electrochemistry, photoelectrochemistry at liquid–liquid interfaces, molecular dynamics and quantum–mechanical calculations. The work in our WG has been distributed according to the expertise and experimental facilities acquired over the years by the different groups. In such a way, the groups from EPFL and JHIPC have centered their attentions on the electrochemical aspects of oxygen reduction at liquid-liquid interfaces, including classical four-electrode electrochemistry, surface tension measurements and modelling of the electrochemical processes.

1 Molecular Catalysis and Photocatalysis at Soft Interfaces

Analogously, the LIMSAG has been in charge of the development of synthetic strategies for the obtention of macrocyclic compounds capable of acting as surface–active catalysts towards the oxygen reduction reaction (see Figure 2). On the pursuit of a very efficient catalyst, water–soluble porphyrins have been recently synthesized, namely Tetramethylpyridinium–porphyrin, Dodecylpyridinium–porphyrin and Tetrasulphonate– porphyrin, whose catalytic activities are still to be evaluated. The group in BUTE has been working on the computer simulations on the interfacial microscopic structure and roughness. Thus, molecular dynamics calculations at the liquid–liquid and liquid–vapor interface have been conducted. In the same way, during the last year the group in TKK has made the first preliminary essays on the construction of a porphyrin–based fuel cell (see Figure 1). The operating principle of this device is mainly based on the catalytic cycle proposed for the oxygen reduction reaction at the classical liquid–liquid interfaces. It is also with great joy that we have seen our WG expanding since the Selçuk University from Turkey has also joined our working group this year as a consequence of the very fruitful collaboration that started late in 2008 with Prof. Ersoz and Ms. Imren Hatay.

Fig. 1. Schematic representation of a porphyrin–based fuel cell.

2 Molecular Catalysis and Photocatalysis at Soft Interfaces

It has also to be pointed out that during the last year, special emphasis has been made on the hydrogen evolution process catalyzed by metallocenes. The latter opened new horizons for the development of a liquid–liquid interface based–system for water photo– splitting. At present, the evaluation of different metallocenes towards a controlled hydrogen evolution reaction is under study. Briefly, the influence on their reactivity is being evaluated by systematically varying either the cyclopentadienyl ring substituents or the metallic center.

Fig. 2. Catalytic cycle proposed for the oxygen reduction reaction catalyzed by CoTPP.

As a promising branch derived from this project, during the second semester of 2009 at the EPFL, the first investigations on the reduction of CO2 at the novel liquid–liquid interfaces formed between water and supercritical CO2 have been carried out. The latter thanks to the experience acquired in the development of the oxygen and proton reduction reactions. Indeed, it is very common to have a competition between CO2 reduction and hydrogen evolution given that the potentials required for these processes are in close proximity. Furthermore, theoretical confirmation of the reaction pathways has also been considered as an important point. This has been accomplished by an internal collaboration at the EPFL with Prof. Corminboeuf. In particular, special attention has been paid to the free–

3 Molecular Catalysis and Photocatalysis at Soft Interfaces base porphyrin catalyst reaction mechanism, where quantum–mechanical calculations have proven to be vital on the formulation of a reaction pathway.

-1 +0.834 kcal mol (+0.036 eV) -5.47 kcal mol-1 (-0.237 eV)

… + … 2+ Fig. 3. Structures of the [H3FAP O2] (Left) and [H4FAP O2] adduct. Unrestricted M05-2X/6-31G* binding energies are zero-point and counterpoise corrected. Averaged closest O-H distances are given in Angstrom.

4 Molecular Catalysis and Photocatalysis at Soft Interfaces

Molecular Catalysis and Photocatalysis at Soft Interfaces: Experimental and Modelling

COST Action, D36/007/06 Proposed Start Date: 01.01.2007; Duration: 4 years;

List of Publications related to the projects (in bold joint communications):

