COST Domain Committee

"Chemistry and Molecular Sciences and Technologies"

COST Action D36 Molecular Structure-Performance Relationships at

the Surface of Functional Materials

MONITORING PROGRESS REPORT

Period: from 24/02/2006

to 31/12/2008

This Report is presented to the relevant Domain Committee and contains two parts:

I. Management Report prepared by the COST Office

II. Scientific Report prepared by the Chair of the Management

Committee of the Action

The report is a “cumulative” report, i.e. it is updated annually and covers the entire period of the Action. Confidentiality: the documents will be made available to the public via the COST Action web page except for chapter II.C. Self evaluation. Based on the monitoring results, the COST Office will decide on the following year’s budget allocation.

I. Management Report prepared by the COST Office I.A. COST Action Fact Sheet

● COST Action D36 Molecular Structure-Performance Relationships at the Surface of

Functional Materials

• Domain Chemistry and Molecular Sciences and Technologies ”CMST”

• Action details: Details

Draft Mou: 299/05 Mou: 208/06 Start of Action: 24/02/2006 Entry into force: 14/10/2005 End of Action: 23/02/2011 CSO approval date: 14/06/2005

• Objectives (from DB as in About COST)

The main objective of the Action is to increase the fundamental knowledge and

understanding of the chemistry occurring at surfaces and interfaces and the factors that

tune it. An interdisciplinary, combined effort is the approach. A fundamental approach is

advocated, even for industrially oriented research projects. This requires precisely

defined problems at all levels and an interdisciplinary approach i.e. synthesis and

activation of the materials; measurement of the surface properties; understanding

surface properties at the atomic, molecular or cluster level and theoretical understanding

of these properties in relation to chemical composition and the structure of the surface.

As a consequence, the secondary objective is to gain advanced knowledge for

modelling/predicting of the structure/composition reactivity/surface properties

relationships of the materials, by means of characterisation of the bulk and surface

properties under real operation conditions and for preparing materials with tuneable properties • Parties: list of countries and date of acceptance Country Date Country Date Country Date Country Date

Austria 17/02/2006 Belgium 14/10/2005 Bulgaria 21/11/2005 Czech Republic

15/11/2005

Denmark 14/10/2005 Finland 02/05/2006 France 06/06/2006 Germany 13/10/2005 Greece 14/10/2005 Hungary 25/10/2005 Ireland 19/10/2005 Italy 05/01/2006 Latvia 15/12/2005 Netherlands 13/10/2005 Norway 14/10/2006 Poland 14/10/2005

Portugal 22/05/2006 Romania 14/10/2005 Slovenia 06/12/2005 Spain 17/10/2005 Sweden 14/10/2005 Switzerland 14/10/2005 United

Kingdom 24/10/2005

Total: 23 • Intentions to accept: list of countries and date Intentions to accept the MoU Country Date Country Date Country Date Country Date

Turkey N/A Total: 1

● Other participants: (Institution Name, Country, Town) Country Date Country Date Country Date Country Date Total: 0 Management Commitee Chair Vice Chair DC Rapporteur Dr. Miguel BANARES CSIC - Instituto de Catalisis Marie Curie, 2 E-28049 Madrid, Spain banares@icp.csic.es

Professor Robert SCHOONHEYDT Centre for Surface Chemistry and CatalysisFLTBWCatholic University of Leuven Kardinal Mercierlaan 92 3001 Louvain Belgium robert.schoonheydt@agr.kuleuven.ac.be

Professor Vasile PARVULESCU Department of Chemical Technology & CatalysisFaculty of Chemistry University of Bucharest B-dul Regina Elisabeta 4-12 030016 Bucharest Romania vasile.parvulescu@g.unibuc.ro

Contacts MC Chair Science Officer: Administrative Officer: Dr. Miguel BANARES Tel. +34 91 585 4788 Fax. +34 91 585 4760 banares@icp.csic.es

Javier CALDENTEY COST Office +32 2 533 38 17 jcaldentey@cost.esf.org

Svetlana VOINOVA COST Office +32 2 533 38 48 svoinova@cost.esf.org

• Action Web site: http://www.cost.esf.org/index.php?id=189&action_number=d36

• Grant Holder(name, e-mail)

• Working Groups (list of WGs and name) ►D36-0001-05 Redox activity of host organometallic and structures at electrode

interfaces

►D36-0003-06 Interfacial functionalization of (bi)-metallic nanoparticles to prepare

highly active and selective catalysts: understanding synergy and/or promotion effect

►D36-0005-06 Structure-Reactivity Relationship of Pt and Pd Nanoarrays

►D36-0006-06 Understanding the chemical reactivity of alcohols over catalytic

materials: from probe molecules to practical applications

►D36-0007-06 Molecular Catalysis and Photocatalysis at Soft Interfaces: Towards

chemical fuel cells

►D36-0008-06 Biopolymers based surfactants- Stabilization and functionalization of

particles and surfaces

Austria

Dr. Volker RIBITSCH Kolloide - Polymere Institut für physikalische Chemie Universität Graz Heinrichstrasse 28 Graz AT volker.ribitsch@uni-graz.at

Belgium

Professor Eric GAIGNEAUX Faculté d'ingénieurie Biologique, Agronomique et Environementale Université Catholique de Louvain Croix du Sud 2/17 Louvain-la-Neuve BE gaigneaux@cata.ucl.ac.be

Bulgaria

Professor Donka ANDREEVA Institute of Catalysis Bulgarian Academy of Sciences Acad. G. Bonchev” str., bl. 11 Sofia BG andreev@ic.bas.bg Czech Republic

Professor Hynek BIEDERMAN Mathematics & Physics Faculty Charles University VXO. Holešovickách 2 Prague 8 CZ bieder@kmf.troja.mff.cuni.cz

Professor Lubomir POSPISIL Organic and Organometallic Electrochemistry J. Heyrovsky Institute of Physical Chemistry Academy of Sciences of the Czech Republic Dolejskova 3 Praha CZ lubomir.pospisil@jh-inst.cas.cz

Denmark

Professor Preben J. MØLLER University of Copenhagen Universitetsparken 5 Copenhagen DK pjm@kiku.dk

Finland

Dr. Sanna AIRAKSINEN Laboratory of Industrial Chemistry Helsinki University of Technology FI-02015 TKK FI sanna.airaksinen@hut.fi

France

Professor Jacques FRAISSARD Laboratoire de Physique Quantique - ESPCI 10 rue du Vauquelin Paris FR jfr@ccr.jussieu.fr

Professor Christian FERNANDEZ UMR 6506 Université de Caen LCS - CNRS 6 boulevard du Maréchal Juin Caen FR christian.fernandez@ensicaen.fr

Dr. François GARIN Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse Ecole Européenne Chimie Polymères Matériaux Université Louis Pasteur 25, rue Becquerel Strasbourg FR garin@chimie.u-strasbg.fr

Germany

Professor Franz-Peter MONTFORTS Institut für Organische Chemie Universität Bremen Leobener Straße NW 2 Postfach 33 04 40 Bremen DE mont@slater.chemie.uni-bremen.de

Dr. Klaus D. SCHIERBAUM Institut für Physik der kondensierten Materie Heinrich-Heine-Universität Düsseldorf Universitätsstr. 1 Geb. 25.23 Düsseldorf DE schierb@uni-duesseldorf.de

Greece

Dr. Kostas S. TRIANTAFYLLIDIS Center for Research and Technology Hellas Chemical Process Engineering Research Institute PO Box 361 Thermi 6th km Harilou-Thermi road Thessaloniki GR ktrianta@cperi.certh.gr

Professor Soghomon BOGHOSIAN Chemical Technology and Applied Physical Chemistry University of Patras Patras GR bogosian@iceht.forth.gr

Hungary

Professor András ERDOHELYI Institute of Solid State and Radiochemistry University of Szeged POB 168 Szeged HU erdohely@chem.u-szeged.hu

Professor Lászlň GUCZI Institute of Isotopes and Surface Chemistry Hungarian Academy of Sciences P.O. Box 77 Budapest HU guczi@sunserv.kfki.hu

Ireland

Dr. James SULLIVAN School of Chemistry & Chemical Biology University College Dublin Belfield Dublin IE james.sullivan@ucd.ie

Professor Julian R.H. ROSS College of sciences University of Limerick Limerick IE Julian.Ross@ul.ie

Italy

Dr. Anna Maria VENEZIA ISMN CNR Via Ugo La Malfa 153 Palermo IT venezia@pa.ismn.cnr.it

Latvia

Dr. Ludmila LEITE Laboratory of Catalytic Synthesis Latvian Institute of Organic Synthesis Aizkraukles iela 21 Riga LV leite@osi.lv

Netherlands

Professor Guido MUL Faculty of Applid Sciences Delft University of Technology Julianalaan 136 NL G.Mul@tudelft.nl

Professor Bert WECKHUYSEN Debye Instituut Utrecht University Sorbonnelaan 16 Utrecht NL b.m.weckhuysen@chem.uu.nl

Norway

Dr. Gisle ŘYE Norwegian University of Science and Technology - NTNU Ugelstad Laboratory TRONDHEIM NO gisleoy@nt.ntnu.no

Poland

Professor Maria ZIOLEK Faculty of Chemistry Adam Mickiewicz University 6 Grunwaldzka Str. Poznan PL ziolek@amu.edu.pl

Professor Barbara GRZYBOWSKA-SWIERKOSZ Institute of the Catalysis and Surface Chemistry Polish Academy of Sciences 8 Niezapominajek str. Kraków PL ncgrzybo@cyf-kr.edu.pl

Portugal

Professor Luisa Maria ABRANTES Faculdade de Ciencias Universidade de Lisboa R. Ernesto Vasconcelos, Ed.C8 Lisboa PT luisa.abrantes@fc.ul.pt

Romania

Dr. Viorica PARVULESCU Laboratory of Surface Chemistry and Catalysis Institute of Physical Chemistry I.G. Murgulescue Romanian Academy Spl. Independentei, 202 Bucharest 6 RO vpirvulescu@chimfiz.icf.ro