1) 3D-ITIES supported on porous reticulated vitreous carbon, S. Tan, M. Hojeij, B. Su, G. Meriguet, N. Eugster and H. H. Girault, Journal of Electroanalytical Chemistry, 604, 2007, 65-71. 2) Molecular electrocatalysis of the oxygen reduction at a polarized interface between two immiscible electrolyte solutions by Co(II) tetraphenylporphyrin, A. Trojanek, V. Marecek, H. Janchenova and Z. Samec, Electrochemistry Communications, 9, 2007, 2185-2190. 3) Cyclic voltammetry of ion transfer across a room temperature ionic liquid membrane supported by a microporous filter, J. Langmaier and Z. Samec, Electrochemistry Communications, 9, 2007, 2633-2638. 4) Random nucleation and growth of Pt nanoparticles at the polarized interface between two immiscible electrolyte solutions, A. Trojanek, J. Langmaier and Z. Samec, Journal of Electroanalytical Chemistry, 599, 2007, 160-166. 5) Selective chemisorption of carbon monoxide by organic-inorganic hybrid materials incorporating cobalt(II) corroles as sensing components, J.-M. Barbe, G. Canard, S. Brandes, R. Guilard, Chemistry – A European Journal, 13, 2007, 2118-2129. 6) Through space singlet-singlet and triplet-triplet energy transfers in cofacial bisporphyrins held by the carbazoyl spacer, C. P. Gros, S. M. Aly, M. El-Ojaimi, J. –M. Barbe, F. Brisach, A. Abd-Ei-Aziz, R. Guilard, P. D. Harvey, Journal of Porphyrins and Phthalocyanines, 11, 2007, 244-257. 7) Temperature dependence of the structure of the liquid-vapour interface of aqueous

5 Molecular Catalysis and Photocatalysis at Soft Interfaces

methanol solutions, L. B. Partay, P. Jedlovszky, G. Horvai, Journal of Molecular Liquids, 134, 2007, 111-119. 8) Protoporphyrin IX sensitized titanium oxide gel electrode, S. Tan, B. Su, C. Roussel and H. H. Girault, Inorganica Chimica Acta, 361, 2008, 746-760. 9) Nanoporous Photocathode and Photoanode Made by Multilayer Assembly of Quantum Dots, M. Hojeij, B. Su, S. Tan, G. Meriguet and H. H. Girault, ACS Nano, 2, 2008, 984-992.

10) H2O2 Generation by Decamethylferrocene at a Liquid-Liquid Interface, B. Su, R. N. Partovi, F. Li, M. Hojeij, M. Prudent, Z. Samec, H. H. Girault, Angewandte Chemie International Edition, 47, 2008, 4675-4678. 11) Porphyrin ‘‘Mille-Feuilles” photo-electrodes, S. Tan, B. Su, M. Hojeij and H. H. Girault, Journal of Electroanalytical Chemistry, 621, 2008, 322-329. 12) Evidence of tetraphenylporphyrin monoacids by ion-transfer voltammetry at polarized liquid-liquid interfaces, B. Su, F. Li, R. Partovi-Nia, C. Gros, J.-M. Barbe, Z. Samec and H. H. Girault, Chemical Communications, 2008, 5037- 5038. 13) Properties of free surface of water-methanol mixtures. Analysis of the truly interfacial molecular layer in computer simulation, L. B. Partay, P. Jedlovszky, A. Vincze, G. Horvai, Journal of Physical Chemistry B, 112, 2008, 5428-5438. 14) Behavior of molecular oxygen at the liquid-liquid interface: A molecular dynamics simulation study, A. Vincze, P. Jedlovszky, L. B. Partay and G. Horvai, Chemical Physical Letters, 457, 2008, 78-81. 15) A new method for determining the interfacial molecules and characterizing the surface roughness in computer simulations. Application to the liquid-vapor interface of water, L. Partay, G. Hantal, P. Jedlovsky, A. Vincze, G. Horvai, Journal of Computational Chemistry, 29, 2008, 945-956. 16) Molecular level structure of the liquid-liquid interface. Molecular dynamics simulation and ITIM analysis of the water-chloroform system, L. Partay, G. Horvai and P. Jedlovsky, Physical Chemistry Chemical Physics, 10, 2008, 4754- 4764. 17) Use of the 1,1’-dimethylferrocene oxidation process for the calibration of the

6 Molecular Catalysis and Photocatalysis at Soft Interfaces

reference electrode potential in organic solvents immiscible with water, J. Langmaier, A. Trojanek, Z. Samec, Journal of Electroanalytical Chemistry, 616, 2008, 57-63. 18) Acid-base-driven interconversion between a mononuclear complex and supramolecular coordination polymers in a terpyridine-functionalized dioxocyclam ligand, A. Gasnier, J. –M. Barbe, C. Bucher, F. Denat, J. –C. Moutet, E. Saint-Aman, P. Terech, G. Royal, Inorganic Chemistry, 47, 2008, 1862-1864. 19) Efficient two-step synthesis of face-to-face meso-substituted bis(corrole)dyads, M. El-Ojaimi, C. P. Gros, J. –M. Barbe, European Journal of Organic Chemistry, 7, 2008, 1181-1186. 20) Face-to-face pacman-type porphyrin-fullerene dyads: design, synthesis, charge- transfer interactions, and photophysical studies, F. D'Souza, E. Maligaspe, P. A. Karr, A. L. Schumacher, M. El-Ojaimi, C. P. Gros, J. –M. Barbe, K. Ohkudo, S. Fukuzumi, Chemistry - A European Journal, 14, 2008, 674-681. 21) Clarification of the Oxidation State of Cobalt Corroles in Heterogeneous and Homogeneous Catalytic Reduction of Dioxygen, K. M. Kadish, J. Shen, L. Fremond, P. Chen, M. El-Ojaimi, M. Chkounda, C. P. Gros, J. –M. Barbe, K. Ohkubo, S. Fukuzumi, R. Guilard, Inorganic Chemistry, 47, 2008, 6726-6737. 22) Solvent, anion, and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles, J. Shen, M. El-Ojaimi, M. Chkounda, C. P. Gros, J. –M. Barbe, J. Shao, R. Guilard, K. M. Kadish, Inorganic Chemistry, 47, 2008, 7717-7727. 23) Proton pump for oxygen reduction catalyzed by CoTPP, R. N. Partovi, B. Su, F. Li, C. P. Gros, J. –M. Barbe, Z. Samec and H. H. Girault, Chemistry - A European Journal, 15 (2009) 2335-2340. 24) Hydrogen evolution at liquid-liquid interfaces, I. Hatay, B. Su, F. Li, R. Partovi-Nia, H. Vrubel, X. Hu, M. Ersoz, H. H. Girault, Angewandte Chemie–International Edition, 48 (2009) 5139-5142. 25) Voltammetry for surface-active ions at polarisable liquid|liquid interfaces, M. A. Méndez, B. Su, H. H. Girault, Journal of Electroanalytical Chemistry, 634 (2009)

7 Molecular Catalysis and Photocatalysis at Soft Interfaces

82-89 26) Proton-Coupled Oxygen Reduction at Liquid-Liquid Interfaces Catalyzed by Cobalt Porphine, I. Hatay, B. Su, F. Li, M. A. Méndez, T. Khoury, C. P. Gros, J.-M. Barbe, M. Ersoz, Z. Samec, H. H. Girault, Journal of the American Chemical Society, 131 (2009) 13453-13459. 27) Electrochemical evidence of catalysis of oxygen reduction at the polarized liquid-liquid interface by tetraphenylporphyrin monoacid and diacid, A. Trojanek, J. Langmaier, B. Su, H. H. Girault, Z. Samec, Electrochemistry Communications, 11 (2009) 1940-1943. 28) Oxygen reduction by decamethylferrocene at liquid/liquid interfaces catalyzed by dodecylaniline, B. Su, I. Hatay, F. Li, R. Partovi-Nia, M. A. Méndez, Z. Samec, M. Ersoz and H. H. Girault, Journal of Electroanalytical Chemistry, Accepted for publication.

Conferences and seminars: Prof. Hubert H. Girault participated at the 42nd Heyrovsky discussion held in Trest, Czech Republic on June 2009. In his plenary lecture entitled “Hydrogen Production at Soft Interfaces” the concept of reactivity at the liquid–liquid interfaces towards energy generation alternative methods was presented.

Prof. Hubert H. Girault was invited as a guest professor at the Selçuk University in Turkey on October 2009, and gave a keynote lecture at the 8th Turkish Electrochemistry Meeting entitled: “Bio-inspired electrochemistry: H2 production and O2 reduction” to the present the WG activities.

Dr. Bin Su, now Professor at the Department of Chemistry at Zhejiang University, participated at the 60th International Society of Electroshemistry Annual Meeting held in Beijing, China in September 2009 and gave a seminar entitled “Oxygen Reduction at Liquid/Liquid Interfaces”.

8 Molecular Catalysis and Photocatalysis at Soft Interfaces

Ms. Raheleh Partovi Nia participated at the 60th International Society of Electrochemistry Annual Meeting held in Beijing, China in September 2009 and gave a seminar entitled “Proton pump for oxygen reduction catalyzed by CoTPP”.