Mr. Ioan SANDULESCU Faculty of Chemistry University of Bucharest 36-46, M. Kogalniceanu Bd, Sector 5 Bucharest RO ioansandulescu@yahoo.com

Slovenia

Professor Karin STANA-KLEINSCHEK Faculty of Mechanical Engineering University of Maribor Maribor SI karin.stana@uni-mb.si

Professor Venceslav KAUCIC National Institute of Chemistry University of Ljublijana Hajdrihova 19 PO Box 660 Ljubljana SI kaucic@ki.si

Spain

Dr. Maria Rosa INFANTE Instituto de Investigaciones Quimicas y Ambientales CSIC Jordi Girena Salgado 18-26 Barcelona ES rimste@cid.csic.es

Sweden

Professor Sven Gunnar JARAS Division of Chemical Technology Royal Institute of Technology - KTH Teknikringen 42 Stockholm SE svenj@ket.kth.se

Dr. Magali BOUTONNET Division of Chemical Technology Royal Institute of Technology - KTH Teknikringen 42 Stockholm SE magali@ket.kth.se

Switzerland

Professor Hubert H. GIRAULT Laboratoire d`électrochimie physique et analytique Faculté des Sciences de Base Ecole Polytechnique Fédérale de Lausanne EPFL-SB-ISIC-LEPA Station 6 Lausanne CH hubert.girault@epfl.ch

United Kingdom

Professor Robert JONES School of chemistry University of Nottingham Nottingam UK robert.g.jones@nottingham.ac.uk

Dr. Wendy BROWN University College London 20 Gordon Street London UK w.a.brown@ucl.ac.uk

IC. Overview activities and expenditure

Action D36 - budget from 24-Feb-2006 to 31-Dec-2008

MeetingsMeeting Type Date Place Paid part Cost TotalManagement Committee 24-Feb-2006 Brussels (BE) 29 17930.14Management Committee 25-Sep-2006 Brussels (BE) 4 1833.59Management Committee 02-Oct-2006 Brussels (BE) 28 15255.57Working Group 19-Nov-2006 Prague (CZ) 4 1978.31Working Group 24-Nov-2006 Bruckmuhl (DE) 8 3473.28Working Group 30-Nov-2006 Lausanne (CH) 4 2859.43Working Group 01-Dec-2006 Warwick (uk) 8 4226.86Working Group 01-Dec-2006 Palermo (IT) 7 5916.26Working Group 08-Dec-2006 Barcelona (ES) 11 8385.23Working Group 17-May-2007Coimbra (PT) 10 8798.08In conjunction with Workshop/Conference01-Sep-2007 Espoo (FI) 41 32030.3Working Group 05-Oct-2007 Stockholm (SE) 8 7065.89Working Group 16-Nov-2007 Prague (CZ) 5 2719.79Working Group 26-Nov-2007 Arcavacata di Rende (IT) 10 7401.25Working Group 16-Dec-2007 Burgos (ES) 6 3326.08Working Group 04-Apr-2008 Dijon (FR) 5 3125.15Working Group 10-May-2008Poznan (PL) 7 4376.94Working Group 15-May-2008Graz (AT) 6 7340.41In conjunction with Workshop/Conference04-Sep-2008 Dublin (IE) 28 19402.76Working Group 26-Sep-2008 Villars (CH) 4 2655.7Working Group 24-Oct-2008 Nice (FR) 14 12644.27Working Group 14-Nov-2008 Delft (NL) 8 5336.46Working Group 28-Nov-2008 Leiden (NL) 5 2361.52Working Group 11-Dec-2008 Rome (IT) 10 8000

188443.3

STSMBeneficiary Date From To Cost TotalMr Jianjun Zhao 03-Dec-2006Berne (CH) Coventry (uk) 1280Dr Monica Calatayud 20-Dec-2006Paris (FR) Madrid (ES) 627Mr Akintayo Adisa 05-Mar-2007 Manchester (uk) Burgos (ES) 2440Ms Jana Bulickova 02-May-2007Prague (CZ) Dresden (DE) 852Ms Ilaria Degano 07-May-2007PISA (IT) Prague (CZ) 1200Ms Satu Korhonen 14-May-2007FI-02015 TKK (FI) 75252 Paris (FR) 1100Mr Jan Fiedler 16-May-2007Prague (CZ) 10125 Torino (IT) 1550Dr. Izabela Sobczak 01-May-2007Poznan (PL) Delft (NL) 2470Dr Maciej Trejda 01-May-2007Poznan (PL) Delft (NL) 2470Mr Gérôme Melaet 05-May-20071050 Bruxelles (BE) 90146 Palermo (IT) 2450Dr Michèle Salmain 24-Sep-2007Paris 75005 (FR) Prague 8 (CZ) 1500Dr Viorel Chihaia 01-Oct-2007 Bucharest (RO) Budapest (HU) 2000Ms Diana Costa 15-Sep-20073004-535 Coimbra (PT)Graz (AT) 2500Ms Satu Korhonen 01-Oct-2007 FI-02015 TKK (FI) Paris (FR) 2500Pr Björn Lindman 03-Jan-2008 Lund (SE) Maribor (SI) 1400Mr Alberto Martinez 02-Feb-2008 Burgos (ES) Manchester (uk) 2500Mr Edgar Ventosa 03-Feb-2008 Burgos (ES) Coventry (uk) 2500Ms Nika Veronovski 01-Mar-2008 2000 Maribor (SI) 00185 Roma (IT) 2500Mr Ivan Ivanov 14-Apr-2008 1113 Sofia (CZ) 90146 Palermo (IT) 2100Dr Anna Elzbieta LEWANDOWSKA18-May-2008MADRID (ES) UTRECHT (NL) 1470Ms Tímea Benkó 24-May-2008Budapest (HU) Palermo (IT) 1410Dr Filipe Antunes 17-May-2008Coimbra (PT) Rome (IT) 2280Ms Tina Tkavc 01-Apr-2008 Maribor (SI) Lund (SI) 2500Dr Romana Sokolova 23-Jun-2008 Prague (EE) Pisa (IT) 1380Mr Germán Soldano 15-Jun-2008 D89069 Ulm (DE) Leiden (NL) 2500Dr Agnieszka RUPPERT03-Aug-2008Utrecht (NL) Paris (FR) 1560Ms Anna Wojtaszek 05-Nov-2008 60-780 Poznań (PL)Paris (FR) 2500Ms Hanna Golinska 05-Nov-2008 60-780 Poznan (PL) E-28049 Madrid (ES) 2500

54,039

WorkshopsTitle Date Place Cost TotalWG 01 meeting: Redox activity of host-guest. organometallic and molecular structures at electrode interfaces19-Nov-2006 Prague (CZ) 545WG D38-06-06 meeting 24-Nov-2006 Bruckmuhl (DE) 600WG D36-003-06 meeting01-Dec-2006Palermo (IT) 700WG D36-008-06 meeting08-Dec-2006Barcelona (ES) 700Action D36 WG 008 meeting17-May-2007Coimbra (PT) 730Annual Workshop and MC meeting01-Sep-2007Espoo (FI) 3,426D36 WG06 meeting 03-Sep-2007Espoo (FI) 329WG 003-06 meeting 05-Oct-2007 Stockholm (SE) 573WG D36/007-06 meeting16-Nov-2007 Prague (CZ) 445WG D36/0008/06 Biopolymer based surfactants – stabilisation and functionalisation of particles and surfaces26-Nov-2007 Arcavacata di Rende (IT) 650WG D36/05/06 meeting 15-Dec-2007Burgos (ES) 600WG D36/007-06 meeting04-Apr-2008 Dijon (FR) 445WG D36/006/06 meeting10-May-2008Poznan (PL) 650WG D36/008 meeting 15-May-2008Graz (AT) 520COST D36 Annual Workshop+MC meeting04-Sep-2008Dublin (IE) 2,222COST WG D36/07 meeting26-Sep-2008Villars (CH) 200WG D36/03 meeting 24-Oct-2008 Nice (FR) 1,324WG D36/06-06 meeting 14-Nov-2008 Delft (NL) 284WG D37/005-06 meeting28-Nov-2008 Leiden (NL) 360

15,303

General Support GrantsTitle Date Cost Total

0

SchoolsType Date Place title Cost TotalSCHOOL_STUDENTS 24-Nov-2008 Leiden (NL) D36 TRAINING SCHOOL on ELECTROCATALYSIS at NANOSCALE techniques and applications9000

9000

HonorariaTitle Date Expert Cost Total

0

GrantGrant Holder Date Cost Total

0

266785.6

II.B. Dissemination of results During hardly more than one year, the groups have been most active, and there has been an important degree of dissemination, in several fields. The total number of papers done under COST D36 is already 76, which on average, means almost two papers per laboratory. Two of them are reviews. In addition, there have been three book chapters and members in two laboratories in WG D36/008/06 have filed two patents. The WG members have been very active and they have already reported their activities on 44 occasions at conferences and workshops. I’d like to highlight that among these, there have been several keynote and plenary lectures. One of them, within the exchange between COST D41 and COST D36, which is commented below. - Invited Plenary Lecture H. Girault, at 14th annual meeting of the Chinese Electrochemical

Society, Xiamen, China on 7-9, Nov., 2007 - Invited presentation, M. A. Bañares "Molecular structure-activity relationships on supported

oxide catalysts, relevance of additives and reaction conditions. A case study from COST D36 Action", COST Action D41 “Inorganic Oxides: Surfaces and Interfaces“ 2007 Annual Meeting of the COST D41 Action, Berlin, 21-23,Oct. 2007

- KEYNOTE LECTURE “Operando Raman Methodology: the combination of kinetic and structural information in a single experiment to understand catalytic operation”; 6-8.Dec.2006, in APCAT-4 (Asia Pacific Conference on Catalysis), Singapore. Miguel A. Bañares.