Prof. Girault gave a plenary lecture to the Chinese Electrochemical special meeting in Beijing (August 2009) entitled “ Bio-inspired electrochemistry at soft interfaces”.

9 WG D36/008/06 2009 Annual Report

II.A. Innovative networking

The basic ideas underlying the project dealt on colloid entities prone to interactions with bio-systems and on the interactions between such objects and surfactants, polymers and proteins, to form new colloid entities. Techological as well as fundamental implications may be forecast. According to the aforementioned statements, a collaboration involved studies on the interactions between surfactant- based vesicles and nano-particles, on the fundamental aspects of associative block co- polymers and so forth. This work has been performed from a collaboration with the group in Barcelona, whereas the part relative to interactions between surfactants in molecular form and nano-particles was mostly developed in collaboration with Maribor and Graz. Work on novel surfactants was essentially performed in collaboration with Calabria. Examples of the links occurring between the above groups can be inferred from the following list:

Interactions between nano-particles and surfactant assemblies. 1. Stable TiO2 dispersions for nano-coating preparation. N. Veronovski, P. Andreozzi, C. LaMesa, M. Sfiligoj-Smole Surface & Coatings Technology, 204 (2010) 1445–1451. (jointly with Maribor) Use of Gemini Surfactants to stabilize TiO2 P25 colloidal dispersions. 2. N. Veronovski, P. Andreozzi, C. La Mesa, M. Sfiligoj-Smole, V. Ribitsch Colloid Polym.Sci., (2009), publ. online 21 Oct., DOI 10.1007/s00396-009-2133-x. (jointly with Maribor and Graz) 3. Gemini Surfactant Binding onto Hydrophobically Modified Silica Nanoparticles. Andreozzi, P.; Pons, R.; Perez, L.; Infante, M.R.; Muzzalupo, R.; Suber, L.; La Mesa, C. Journal of Physical Chemistry C, (2008), 112(32), 12142- 12148. (jointly with Barcelona and Calabria)

Vesicle-based systems. 4. Catanionic Vesicles Formed with Arginine-Based Surfactants and 1,2- Dipalmitoyl snglycero-3-phosphate Monosodium Salt. Lozano, N.; Pinazo, A.; La Mesa, C.; Perez, L.; Andreozzi, P.; Pons, R. Journal of Physical Chemistry B, (2009), 113(18), 6321-6327. (jointly with Barcelona)

Novel surfactant systems. 5. Solubilization of Lipo-philic Species by Aqueous Pluronics, S. Pede, G. Gente, F. Tardani, P. Andreozzi, C. La Mesa, G.A. Ranieri, C. Oliviero Rossi. In preparation. (jointly with Calabria) 6. Niosomes from a ,w - trioxyethylene-bis (sodium 2- dodecyloxypropylenesulfonate) : Preparation and characterization. Muzzalupo, R.; Tavano, L.; Trombino, S.; Cassano, R.; Picci, N.; La Mesa, C. Colloids and Surfaces, B: Biointerfaces, (2008), 64(2), 200-207. (jointly with Calabria)

Spin off of new ES RTD Framework programme. The work on the interactions between nano-particles and vesicles is expected to be of relevance in Spin-off projects, due to its possible implications in bio- medicine. The same holds for perspectives in National projects.

Interdisciplinarity This is a long terms strategy we formerly used and still continue to deal with. As a matter of facts, collaborations are effective between physicists, chemists, biologists and chemical engineers. It would be great to extend our knowledge to other scientifically oriented disciplines in COST Action projects and we are doing our best on this regard. At present we feel that socio-economic impacts of the project may come from previous work and from the acceptance from national scientific and research groups.

• Spain (IQAC-CSIC): Mª Rosa Infante (coordinator), Aurora Pinazo, Lourdes Perez, Ramon Pons, Aurora Colomer, Jordi Morros, Neus Lozano

• Lund (Lund University): Bjorn Lindman, Gerd Olofsson, Dan Lundberg and Olle Söderman

• Portugal (Coimbra University): Maria G. Miguel, Carmen Moran, Rita Dias, Diana Costa, Artur Valente, Filipe Antunes

• Italy (La Sapienzza University of Roma): Camillo La Mesa,Patrizia Andreozzi, Adalberto Bonincontro, Luigi Coppola, Federica De Persiis, Luciano Galantini, Claudia Leggio, Isabella Nicotera, Nicolae V. Pavel, Cesare Oliviero-Rossi, Giuseppe A. Ranieri, Gianfranco Risuleo, Franco Tardani, Mohamed Youssry, Piero Rainieri and Fioretta Asaro