- PLENARY LECTURE - “Niobium as a promoter for oxidation catalysts”, 6th International Symposium on Group Five Elements, May 7-10, 2008, Poznañ, Poland -

- KEYNOTE - “Structure-Performance Relationships in Supported Vanadia Catalysts under Working Conditions based on Complementary Operando Raman-GC and in situ XANES spectroscopies”, SNBL Workshop on simultaneous Raman-X-ray diffraction/absorption studies for the in situ investigation of solid-state transformations, and reactions at non ambient conditions. 18

-19 June 2008, ESRF, Grenoble, Francia

- Web site WG D36-007-06 GIRAULT has already established a wiki site (WIKI.EPFL.CH) to allow al WG members share results, presentation, articles. A general access site is in preparation now, it provides links to COST D36 events and information about the WG’s involved in this action. Publication of a special issue in “CATALYSIS TODAY” on the first COST D36 workshop

On December 2008, a special issue in Catalysis Today, edited by Dr. Sanna Airaksinen - host and organizer of the symposium- has been published. It is devoted to the First COST D36 workshop, celebrated in Helsinki on Sepember 2007 (As described in Annex IV). Catalysis Today is a top-notch international journal. The special issue reports 13 papers reflecting the contributions presented there. This special issue is an important vehicle to disseminate the activities run at this Action and raises its visibility. It should be underlined that several non-COST participants attended this workshop, and this trends is expected to rise during the next workshop, to be beld near Malaga, Spain, in 2009. An outline of the issue is presented here: Catalysis Today Volume 139, Issue 3 pp. 153-242 (30 December 2008) First Workshop of COST Action D36 "Molecular Structure - Performance Relationships at the Surface of Functional Materials", Edited by Sanna Airaksinen

1. “Preface”, , Sanna Airaksinen 2. “Selective H–D exchange catalysed by aqueous phase and immobilised Pd

nanoparticles”, Pages 154-160, James A. Sullivan, Keith A. Flanagan, Holger Hain 3. Hydrotalcite docked Rh-TPPTS complexes as efficient catalysts for the arylation of 2-

cyclohexen-1-one in neat water, Pages 161-167 F. Neaţu, M. Besnea, V.G. Komvokis, J.-P. Genêt, V. Michelet, K.S. Triantafyllidis, V.I. Pârvulescu

4. NO reduction by CO over gold based on ceria, doped by rare earth metals, Pages 168-173, Lyuba Ilieva, Giuseppe Pantaleo, Ivan Ivanov, Radka Nedyalkova, Anna Maria Venezia, Donka Andreeva

5. Support effect on the catalytic performance of Au/Co3O4–CeO2 catalysts for CO and CH4 oxidation, Pages 174-179, L.F. Liotta, G. Di Carlo, A. Longo, G. Pantaleo, A.M. Venezia

6. Formation and structure of Au/TiO2 and Au/CeO2 nanostructures in mesoporous SBA-15, Pages 180-187, A. Beck, A. Horváth, Gy. Stefler, R. Katona, O. Geszti, Gy. Tolnai, L.F. Liotta, L. Guczi

7. Gold, vanadium and niobium containing MCM-41 materials—Catalytic properties in methanol oxidation, Pages 188-195, Izabela Sobczak, Natalia Kieronczyk, Maciej Trejda, Maria Ziolek

8. Nb-containing mesoporous materials of MCF type—Acidic and oxidative properties, Pages 196-201, Maciej Trejda, Jolanta Kujawa, Maria Ziolek, Julita Mrowiec-Białoń

9. Sb–V–O-based catalysts for the ammoxidation of propane with a fluidized bed reactor, Pages 202-208, M. Olga Guerrero-Pérez, José L. Rivas-Cortés, J.A. Delgado-Oyagüe, J.L.G. Fierro, Miguel A. Bañares

10. Combining theoretical description with experimental in situ studies on the effect of alkali additives on the structure and reactivity of vanadium oxide supported catalysts, Pages 209-213, Anna E. Lewandowska, Mònica Calatayud, Enrique Lozano-Diz, Christian Minot, Miguel A. Bañares

11. A DFT study of methanol dissociation on isolated vanadate groups, Pages 214-220, L. Gracia, P. González-Navarrete, M. Calatayud, J. Andrés

12. Nature of vanadium species in V substituted zeolites: A combined experimental and theoretical study, Pages 221-226, F. Tielens, M. Trejda, M. Ziolek, S. Dzwigaj

13. CO2 adsorption on (0 0 1) surfaces of metal monoxides with rock-salt structure, Pages 227-233, Ramzi Hammami, Adnene Dhouib, Sébastien Fernandez, Christian Minot

14. Modeling of gas transport in a microporous solid using a slice selection procedure: Application to the diffusion of benzene in ZSM5, Pages 234-240, Michel Petryk, Sebastien Leclerc, Daniel Canet, Jacques Fraissard

Second COST D36 Workshop, in September 2008, Dublin The second COST D36 workshop took place in Dublin on Septemer 2008. Several non-COST speaker participated actively, as invited speakers. Training School (in collaboration with Lorentz Workshop) on “Electrocatalysis@nanoscale: techniques and applications” Lorentz Center, Leiden University, The Netherlands, 24-28 November 2008 Local Organizers: Prof. Dr. Marc Koper, Dr. Alex Yanson International Organizers: Dr. David Fermin (Bristol), Prof. Dr. Patrick Unwin (Warwick) (WG D36-005-06) The purpose of this Training School was to bring together junior scientists from all WG’s in COSTD36 Action and

non-COST students to learn about the principles and possible applications of the various experimental techniques applicable to the study of the electrocatalytic systems. The Training School was held in the framework of a “Lorentz Workshop” at the Lorentz Center of Leiden University. The format of the meeting was set up so as to actively involve participants in solving their own research questions. Student participants were asked to formulate a pertinent research question from their own research before the start of the Training School. After the specialist training lectures in the morning and early afternoon sessions, in the afternoon discussions, students presented their research questions in small groups of 6 students and two experts. Electrocatalysis is a highly interdisciplinary discipline of science of great importance for our future energy economy (batteries, fuel cells, hydrogen production…). A good background in electrocatalysis, which would enable one to tackle all the important research problems in this area, requires knowledge of chemistry, physics, catalysis, materials science, electronics, nanotechnology, biochemistry, etc. This aspect is also reflected in the many different experimental techniques that are available to study electrocatalytic and electrochemical processes, which range from modifications of the classical spectroscopic techniques (Infrared, Raman, UV-VIS) to scanning probe microscopies (AFM, STM) to techniques based on electrical response (voltammetry, impedance spectroscopy, scanning electrochemical microscopy). Such a School was most successful, bringing COST and non-COST participants among professors and students. Many interactions are crystallizing among participants from different groups, inside and outside D36. Scientific and Technological Cooperation - Cooperation and contacts with scientific institution, other research programmed and potential

users. o An interaction has been established with Prof. G. Pacchioni, Chairman of COST D41 due

to complementary approaches in the area of oxide materials. It was agreed to promote mutual interactions by arranging a joint workshop after the second year, when a body of research is significant in both Actions. As a first Approach, Prof. Pacchioni, presented the Action D41 and representative results to D36 members at the First D36 Workshop, in Espoo, Finland, September 2007. In turn, Dr. Bañares presented the Action D36 and representative results to D41 members at the 2007 D41 Workshop, in Berlin, Germany, October 2007. Preliminary contacts have already been established between specific laboratories in D36 and D41.

o COST Action D36-006-06. The group of Paris has joined the Group of Madrid in a multidisciplinary project funded by CSIC in Spain on magnetic and catalytic properties of nanoscaled mixed oxide materials (Materials with new interface magnetism: origin, and application screening (MAGIN) 200680F0123, 199 000 €. (January 2007-December 2008). A workshop shall be organized on March.2008 among all groups involved (physics, chemists, materials science, magnetism, DFT modellization).

- Transfer of results o The WG initiated their activities ca. three months ago, so there has not been transfer yet.

It should be highlighted that two WG’s possess industrial partners involved. o Laboratories in WG-008-06 INFANTE have filed two patents.

- Contacts in the ERA (EUREKA, ESF, European coordinative research frameworks …) o The results obtained within the WG’s should constitute a seed for project proposals under

FP7 in the near future. Several consortia are now in progress of building up. o The First COST Workshop in Espoo, Finland, resulted in a proposal for a new Action,

coordinated by one of the non-COST invited speakers, Prof. G. Rupprechter ref. OC-2007-1457 “SPECTROSCOPY OF FUNCTIONING CATALYSTS” (under DC CMST)

ANNEXES

o I. Scientific achievements by the WG’s o II. Joint publications

ANNEX I: SCIENTIFIC ACHIEVEMENTS

WG D36-001-06 POSPISIL “Redox activity of host-guest, organometallic and molecular structure at electrode interfaces” L. Pospisil, WG coordinator

Joint research within this project was launched prior to its approval by the MC. Therefore, during 2006, we are able to report realization of 8 mutual scientific missions to partner laboratories amounting total 18 weeks of duration. Experimental work resulted in 5 joint publications and 5 congress communications. Two publications involved cooperation with a D35 project and with NSF. Results published can be summarized as follows. The joint research of host-guest complexes and their electrochemical reactivity involved complexes of fullerene and cyclodextrins. Two types of the research lines were followed: (a) Electrochemical generation of reactive anions of an inclusion complex of fullerene and gamma-cyclodextrin, which served as redox mediators for the conversion of gaseous nitrogen to ammonia. This activity produced one published and one accepted paper. (b) Water-soluble conjugates of fullerene and beta-cyclodextrin are currently studied with the aim to estimate the degree of internal complexation between the fullerene moiety and cyclodextrin cavity. In these studies participated the Prague group, ENS Paris and the Pisa group. New organometallic compounds were synthesized and the redox characterization was aimed at finding the correlation between the structure and communication of multiple redox centers. Compounds included ruthenium and other platinum-group central atoms with various bridging ligands. These studies identified mixed-valence states, the delocalization of the electron density and intervalence absorption. Research was performed and published jointly with another D35 project. The research targeted for a construction of surface structures dealt with newly prepared sandwich complexes of cobalt. One of the ligands was per–substituted cyclopentadienyl having mercury-alkane "arms" terminated by a sulfur group. This part of the complex was designed for anchoring of the future structure to the electrode surface. The upper deck of the complex contained the cyclobutadien ligand substituted with estheric functions, which are intended for chemical modifications of low-dimensional anchored structures. The methodology combined the electrochemical impedance and the Langmuir-Blodgett trough at mercury–acetonitrile interface. The structure–properties relationships were sought in a series of [n]helicenes with n=1 to 14. Helicenes are unique three-dimensional condensed poly-aromatics used as models of screw–shaped biomolecules or as new materials in the field of nano-science. The published work indicated the convergence of various properties with n→14. The WG published 7 papers and 11 congress presentations. Four STSM were granted. January-December 2008