• Austria (Graz University): Volker Ribitch, Martin Reischl, Heike Ehmann, Doris Breitwieser,

• Slovenia (Maribor University): Karin Stana-Kleinschek, Lidija Fras Zemljič, Aleš Doliška, Silvo Hribernik, Majda Sfiligoj Smole, Simona Strnad, Tatjana Kreže, Olivera Šauperl, Zdenka Peršin, Matej Bračič, Manja Kurečič

• Brusels (Beneo Co.) Bart Levecke

STSM

Jordi Morros; 9 Dec-23 Dec 2009; University of Coimbra (Portugal) COST-STSM-D36- 05478

New Networking

We are rising funding from companies active in the EU areas (BASF, in primis).

Articles in collaboration published in 2009-

1. Physicochemical and toxicological properties of novel amino acid-based amphiphiles and their spontaneously formed catanionic vesicles. R.O. Brito et al Colloids and Surfaces B: Biointerfaces 2009, 72, 80–87 (Portugal/Spain) 2. Interaction of arginine-based cationic surfactants with membranes. An experimental and molecular simulation. S. Almeida et al. Arkivoc 2010 (v) 34-50 ; (Portugal/ Sweden/ Spain) 3. Catanionic Vesicles Formed with Arginine-Based Surfactants and 1,2-Dipalmitoyl- sn-glycero-3-phosphate Monosodium Salt Lozano, N. et al Journal Physical Chemistry B, 2009,113, 6321-6327 (Italy/Spain) 4. Modeling the Surfactant Uptake in Cross-Linked DNA Gels. Costa, D et al. Journal of Dispersion Science and Technology, 2009, 30, 954 - 960 (Portugal/Sweden/Austria) 5. Cotton Cellulose 1, 2, 3, 4 Buthanetetracarboxylic Acid (BTCA) Crosslinking Monitored by some Physical-chemical Methods . Sauperl, O. et al Textile Research Journal 2009,79, 780-791 (Austria/Slovenia/Italy) 6. Electrokinetic Properties of Polypropylene-Layered Silicate Nanocomposite Fibers Smole MS et al. Journal of Applied Polymer Science 2009, 113,1276-1281 (Austria/Slovenia) 7. Enzymatic Degradation of Model Cellulose Film Pre-Treated with Antimicrobial Agent Jausovec D et al. Journal of Dispersion Science and Technology 2009, 30, 929-936 (Slovenia/Sweden) 8. M.Youssry, L.Coppola, I. Nicotera, M. C.Morán; Swollen and collapsed lyotropic lamellar rheology; J. Colloid Interface Sci, 321, 459-467, 2008. 9. S. Gaweda, M. C. Morán, A.A.C.C. Pais, R. S. Dias, K. Schillén, B. Lindman, M. G. Miguel; Cationic agents for DNA compaction; J. Colloid Interface Sci, 323, 75-83, 2008. 10. L. Coppola, M. C. Morán, M. R. Infante, L. Pérez, M. Youssry, I. Nicotera, A. Pinazo; Aqueous self-assembly and physicochemical properties of 1,2-dilauroyl- rac-glycero-3-(N-alpha-acetyl-L-arginine); Colloids and Surfaces A: Physicochemical and Engineering Aspects, 327, 111-121, 2008. 11. RS Dias, LM Magno, AJM Valente, PK Das, S Maiti, MG Miguel, B Lindman Interaction between DNA and cationic surfactants: effect of DNA conformation and surfactant headgroup; J Phys Chem B. , 112, 11310-11316, 2008. 