The joint research of host-guest complexes and their electrochemical reactivity was extended to other type of possible complexes of fullerene and cyclodextrins. This WG investigated new compounds with cyclodextrin moiety covalently attached to the fullerene structure. The water-soluble complex of fullerene and gamma-cyclodextrin was characterized by the electrochemical impedance spectroscopy. This work was aimed at the optimization of conditions for the electrocatalytic nitrogen conversion to ammonia at mild conditions. Modeling of experimental data involved a search of parameters of the equivalent circuit of the

CD-C60-CD

CD-C60-CD2-

CD-C60-CD2-

2e-

N2

N2H2

N2H4

NH3

2e-

2e-

C60 + CD

CD-NH4+

NH4+

Mechanism of electrocatalytic conversion of nitrogen to ammonia

electrode impedance. Results were jointly published. We described a new type of cationic catalysis, which is based on ion pair interactions of nitro-aromatic radical anions generated at the electrode surface with alkali metal cations. The ion pair formation effectively diminishes the electrostatic repulsion of radicals from the interface. The effect is a strongly enhanced further reduction to reactive dianions of nitro-compounds. Furthermore, the described system yields a new type of spontaneous electric oscillations. The joint work also involved modeling of stability/oscillatory conditions. Results were jointly published and presented at the COST workshop in Dublin. The structure–properties relationships were sought in a series of [n]helquats with n=5 to 7.

Helquats are unique three-dimensional condensed polyaromatics, which fill the gap between helicenes and poly-viologenes. They are designed as models of screw–shaped biomolecules or as new materials in the field of the surface science. One communication was accepted and one conference presentation was made. Experiments, which could confirm the formation of biradicals are still in progress. Research of the electron transfer in new organometallic compounds included derivatives having various tri-dentate ligands binding multiple Ru and Os redox centers. The X-ray diffraction, DFT calculation and in situ spectroelectrochemistry confirmed the existence of singlet diradical complexes of Ru(IV) and Os(IV). Structural effects (N-N bond shortening), EPR characteristics (metal-centered spin) and UV-Vis spectra indicate the oxidation of two ligands and the reduction of the metal in the first oxidation step. This work proceeded jointly with a COST D35 project and resulted in 1 publication and 9 other papers reported by the partner’s project. Our WG published 4 papers and 6 congress presentations during 2008 (see Annexes). One STSM was granted. Three other exchange visits were financed from other local sources.

WG D36-003-06 VENEZIA Interfacial functionalization of (bi)-metallic nanoparticles to prepare highly active and selective catalysts: understanding synergy and/or promotion effect A. M. Venezia, WG coordinator The proposal of our working group, aims at determining the structure-property relationships in oxide and/or carbon supported metal catalysts to develop active materials approaching 100% selectivity for catalytic processes involved in environmental protection including removal of pollutant and search for cleaner source of energy. The project is organised in 7 tasks with the last two consisting of dissemination and exploitation of results. From the 1st of October 2006 until now, each team has carried out activities related with the main topic of the project. The first couple of months were devoted to strengthen the partnership, by exchanging ideas and planning exchange of researchers between different laboratories. During the first year the participant teams have focused their activity according to the schedule given in the proposal. The activities of each participant group are summarised as it follows: The Italian team lead by Prof. Anna M. Venezia from the Institute of Nanostructured Materials, CNR, Palermo, Italy has worked on the development of new catalytic systems of interest in fuel upgrading and total combustion of methane. Concerning the first application, noble metal catalysts

10 15 200

1

2

3

cu

rren

t /

µµ µµA

time / s

Current oscillations on dropping Hg electrode originating from the cationic

catalysis of nitro-aromatic radical reduction reduction.

Spiral-shaped di-quarternary polycondensated aromatic molecule of

(Pd, Au, Pt, mono and bi-metallic) and Co based catalyst promoted with noble metals were prepared, which were tested in the hydrodesulfurization of thiophene. Home made mesoporous silica such as MCM-41, HMS, SBA 15 were also used as supports. Interesting catalytic results were obtained with a pure monometallic Pd/HMS, exhibiting much higher and stable catalytic performance as compared to a Co catalyst. Its behavior was ascribed to a bi-functional mechanism. In the field of the methane combustion, in collaboration with the group lead by Prof. Norbert Kruse, some new Pd catalyst supported on TiO2 doped silica supports, prepared by sol-gel method, were studied. The effect of SO2 in the reaction feed was evaluated. A superior behavior in the total oxidation of methane, in terms of conversion and also resistance to sulfur poisoning was obtained. Such results were presented at the COST Chemistry D36, 1st Workshop, Helsinki, Finland, 1-2 September 2007. The Hungarian team lead by Prof. Laszlo Guczi from the Institute of Isotopes of the Hungarian Academy of Sciences has focused its activity on functionalizing Au/SiO2 catalyst, as well as on gold and promoter deposition over SBA-15 materials. Preparation of gold nanoparticles was carried out using 2 techniques: one based on the reduction of HauCl4 with citric and tannin acid, and the other based on the reduction by NaBH4. While the first approach gave Au average size of about 5-6 nanometer, the second one allowed to achieve 2 nm gold sols. After deposition of the Au sols, some surface modification was performed, which made the normally very inactive Au/SiO2 and AuSBA-15 samples highly active catalyst in both CO oxidation and in preferential CO oxidation (PROX). Iron oxide, TiO2 and CeO2 as promoter oxides were employed and the characterization of the samples were performed using HRTEM, XPS, XRD, TPR, etc. It was established that the surface morphology of the oxides is the decisive factor in controlling the catalytic activity. Part of this research was in collaboration with the Palermo team. The research of the French team lead by Prof. Jacques Fraissard from the Laboratory “Physique Quantique” ESPCI, Paris has been devoted mainly to the preparation of new catalysts, in particular those on carbons and bimetallic catalysts based on gold, in collaboration with colleagues from laboratories in Russia, Ukraine and the USA. They prepared bimetallic catalysts based on platinum or palladium added with gold, which was found to have a beneficial effect on the activity and selectivity of the main metal. The reactions considered were: a) oxidation of CO and hydrocarbons, in collaboration with the Krakow Catalysis Institute and b) isomerization of alkane. Moreover they find a technique for the study of the co-diffusion and co-adsorption (out of the equilibrium) of several species in a porous bed to be able to obtain the real intrinsic reaction rates. To this end they use 1H NMR imaging, developing an original apparatus which allows to select very rapidly (time of the order of the micro second to the millisecond) very thin layers (order of µm) of the catalysis bed moving rapidly vertically within the NMR magnet. In this way the classical NMR signals of the components at each level of the bed and their evolution with time could be obtained. They have also exploited the chemical shift associated with Xe-Xe interactions to define the pore structure of oxides like zeolites and also of micro and mesoporous carbon solids. The Bulgarian team lead by Prof. Donka Andreeva of the Institute of Catalysis, BAS, Sofia, Bulgaria, was focused on NOx removal and Water Gas Shift Reaction (WGS) of interest in the hydrogen technology. The results of the topic of NOx reduction by CO were obtained mainly in the framework of the research collaboration with the Palermo team. The influence of the preparation methods on the catalytic activity of supported gold catalysts in the reduction of NOx by CO was studied. The supports consisting of ceria modified by alumina were prepared by 2 different methods – by co-precipitation (CP samples) and by mechano-chemical activation (MA samples). Gold was loaded using deposition-precipitation method. The samples CP exhibited higher activity in comparison with the MA samples. A high a stable activity of gold supported on CeO2-Al2O3 catalysts has been established also in the WGS reaction, but differently from the previous reaction, MA samples behave better than the CP ones. The superior performance of the gold over MA prepared supports as compared to the CP one was related to the creation of surface oxygen vacancies. On the basis of the obtained results, a model of the active sites and the mechanism of WGS on gold/ceria catalysts was proposed. In accordance to tasks planned for the Krakow group, lead by Prof. Barbara Grzybowska, before her withdrawal from the project due to her retirement, they have prepared new series of supports such as chromites of transition metals, MIICr2O4 . MII = Co, Mg and Zn . The studies included the optimization of the calcination time and temperature. The samples (~5 g) of the above given supports were made available to other members of the WG for catalytic tests. The contribution given by the Brussels group lead by Prof. Norbert Kruse was in cooperation with three different partners and was dealing with the following topics: 1) Resistance of Pd-based catalysts to sulphur poisoning in cooperation with the Palermo group; 2) development of highly active Ag-based catalysts for CO oxidation in cooperation with the Budapest group; 3) Elucidation of

mechanistic details of the Fischer Tropsch reaction , planned cooperation with the Stockholm group for 2008. With respect to 1), as described above, the influence of titania doping on SiO2/TiO2-supported Pd catalysts with varying TiO2 amounts was studied. Thermal desorption of SO2 was observed to coincide with the onset of methane combustion, i.e. SO2 release triggered methane combustion in the presence of reactive gas mixtures. With respect to topic 2), TiO2-supported Ag catalysts were prepared by the co-precipitation of TiO- and Ag oxalates in the absence of water. After decomposing catalyst precursors in temperature programmed oxidation, the catalytic activity in CO oxidation was tested. With respect to 3), Ni- and Co- based catalysts were prepared according to the oxalate route. To study the microscopic mechanism of the Fischer Tropsch reaction (CO hydrogenation), transient chemical kinetics were applied under CO/H2 co-adsorption conditions. This allowed demonstrating that chain lengthening to form C2+ hydrocarbons proceeds via CO insertion, most probably into the O-H bond of surface hydroxyl groups. Formate-type species therefore seem to be important intermediates and have indeed been identified by IR spectroscopy. The contribution of the Rumenian team lead by Prof. Gabriel Munteanu consisted in the theoretical modeling of non-isothermal experiments to investigate the effect of particle dispersion, catalyst composition and catalyst pre-treatment on the reducibility of catalytic systems. In collaboration with Sofia and Palermo the TPD study of CO and NO over gold-ceria catalysts for NOx reduction by CO was afforded. It was shown that the adsorption of NO both on gold/ceria and gold/ceria-alumina is reversible. The contribution by Prof. Magali Boutonnet of Dept. Chem. Eng. and Tech. CTC, Stockholm consisted in the preparation of Co catalysts promoted by Re and supported on TiO2 (mostly rutile) for use in the Fischer-Tropsch synthesis (FTS) run in conditions to favour the production of high hydrocarbons (waxes), which are subsequently hydrocracked to the diesel fraction. The bimetallic particles were prepared in microemulsion (Berol 02 / cyclohexane / water) as well as by conventional incipient wetness impregnation. The metal particles prepared as microemulsion were deposited onto the TiO2 support by destabilization with acetone. This technique allows to prepare quite smaller CoRe particles (12 nm) in large pores as compared to the impregnation method. Moreover the group has developed new Ceria doped ZrO2 as catalyst support of Rh for partial oxidation of methane. The same method of microemulsion was used to prepare mixed oxide supports for nickel catalysts for the selective catalytic oxidation of ammonia in gasified biomass. Promising results were obtained at λ = 0.25 using the 10 wt.% Ni on Ce0.9La0.1O2 with a 65 and 97% N2 yield at 500 and 750 °C, respectively. Moreover, NOx emissions maintained at low levels depending on the experimental conditions. Constant conversion and negligible carbon deposition were also two other important findings from the mixed metal oxide supported catalysts. On the contrary, all the alumina-based catalysts displayed the lowest performance. A closer collaboration with the Palermo team is planned for the 2008. Other activities: Kick off meeting, 1-2 December 2006, Istituto dei Materiali Nanostrutturati del Consiglio Nazionale

delle Ricerche (ISMN-CNR) , Palermo, Italy WG Meeting, 5-6 Oct 2007, Department of Chemical Engineering, Chemical Technology, KTH,

Stockholm, Sweden STSM granted to Mr Gérôme Melaet, Université Libre de Bruxelles (Prof. Kruse)for the period of

01/05/2007 to 31/05/2007 in Palermo (Prof. Venezia) STSM granted to Dr. Viorel Chihaia from Institute of Physical Chemistry, Bucarest, (Prof. Munteanu)

for a period of 4 weeks from 1/10/ 2007 in Budapest at the Institute of Chemistry (Prof. Guczi).

January-December 2008

The objective of our working group is to develop catalytically active materials, consisting of oxide and/or carbon supported metal catalysts, through the investigation of structure-property relationships. The final and practical aim is to achieve 100% selectivity for catalytic processes involved in environmental protection including removal of pollutant and search for cleaner source of energy. The project is organized in the following 5 work packages:

� WP1- Development of model catalysts mainly formed by controlled deposition of mono (Au, Pd, Pt) and then bimetallic (Au/Pd, Pd/Rh) layers over single crystal support in order to study interface properties, reactivity of defects sites and adsorption of simple molecules;

� WP2- Preparation of real heterogeneous catalysts through a variety of wet chemistry methods; � WP3-Characterization through XPS, XRD, NMR, TPR/TPO, FIM, TEM, STM; � WP4-Catalytic tests in PROX, WGS, HDS and HDA, CH4 and VOC oxidation; � WP5- Theoretical modeling of the reactions; � WP6- evaluation of the relationship between structure and activity; WP3 to WP6 cannot be considered as separate activities since they are always auxiliary to WP1 and WP2.

Concerning the first work package focused on the development of model catalysts, as a collaboration between the groups in Budapest (prof. Guczi) and in Palermo (Prof. Venezia), nanostructures of Au/TiO2 and Au/CeO2 supported on Mesoporous SBA-15 were prepared and investigated in order to understand the effect of Au/oxide interface on catalytic activity. 2 wt% Au was deposited from HAuCl4 precursor by different ways: (i) by deposition precipitation (DP) using Na2CO3 (AuTiSBA_DP); (ii) by preparation of Au colloid (Au_PVA), reducing HAuCl4 at room temperature with NaBH4 in presence of PVA as stabilizer, followed by its impregnation on silica SBA-15 (pH =1,5 (AuTiSBA_PVA); (iii) by reduction of Au precursor with NaBH4 in presence of poly(diallyldimethylammonium) chloride (PDDA) (86 mg/l) in the aqueous suspension of the support (AuTiSBA_PDDA); (iV) by impregnation of AuSBA_PVA by aqueous solution of Ti(IV) bis(ammoniumlactato) dihydroxide (TALH) yielding (AuSBA_PVA_T.) Quite interestingly, the catalytic activity of the inert oxide supported Au-active oxide system in the CO oxidation was primarily controlled by the anchoring properties between the active oxides and the gold nanoparticles. It was shown that the activity was strongly affected not only by the Au particle size, but by the length of Au/TiO2 or Au/CeO2 perimeter, related to the surface charges of the components in the different preparations (electrostatic interaction between the three components (Au, TiO2 or CeO2 and SiO2). As shown in Fig.1, over the titania doped SBA-15 the Au particles prepared by the DP or by PVA are well dispersed and stable after the reaction. The catalysts were tested in the oxidation of propene as a model compound for the VOC abatement. Among the three gold catalysts over pure oxides the activity decreased as AuCe > AuTi > AuSBA. Over mixed oxides, AuSBACe was the best performing catalyst. The different catalytic behaviour was explained in terms of stabilization of particle size and atomic distribution as derived from TEM and XPS analyses. Some recent works has also addressed the importance of the morphology and crystal structure of the active support. It was proven how the change in TiO2, Fe2O3 and CeO2 morphology affects the surface structure and catalytic activity in the CO oxidation. The crucial point in developing interaction between 3 dimensional nanoparticles and supporting materials is the nature, morphology and electron properties of the support.

Fig.1 TEM images of AuTiSBA_DP and AuTiSBA_PVA after catalytic test

The activity carried out by the Surface, Thin Films and Nanostructure group lead by Prof. Josef Korecki at the Institute of Catalysis and Surface Chemistry, in Krakow fits within this workpackage WP1. It should be reminded that the group has joined the WG late, in January 2008, replacing Prof. Grzybowska. As it was discussed in Nice at our recent WG meeting, the involvement of the polish group would be in comparative studies of model and real bi-metallic catalyst. The facilities they have available for such approach consist of two ultrahigh vacuum (UHV) systems equipped with spectroscopic and microscopic techniques that allow complex post-preparation treatment and characterization of single crystalline and powder samples. Moreover a catalytic reactor, attached to one of the UHV systems has been developed and is currently under tests. As suitable support for

model catalysts, they studied Fe3O4(001) films on MgO(001) as a function of annealing for better understanding of their composition and crystallinity [5]. Fe3O4(001) surfaces with different terminations, iron rich or oxygen rich, were used to study electronic properties of gold nanoclusters [6,7]. It was shown that the Au clusters prefer Fe-surface sites for nucleation. As a starting point for bi-metallic systems, the growth of gold and silver on the Fe-rich Fe3O4(001) surface was compared. Striking growth differences were observed. Indeed, as shown in Fig.2, at the same deposition temperature, despite higher surface energy, gold showed a flat growth, while for silver with lower surface energy, which should favour a layer-by-layer growth, three-dimensional growth was observed. Since the crystal structure of Au and Ag are identical (fcc) and the lattice constants are practically the same, the difference of the growth mode must come from a strong Au-Fe3O4 interaction of an electronic origin. According to the results, in the bi-metallic Au-Ag/ Fe3O4 system, the morphology of the cluster assembly can be tuned by changing composition and deposition condition. Such research is fundamental for the understanding of the catalytic behavior of gold catalysts supported on iron oxides, widely investigated by the other WG participants in several reactions such, the oxidation reaction of CO, water-gas shift reaction, and also oxidation of VOC.

Fig.2 Gold (a,b) and silver (c) adsorbates (nominal thickness 5 ML) deposited at room temperature on the Fe3O4 surface. The LEED pattern (a) shows epitaxial character of the gold film. STM images (b,c) were taken in the topographic mode.