12. A Papancea, AJM Valente, S Patachia, MG Miguel, B Lindman; PVA – DNA cryogel membranes: characterization, swelling and transport studies. Langmuir , 24, 273–279, 2008 13. M. Rosa, N. Penacho, Sérgio Simões, M.C.P. de Lima and B. Lindman, M.da G. Miguel ; DNA Pre-Condensation with Amino Acid-Based Cationic Surfactants - A Viable Approach for Liposome-Based Gene Delivery, ; Molecular Membrane Biology, 25, 23-34, 2008. 14. V. Jadhav, S. Maiti, A. Dasgupta, P. K. Das, R. S. Dias, M. G. Miguel, B. Lindman; Effect of the head-group geometry of amino-acid based cationic surfactants on interaction with plasmid DNA, Biomacromolecules, 9, 1852-1859, 2008. 15. T. Santos, B. Medronho, F. Antunes, B. Lindman, M. G. Miguel; How does a non-ionic hydrophobically modified polymer interact with a non- ionic vesicle? ; Colloids and Surfaces A, 319, 173-179, 2008. 16. B. Medronho, S. Shafaei, R. Szopko, M G. Miguel, U. Olsson, C. ; chmidt, Shear-induced transitions between a planar lamellar phase and multilamellar vesicles: Continuous versus discontinuous ; ransformation, Langmuir, 24, 6480, 2008. 17. M. C. Morán, T.Laranjeira, A. Ribeiro, M. G. Miguel, B. Lindman; Chitosan-DNA particles for DNA delivery: Effect of chitosan molecular weight on formation and release characteristics; J. Dispersion Sci. Technol.10, 1494-1499, 2009. 18. M. C. Morán, F. R. Baptista, A. Ramalho, M. G. Miguel, B. Lindman; DNA gel nanoparticles: preparation and controlling the size ; Soft Matter, 5, 2538-2542, 2009. 19. M. F.V. Pinto, M. C. Morán, M. G. Miguel, B. Lindman, A.S. Jurado, A.A.C.C. Pais; Controlling the morphology in DNA condensation and precipitation; Biomacromolecules, 10, 1319-1323, 2009. 20. M. C. Morán, A.A.C.C. Pais, A. Ramalho, M. G. Miguel, B. Lindman; Mixed protein carriers for modulating DNA release ; Langmuir, 25, 10263–10270, 2009. 21. M. Davies, H. Burrows, S. Cheng, M. C. Morán, M. G. Miguel, P. Douglas; Cationic fluorene- based conjugated polyelectrolytes induce compaction and bridging in DNA; Biomacromolecules, 10, 2987-2997, 2009. 22. Filipe E. Antunes, Eduardo F. Marques, Maria G. Miguel, Björn Lindman, Polymer–vesicle association,; Advances in Colloid and Interface Science 147–148, 18–35, 2009. 23. M.C. Morán, M. R. Infante, M. G. Miguel, B. Lindman. R. Pons. ; Novel biocompatible DNA gel particles. ; Langmuir, submitted 24. J. A. S. Almeida, M. C. Morán, M. R. Infante, A.A.C.C. Pais; Interaction of arginine- based cationic surfactants with lipid membranes. An experimental and molecular simulation study.; Arkivoc, V, 34-50, 2010.

Book Chapters

1. Interactions of DNA with surfactants. R. S. Dias, K. Dawson, M. G. Miguel, In DNA Interactions with Polymers and Surfactants; R. S. Dias, B. Lindman,(Eds). ; Wiley- Blackwell, New Jersey, 2008.

2. Cross-linked DNA Gels and Gel Particles. D. Costa, M. C. Morán, M. G. Miguel, B. Lindman In DNA Interactions with Polymers and Surfactants; R. S. Dias, B. Lindman, (Eds.);Wiley-Blackwell, New Jersey, 2008.

3. Manipulation of DNA by Surfactants. B. Lindman, R.S. Dias, M. G.Miguel, M. C Morán D. Costa. In Highlights in Colloidal Science ; D. Platikanov, D. Exerowa (Eds.): Wiley-VCH, Weinheim, 2009

4. DNA-Surfactant Systems: Particles, Gels and Nanostructures, B. Lindman, R. S. Dias, M. G. Miguel, M. C. Morán, D. Costa, V. Starov(ed.), in Nano-Science: Colloidal Background, Taylor & Frances, 2009, in press.

Conference attended

1. M.C. Morán, A. Ramalho, A.A.C.C. Pais, M. G. Miguel, B. Lindman; Lysozyme- protamine particles as new DNA carriers; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Oral presentation. 2. M. L. Davies, H. D. Burrows, P. Douglas, M. G. Miguel, M. C. Morán; Investigation into the interaction of a novel cationic conjugated polyelectrolyte with DNA;7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 3. J. Balogh, M. C. Morán, M. G. Miguel, B. Lindman; Non-ionic microemulsion networked by DNA; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 4. P.A.M.M.Varandas, A.J.M.Valente, D.M.B. Murtinho, M.E.S. Serra, M.C. Morán, R.S. Dias,M. G. Miguel, B. Lindman; Interaction between DNA and bolaform surfactants: effect of surfactant headgroups and chain lengths; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 5. D.A. Cerqueira, A.J.M. Valente, H.D. Burrows, M. C. Morán, R.F.P. Pereira, A. Salinas-Castillo, R. Mallavia, G.R. Filho, V.M.M Lobo; Cellulose acetate-poli- (9,9-bis(6´-bromohexyl)fluorene phenylene) blend films as solid matrices for recognition of ss-DNA; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 6. M. F. V. Pinto, M. C. Morán, A.A.C.C. Pais, A.S. Jurado, M. G. Miguel; Controling the compaction/precipitation behaviour of DNA molecules; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 7. T. Laranjeira, M. C. Morán, A. Ribeiro, F. Veiga, M. G. Miguel, B. Lindman; Chitosan particles for DNA delivery: effect of chitosan molecular weight on formation and release characteristics; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 8. F. R. Baptista, M. C. Morán, M. G. Miguel, B. Lindman; DNA gel particles: effect of the cationic agent on the particle size; 7th International Symposium on Polyelectrolytes (Polyelectrolytes 2008); June 2008. Coimbra (Portugal). Poster presentation. 9. M. C. Morán, A Ramalho, A. A. Pais, M. G. Miguel, B.Lindman ; New approaches in DNA- gel particles ; 22nd Conference of the European Colloid and Interface Society (ECIS); September 2008. Cracow (Poland). Oral presentation. 10. M. L. Davies, H. D. Burrows, P. Douglas, M. G. Miguel, M. C. Morán; Investigation into the interaction of a cationic conjugated polyelectrolyte with DNA; 22nd Conference of the European Colloid and Interface Society (ECIS) 11. September 2008. Cracow (Poland). Poster presentation. 12. M. G. Miguel, M. C. Morán, B. Lindman; DNA gel nanoparticles: preparation and controlling the size; Neutrons in Biology meeting (NIB 2009); June 2009. Lund (Sweden). Poster presentation. 13. M. C. Morán, M. R. Infante, M. G. Miguel, B. Lindman, R. Pons; Novel biocompatible DNA gel particles; III Reunión Ibérica de Coloides e Interfases (RICI) –VIII Reunión del Grupo Especializado de Coloides e Interfases (GECI) 14. July 2009. Granada (Spain). Oral presentation. 15. S. M.A. Cruz, A. J. M. Valente, M. C. Morán, M. G. Miguel, B. Lindman; Release kinetics of DNA from PVA/DNA blends gels; III Reunión Ibérica de Coloides e Interfases (RICI) –VIII Reunión del Grupo Especializado de Coloides e Interfases (GECI); July 2009. Granada (Spain). Poster presentation. 16. M. C. Morán, M. G. Miguel, B. Lindman; New challenges in DNA gel particles: from millimeter to nanoscale improving biocompatibility; 23rd Conference of the European Colloid and Interface Society (ECIS); September 2009. Antalya (Turkey). Poster presentation. 17. J. M. Valente, S. M. A. Cruz, D. M. B. Murtinho, M. C. Morán, B. Lindman, M. G. Miguel; DNA-Poly(vinyl alcohol) gel matrices: release properties are strongly dependent on electrolytes and cationic surfactants.; 23rd Conference of the European Colloid and Interface Society (ECIS); September 2009. Antalya (Turkey). Poster presentation. 18. J. Balogh, M. C. Morán, K. Schillén, M. G. Miguel, J. S. Pedersen; Compaction of DNA and interaction between DNA and nonionic microemulsion; 23rd Conference of the European Colloid and Interface Society (ECIS); September 2009. Antalya (Turkey). Poster presentation

Activities and projects with COST network colleagues.

1. Title: 2007PO0050 “Tensioactivos biocompatibles en la complexación de biopolímeros”.; Financial support: MEC-FCT; Date: 2008-2009; IP Dr. M. R. Infante (Spain)-M. G. Miguel (Portugal) 2. Principal investigador Dr. M. R. Infante (Spain)-M. G. Miguel (Portugal) ; Place: Surfactant Technology IIQAB-CSIC/ Chemistry Department-FCTUC 3. Presentation of a project in the 7FP Call title FP7-NMP-2010-SMALL-4; NMP.2010.1.2-2: Substitution of materials or components utilising “green nanotechnology” 4. Resekostnader kurs, Surfactants and polymers in aqueous solution, 16-20 november 2009, i Lisssabon, Portugal.