Fig. 3 0.1 ML Au/FeO/Pt(997) Important results were obtained, by the same research group in Krakow, in the preparation of the so called “vicinal surfaces” consisting of high Miller index planes which can be obtained by cutting a bulk single crystal with a miscut angle of a few degrees with respect to the low index crystal plane. Surfaces obtained in this way consist of a regular structure of steps and terraces of the same width. Vicinal metal surfaces are ideal and simple templates for growing nanostructures. Single-crystalline metal surfaces such as W(540) and Pt(997) were prepared. The W(540) surface, with monoatomic step periodicity of 2 nm was used for the growth of different metallic stepped surfaces. An example was demonstrated for a gold surface [8]. Moreover stepped oxide surfaces can be prepared by epitaxial growth on vicinal metal surfaces. As shown in Fig.3, quite interestingly, the growth morphology of Au on stepped FeO resembled real catalyst. With respect to the second work package, dealing with real catalysts, investigation of gold supported on CeO2 doped by lanthanides ions, by Al3+ and Y3+ have been carried out in collaboration between three groups (Sofia (Andreeva), Palermo (Venezia) and Bucarest (Munteanu)). The catalysts

were tested in the reactions of NO with CO and in the preferential oxidation of CO in the presence of excess hydrogen (PROX). By adopting two different sample preparation methods - by co-precipitation (CP) and by mechanochemical activation (MA)- it was possible to establish a relationship between the catalytic activity and the concentration of oxygen vacancies largely determined by the type of synthesis. The catalysts, characterized by means of XRD, HRTEM, Raman spectroscopy, XPS and TPR exhibited very high dispersion of gold particles (average size below 3 nm) and redox properties ascribable to the different dopant ions, Me3+. The CP samples resulted more catalytically active in the studied reactions as compared to the MA samples. This was due, to a great extent, to the higher concentration of the oxygen vacancies. Generally, the catalytic activity of the samples correlates with the redox activity evaluated by TPR measurements. The addition of water to the gas feed increased substantially the selectivity to N2 in NO reduction of the catalysts doped by rare earth metals compared to the samples doped by alumina. The particular support structure allowed to reach the 100% selectivity in the reduction of NO by CO, in the presence of water within the whole studied temperature range. This result made these gold catalysts promising for practical application. Taking advantage of the theoretical expertise of the Romanian group, the kinetic parameters of the reduction processes of gold based catalysts were evaluated by fitting the experimental TPR curves. On the basis of the obtained results it could be concluded that for CP prepared gold catalysts, oxygen vacancies both at the surface and deeper in the bulk are formed during the redox processes, on the contrary, in the case of MA samples only surface oxygen vacancies participate in the redox processes. These results contributed to the explanation of the catalytic results. Still related to the preparation of real catalysts, the Palermo group has reported interesting results in the preparation of mixed oxides TiO2-SiO2 as support for Pd catalyst for the total oxidation of methane. The effect of SO2 in the reaction feed was evaluated. This part was done in collaboration with the group in Bruxelles. A superior behavior in the total oxidation of methane, in terms of conversion and also resistance to sulfur poisoning was obtained. The combination of a sulfatable support like titania and an inert support like silica was found to improve the catalytic activity and most importantly the tolerance to the sulfur molecule poisoning. Indeed while TiO2 acts as a scavenger for the SO2 molecules, therefore preventing them from reacting with the active palladium, on a long exposure to SO2, whereas the TiO2 would saturate and therefore stop his beneficial effect, the presence of silica would facilitate the sulfur molecule removal by simple thermal treatment. During the 2008, a consistent part of the research activity in Palermo has been devoted to the development of mesoporous materials such as siliceous MCM-41, HMS, SBA 15, modified with reducible oxides. The aim was to use these materials as supports for oxidation reactions of methane and also propene as model compound for the VOC. Indeed it has been proved that the insertion of oxides such as CeO2 and TiO2 in mesoporous silica has an important and active role in several oxidation reactions. In the area of hydrogenation reaction, interesting catalytic results were obtained with a Pd catalyst supported on silica HMS. The catalyst, prepared by conventional method of wet impregnation, was used in the reaction of hydrodesulfurization of thiophene, a model molecule for the testing of the hydrotreatment catalysts. The monometallic Pd/HMS, exhibited much higher and stable catalytic performance as compared to other Pd catalysts supported on mesoporous MCM-41 or amorphous silica, and most unexpected it exhibited a superior activity with respect to a corresponding Co catalyst. Although we do not have yet clear experimental evidence, the possible explanation for the peculiar behaviour probably has to be related with the support properties, e.g morphology, surface acidity. We plan in the near future to start a close collaboration with the group of Prof. Gabriel Munteanu and with his collaborator, Prof. Viorel Chihaia to model the system and to understand the reason for the catalytic performance. Indeed the Romanian group has available new powerful computer facility and expertise in several theoretical methods, from the Empirical Force Fields, Semiempirical methods such as CNDO, INDO, MNDO and First Principle methods such as Hartree-Fock Theory, Density FunctionalTheory, Perturbational Correlation and Quantum Monte Carlo. Moreover a collaboration has just started between the Palermo and the Stockholm groups in order to prepare by microemulsion technique, developed in Stockholm, monometallic Pd and bimetallic Pd-Au particles on the mesoporous HMS support, aiming to obtain larger particle dispersion. The research of the French team (Fraissard) from the Laboratory “Physique Quantique” ESPCI, Paris has been devoted mainly to the preparation of new catalysts, focusing on the development of carbon nanotubes as supports and bimetallic catalysts, in collaboration with colleagues from laboratories in Ukraine. They have studied the activity of catalysts based on the zeolite HY, containing monometallic and bimetallic particles of platinum, palladium, and gold in large cavities, in reduction of nitrogen oxides in the presence of CO and light hydrocarbons. As support, they used the hydrogen form of faujasite (HY) obtained by heating the ammoniated form of the commercial zeolite

NH4Y (Union Carbide) in a dynamic reactor in a stream of He (6 L/h) at 400 °C for 48 h. Some of the catalytic tests, particularly the oxidation of alkane were performed in collaboration with the Krakow Catalysis Institute. The group has an intense research activity in the development of new type of NMR imaging for the visualization of the distribution of adsorbed species in a microporous solid during the adsorption. They developed the analytical solution of the equations of gas diffusion in a heterogeneous zeolite bed. The problem was handled by assuming that the bed consists of a large number of very thin layers of solid, perpendicular to the direction of propagation of the gas. Mass transfer by diffusion in such a material is determined by a system of differential equations with boundary and interface conditions. The results allowed to make the theoretical determination of the time dependence of the concentration profiles and the inter- and intra-crystallite diffusion coefficients of a gas in each layer of the bed. A numerical application concerns the diffusion of benzene in a cylindrical bed of ZSM5 displaced vertically and rapidly, step by step, inside the NMR probe. Thus, the time dependence of the concentration of gas absorbed at the level of each slice and each crystallite can be obtained. These coupled investigations give a better understanding of the diffusion process in this multilayer material. This study ha important inference in catalysis since it is well known that the activity of a catalyst depends not only on its chemical properties but also on the ease of diffusion of the reactants and products. Within the WP2, the activity of the Swedish group(Boutonnet) focused on two main subjects: 1) catalysts development for the co-production of Fischer-Tropsch Diesel and Synthetic Natural Gas (SNG) from biomass-derived syngas; 2) Mo and Rh based catalysts for ethanol production from synthesis gas. Two ways of forming HCs from H2-poor gas from gasified biomass (H/CO=1) were considered: adjust the H2/CO ratio to 2.1 in an external WGS unit, and use a Co-catalyst in the FT reactor; use the H2-poor gas directly (after cleaning) inside the FT reactor. In this case, a catalyst with Water- Gas Shift (WGS) activity (usage ratio = 1.0) is needed. Indeed 100 % syngas conversion is only possible if the usage ratio equals the inlet ratio. The FT activity at low inlet H2/CO ratios is increased by a higher PH2 as a result of the WGS activity. The investigated catalysts were Cu or K promoted Fe catalysts and Co/Al2O3 and mechanical mixture of Co catalyst and WGS Fe catalysts. As results of the study it was possible with the K-promoted Fe-catalysts to match the usage ratio with the inlet ratio of H2/CO = 1. However, at high syngas conversions the usage ratios are too low and the FT activities per catalyst volume too poor to constitute a promising alternative to the external WGS-unit up-stream of a FT-reactor (with a Co-catalyst). It is possible to obtain a significant WGS activity with the Co-catalyst mixtures. However the pure Co shows a higher activity than the mixtures possibly due to the presence of alkali metals in the WGS-catalysts. With respect to the second activity, the production of ethanol from biomass derived syngas, the issue was to develop catalysts tolerant to sulphur molecules present in the synthesis gas produced from biomass gasification and to reach 50% selectivity into ethanol at conversion above 10 %. Among the studied samples, the best performing catalysts were the Mo based ones allowing to obtain ethanol and methanol as main products at 340°C although with rather low conversion. For the future, preparation and characterisation of various catalysts from microemulsion for testing in the other WG laboratories are planned: particularly, as said above, new catalysts based on Pd or Pd/Au from microemulsion to be sent to the Palermo laboratory, for characterisation and testing.; Catalytic tests in high pressure reactor at KTH for samples prepared in Palermo; Characterisation of FT catalysts by XPS at the CNR in Palermo. As complement to the experimental research carried out in Stockholm in the field of FT processes, the Brussels group has recently performed mechanistic studies on the FT reaction using chemical transient kinetics. Either pure or supported Ni and Co catalysts were prepared by oxalate (co-)precipitation. The mechanistic studies demonstrate that CO insertion is in operation. The chemical surface composition of the catalysts was measured during the ongoing reaction and large amounts (in excess of a monolayer) of carbon, oxygen and hydrogen were found under stead-state conditions. Thus the CO insertion cannot occur on a metallic surface, which is different from most of the current opinion. The data are in accordance with a mechanism in which formate-derived species play a key role as most abundant intermediates. Other activities:

• 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)

• STSM granted to Dr. Ivan Bogoev Ivanov from Institute of Catalysis (Andreeva) for a period of three weeks from 14/04/2008 in Palermo at the ISMN-CNR (Venezia).

• 3rd WG meeting, La Maison du Seminare, on 23-26 October 2008, Nice, France

WG D36-005-06 FERMIN Structure-reactivity relationships of Pt and Pd nanoarrays D. Fermin, WG coordinator The research activities in this period generated significant progress towards: (i) preparation and electrocatalytic activity of Pd and Pt nanostructures at a variety of interfaces and (ii) theoretical modelling of structure/reactivity of metal nanostructures. In the context of the workpackages (WP), the most significant advances include: WP2 – Nucleation and growth of metal nanostructures at single-wall carbon nanotubes (CNTs)

networks WP3 – Electrodeposition of Pt and Cu nanostructures at zeolite templated liquid/liquid interfaces WP4 – Electrocatalytic properties of Pd nanoarrays on insulating support employing scanning

electrochemical microscopy (SECM) WP4 – Electrocatalytic activity of Pt nanostructures towards the oxidation of small organic compounds WP6 – Stability studies of metal nanostructures based on Density Functional Theory and Monte Carlo

Simulations WP6 – Theory of H2 oxidation at metal surfaces COST sponsored network activities included the 2nd working group meeting in Burgos (ES) from 15th to 17th December 2007, as well as a STSM at the University of Burgos entitled “Deposition of Catalytically active Pd and Pt particles at the Liquid/Liquid Interface”. 2. Research activities WP2. Electrodeposition of nanoparticles arrays on CNTs (Warwick). The Warwick group has reported key advances in understanding the factors controlling the electrodeposition of Pt and Pd nanoparticles at single walled CNT [1]. A new electrochemical cell based on a microcapillary compartment was developed to study deposition process at small fraction of the surface containing the CNT network. These studies illustrated how the applied potential to the CNT and the deposition time can control the number density, distribution and size of the nanoparticles. WP3. Electrochemical nucleation of metallic clusters at membrane supported liquid/liquid interfaces (Manchester-Burgos-Warwick). The Manchester group reported results obtained on the deposition of metals (Pt and Cu) within zeolite templates (zeolite Y and silicate) consistent with the aims of WP3. Metallic clusters, of < 1 nm diameter, were deposited through this method. Metal deposition at the liquid-liquid (L/L) interface was investigated under potential control, and through the use of in situ absorbance methods – the latter in collaboration with the Burgos group – via COST sponsored STSM of a student from Manchester to Burgos. Kinetic parameters relating to the deposition process were found via both experimental approaches. Finally, the micron-scale aggregation of Au particles at the L/L interface was studied via image analysis methods, and factors affecting the particle aggregation process were probed. Aggregation was found to be sensitive to the identity of the aqueous phase anion (at constant ionic strength). The Warwick group reported an alternative method in which Pd nanoparticles were chemically formed in Nafion membranes [2]. WP4. Electrocatalytic activity of the nanostructured surfaces (Warwick-Leiden-Berne). The groups of Warwick and Berne carried out collaborative work on the evaluation of the electrocatalytic activity of Pd nanoparticles adsorbed at insulating substrates. A methodology based on scanning electrochemical microscopy (SECM) was developed to measure the turnover rate H2 evolution as a function of the number density of Pd nanostructures. This method relies on the rate of electron injection to the nanoparticles by a reduced probe generated by an ultramicroelectrode in the vicinity of the assembly. The initial studies have shown that the average reactivity of a single Pd particle of 10 nm is comparable to that of bulk Pd [3].

Leiden University has been involved in studying the oxidation capacity of platinum nanoparticles on gold for carbon monoxide, methanol and formic acid (WP4). It was found that large nanoparticle aggregates have a higher intrinsic activity for the carbon monoxide and methanol oxidation, whereas formic acid oxidation prefers small particles. This effect is possibly related to the role of certain defects sites in the overall oxidation mechanisms [4]. Simultaneously, Leiden has started a project attempting to address the activity of platinum defect sites for the dissociation of water, combining electrochemistry, ultra-high-vacuum techniques and first-principles density functional theory calculations (WP6). WP6. Theoretical modelling of nanostructure reactivity (Ulm-ZSW). The Ulm group has pursued two related projects pertaining to the WP6: Theoretical modelling of nanostructure reactivity. In the first project, Ulm has investigated the stability and the fluctuations of metal nanostructures by a combination of density functional theory and kinetic Monte Carlo. From capillary wave analysis it was obtained the amplitude of boundary fluctuations, the line stiffness, the kink energy, and their dependence on the electrode potential. The second project was developed in collaboration with the SZW group on an advanced theory for electrocatalysis. A first application to the hydrogen oxidation explained the strong dependence of the reaction rate on the electrode material [5,6]. Ulm and SZW are currently modifying this theory to incorporate results from density functional theory. This will allow investigating the catalytic properties of nanostructures such as steps or foreign metal islands. January-December 2008

WP1. Wet Chemical Synthesis of Nanostructures and Self-Assembly at Solid Supports (UBRI, UWAR,

UBU, HUT).

UBRI has been examining in detail the synthesis of Au-Pd core-shell nanostructures employing seeding-growth methods. The synthesis consists of reducing PdCl4

2- at the surface of 20 nm Au cores in the presence of ascorbic acid. This method allows adjusting the average shell thickness between 1.6 and 9.0 nm. Transmission electron micrograph of the Au cores and Au-Pd (average shell thickness of 9 nm) are contrasted in figure 1. While the citrate stabilised Au particles exhibit a “faceted” surface, Au-Pd is characterised by extensively corrugated surfaces. Furthermore, the narrow size distribution of the bi-metallic nanostructures strongly suggests that the Pd is exclusively nucleated at the surface of the nano-seeds. High resolution electron microscopy and electron diffraction strongly suggest that the Pd layer grows epitaxially on the Au cores. The origin of the high corrugation observed for the 9 nm thick Pd layer remains unclear.

(a)

(b)

Figure 1. HRTEM images of (a) Au nanoparticles (20 nm) and (b) Pd(7nm)@Au(20nm) nanoparticles

Three-dimensional assemblies of citrate/ascorbate stabilised nanoparticles were formed at In-doped SnO2 electrodes by electrostatic layer-by-layer adsorption employing poly-L-lysine (PLL). This method is initiated by the adsorption of an ultrathin (less than 1 nm thickness) layer of PLL, followed by the adsorption of the nanoparticles. The characteristic topographic features for a single PLL-nanoparticle bilayer and five bilayers are exemplified in figure 2. The high corrugation of the multilayer allows increasing the effective surface area of the nanoassembly.

Collaborative work between UWAR, UBU and HUT has focused on exploring conducting polymers as supports for Pt catalysts. In particular, the morphology of Pt nanoparticles electrodeposited on highly oriented pyrolytic graphite (HOPG) and on HOPG modified with ultrathin films of poly(3,4-ethylenedioxythiophene) (PEDOT) with the same deposition conditions has been compared. It was found that the PEDOT coating had a pronounced effect on the resulting nanoparticle (NP) size and NP density of PEDOT-supported Pt arrays. Modifying HOPG with a thin PEDOT layer provided a route for catalytic surfaces with higher density of smaller nanoparticles than in likewise produced HOPG-supported arrays. That is, the conducting polymer coating seems to prevent aggregation of the nanoparticles. The possibility of tuning the morphology and in turn the electrocatalytic properties of Pt NP arrays on PEDOT-modified HOPG surfaces has been demonstrated by comparing the electrocatalytic performance of Pt-PEDOT and Pt-HOPG surfaces toward a series of reaction of interest such as the hydrogen evolution reaction, formic acid and methanol oxidation [1].

(a)

(b)

Figure 2. AFM images 1mm × 1mm of a (a) single bilayer and (b) five bilayers of PLL- Au nanoparticles (20 nm) obtained by

electrostatic layer-by-layer adsorption.

WP2. Electrodeposition of nanoparticles arrays on CNTs HUT has been investigating alternative methods to prepare CNT network electrodes on different supports, including those (like plastics) who cannot stand the high temperatures required for Chemical Vapor Deposition (CVD) of CNTs. The approach involves combining an aerosol CVD method to grow SWCNTs and a simple compression approach to transfer SWCNT films collected directly from the gas phase outside the synthesis reactor on a filter membrane to different supports. The method, which can be regarded as the dry, surfactant-assisted free alternative to vacuum filtration deposition, allows control of the CNT film thickness via collection time on the filter membrane. Thus, it has been demonstrated that very stable CNT electrodes with tuneable sheet resistance/transparency can be prepared reproducibly on a variety of substrates such as silicon wafers, glass, quartz or flexible Polyethylene terephthalate (PET). The use of transparent substrates has enabled using sole CNT networks (without a conductive support) as optically transparent electrodes for spectroelectrochemical investigation of electroactive species, a study undertaken in collaboration with UBU [2]. Ongoing studies aim at providing further insight into the reactivity and electroactivity of CNT networks, both pristine and activated, as it is essential for their use as platforms to immobilise electrocatalysts. The possibility to assemble CNT networks on various substrates by the compression-transfer approach will be exploited in order to address the influence of the underlying support on the electroactivity of CNT networks and CNT-supported electrocatalysts. WP3. Electrochemical Nucleation of metallic clusters at membrane supported liquid/liquid interfaces (UMAN, UBU) The UMAN group is continuing to investigate the deposition of metallic NPs at the liquid-liquid interface, and their use as potential electrocatalysts. Ultra-small (ca 1 nm) particles have been deposited within zeolite membranes, via both electrochemical and spontaneous reduction methods (see Figure 3(a)) at the polarisable water/1,2-dichloroethane interface. Similarly, protected Au NPs have been deposited by chemical reaction at the water/toluene interface (Figure 3(b) and (c)). The general influence of the liquid/liquid interface on the geometry of particles formed by deposition/reaction at this interface is being investigated.

Pd nanoparticles deposition at liquid/liquid interfaces has been studied between the UMAN, HUT and UBU. To that aim, a novel UV-Visible Absorption Spectroelectrochemical cell for the study of electrochemical processes at polarized liquid/liquid interfaces based on the parallel incidence of the light beam with respect to the interface has been developed [3]. The new cell, based on the assembly of the four-electrode set up inside a rectangular quartz spectrophotometric cuvette, proved superior to a previous prototype based on an existing cylindrical cell for liquid/liquid electrochemistry. The work showed that absorption spectroelectrochemistry in parallel-beam configuration can be a very sensitive probe of processes such as ion transfer at the polarized liquid/liquid interface once the contribution from the bulk of the sampled phase is removed. The new cell provides valuable quantitative information on the deposition of Pd at polarized liquid/liquid interfaces.

Figure 3. Transmission electron microscopy of (a) Pt-deposits within zeolite Y membranes – scale bar = 5 nm, (b) phosphine-stabilised Au particles formed at the water/toluene interface after 1.5 hrs and (c) the same particles after 24 hours of interfacial reaction. WP4. Electrocatalytic Activity of the Nanostructured Surfaces (UBRI, UWAR, UBU, HUT) Collaborating work involving UWAR and UBRI have led to the estimating the kinetic of hydrogen evolution on two dimensional assemblies of Pd (10 nm diameter) adsorbed at insulating substrates [4]. The experimental approach was based on scanning electrochemical microscopy (SECM) and a redox mediator in solution. SECM approach curves allow estimating the flux of electron injection by the reduced mediator in to the Pd nanostructures. This flux matches the rate of proton reduction to hydrogen at the nanoparticles surface. Experiments as a function of the nanoparticle number density allowed estimating the average flux of hydrogen evolution at the standard potential (exchange current density) for a single Pd cluster. The UWAR group has also studied functionalised 3D arrays of Pd in Nafion films, also exhibiting a high reactivity towards hydrogen evolution [5]. These results demonstrate the high accuracy of SECM to study interfacial kinetics at nanoparticles assemblies. The UBRI group has been investigating the electrochemical properties of nanostructures in the presence of surface sensitive probes such as underpotential deposited (upd) layers. The voltammetric responses of Au nanoparticle multilayers assembled by electrostatic layer-by-layer (WP1) in the presence of TeO2 in HClO4 exhibits the characteristic upd signals reported for polycrystalline Au surfaces. Estimation of the voltammetric charges indicates that the overwhelming majority of the nanoparticles in the array contribute to the upd signal. These responses are used for probing whether portion of the Au cores are exposed to the electrolyte in the various core-shell structures. In addition, we can also interrogate the interaction energy between the Te adatom and the Pd surface as a function of the shell thickness. The results obtained from these studies validate the use of electrostatic layer-by-layer assembly for generating catalytically active nanostructures at metal oxide electrodes. The UWAR group has also examined the formation of Pt nanoparticles on boron-doped diamond electrodes for the electrocatalytic reduction of oxygen. The functionalised electrodes constructed serve as sensor of oxygen concentration over a wide dynamic range [6]. Simultaneously, joint work between UBU and HUT has resulted in the development of a novel strategy to prepare composite catalytic materials based on the layer-by-layer electrochemical generation of a hybrid material consisting of polyaniline (PANI) and Pt NPs. It has been demonstrated that the number of layers and the nature of the external layer (PANI or Pt) determine the electrocatalytic performance of the composite for the oxidation of methanol. The layer-by-layer approach preparation of the nanocomposite and modification of the Pt nanoparticles with a layer of PANI resulted in substantially higher catalytic efficiency for methanol oxidation [7]. WP5. Electrocatalysis at Nanoparticles at the Liquid/Liquid Interfaces (UMAN, UBU, UBRI)

a b c

Direct methods for addressing the electrocatalytic properties of nanostructures at liquid/liquid interfaces were discussed throughout the meeting. Fundamental questions about the interfacial location of the nanoparticles and the effective potential drop across the molecular boundary are some of the unresolved fundamental issues. On the other hand, the UMAN group investigated the electrocatalytic properties of nanostructures generated at the liquid/liquid interface after transferring to a solid substrate. Figure 4 contrasts the cyclic voltammograms associated with the oxidation of formaldehyde on glassy carbon prior and after adsorption of phosphine-stabilised Au nanoparticles grown at the water/toluene interface (WP3). These results clearly indicate that the Au nanoparticles catalyse this reaction. The next step involves evaluating the catalytic activity of these clusters the polarisable liquid/liquid boundary.

Figure 4. Voltammetry of formaldehyde at a glassy carbon electrode before (blue) and after (green) modification of the surface

with the phosphine-stabilised Au nanoparticles shown in Figure 3b.

Figure 8. d-band densities of states and potential energy surfaces for the hydrogen oxidation on pure Pd (left) and for a

monolayer of Pd on Au(111) (right).

WP6. Theoretical Modelling of Nanostructure Reactivity Both ULM groups joined forces to elucidate the principles of hydrogen catalysis on metal nanostructures, Dr. Santos specializing in structures of foreign metals on metal substrates, Prof. Schmickler in nanowires. First, the groups formulated a general theory of hydrogen electrocatalysis based on extensive calculations with density functional theory (DFT). They first applied this theory successfully to the hydrogen evolution reaction on a series of pure metals (Pt, Au, Cd) [8]. Then they turned to systems of special interest to this COST group: palladium on gold substrate, a system investigated amongst others by the group in UBRI, and nanowires, which were partially studied together with the group of ULEI. In accordance with experimental findings, the energy of activation for the hydrogen reaction was lower on Pd layers on Au(111) than on pure Pd (see figure 8) [9]. Several similar systems are presently under investigation.

The reactivity of monoatomic nanowires was found to significantly enhance with respect to bulk metals. Thus, on platinum wires the energy of dissociation of water is greatly reduced. Likewise, the energy of adsorption for hydrogen on gold wires is much lower, leading to hydrogen adsorption at potentials above the equilibrium potential for hydrogen evolution.

References

[1] E. Ventosa, A. Colina, V. Ruiz, J. López-Palacios, P. R. Unwin, in preparation. [2] A. Heras, A. Colina, J. López-Palacios, A.Kaskela, A. G. Nasibulin, V. Ruiz, Esko I. Kauppinen, Electrochemistry Communications, in press. [3] A. Martinez, A. Colina, R.A.W. Dryfe, V. Ruiz, submitted to Electrochimica Acta. [4] 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. [5] F.Li, P. Bertoncello, I. Ciani, G. Mantovani and P.R. Unwin, Adv. Func. Mat. 18 (2008) 1685 [6] L. Hutton, M. E. Newton, P. R. Unwin and J. V. Macpherson, Anal. Chem. 2009, in press [7] Susana Palmero , Alvaro Colina, Emma Muñoz, Aránzazu Heras, Virginia Ruiz, Jesús López-Palacios, Electrochemistry Communications 11 ( 2009) 122. [8] E. Santos, K. Pötting and W. Schmickler, On the catalysis of the hydrogen oxidation, Disc. Farad. Soc., 140 (2009) 209. [9] E. Santos, A. Lundin, K. Pötting, P. Quaino and W. Schmickler, Hydrogen evolution and oxidation -- a prototype for electrocatalytic reactions, J. Appl. Electrochem., available online.

Training School on “Theory and Modelling of Electrocatalysis and Heterogeneous Catalysis”

The workgroup organized a second Training School within the framework of the Action D36. The School tentatively entitled “Theory and Modelling of Electrocatalysis and Heterogeneous Catalysis” waslocally organised by Dr. Elizabeth Santos and Prof. Wolfgang Schmickler in Ulm. This event featured talks by leading scientists in advanced computer modelling of interfacial reactions as well as hands-on activities by the participants. Some of the topics to be covered include: Marcus theory of electron transfer, the hydrogen evolution reaction and mass transport simulations of heterogeneous reactions.

WG D36-006-06 MUL Understanding the chemical reactivity of alcohols over catalytic materials: from probe molecules to practical applications G. Mul, WG coordinator In the scheme indicated at the kick-off meeting (see below), the activities agreed. Based on this scheme various activities, in particular in the form of STSM agreements, have been carried out. Intensive interactions between the group of: Sanna Airaksinen/Outi Krause (Helsinki, Finland) and the group of Monica Calatayud, Universite Paris, France Between the groups of Miguel Bañares (Madrid Spain) and the group of Monica Calatayud, Universite Paris, France Between the groups of Maria Ziolek, (Poznan, Poland), and Guido Mul, (Delft, The Netherlands).

Between the group of Maria Zioek (Poznan, Poland) and Miguel Bañares (Madrid Spain). Between the group of Gerhard Mestl (Brükmuhl, Germany) and Miguel Bañares (Madrid Spain). Furthermore one working group meeting was held in Helsinki, taking advantage of the MC which was celebrated in Helsinki on the days before the WG meeting. In the following first the outline of the working group meeting is shown and discussed, and furthermore the reports of the various STSM’s presented. Finally, an overview is given of the various papers that have been published in the framework of the topic of the present working group. The annexes describe the WG meeting and the STSM activities, in total the WG has done two WG meetings and six STSM’s. January-December 2008

Activities in group 6 of COST action D36 include the development of kinetic models and fundamental understanding of catalysts active in the conversion of glycerol and alcohols by selective (amm)oxidation or etherification to value added products. In particular focus is on combining information from advanced operando spectroscopy tools, and DFT calculations. In 2008, activities within the framework of this COST action have focused on an enhancement of the interaction of the various groups involved in the form of STSM agreements. In particular, intensive interactions between the groups of Banares/Ziolek, Thielens/Ziolek, and of Calatayud/Weckhuysen were established. Furthermore two working group meetings were held, the first in Poznan, Poland, and the second in Delft, The Netherlands. In the following an extended summary of the various achieved results on the basis of the two working group meetings is provided, including those reported of various STSM’s. Finally, an overview is given of the various papers that have been published as a result of the cooperation of the various parties in our working group. The progress was continuously discussed due to multipuntual interaction among groups, and these were more extensively discussed in the WG meetings, held in Poznan (May 2008) and Delft (November 2009). Scientific results as reported in the working group meeting held in Poznan 10 – 11 May, 2008 Catalyst preparation and characterization Three groups of supports were applied for loading Gold; i) mesoporous MCM-41 and SBA-3 containing vanadium and niobium, ii) aluminum and niobium oxides, and iii) carbons including a mesoporous carbon replica of SBA-15. Gold was introduced during the synthesis of mesoporous materials by coprecipitation, whereas on metal oxides and carbons gold was deposited by a precipitation method using urea as precipitation agent, or by a gold-sol method with THPC (tetrakis – (hydroxymethyl) – phosphonium chloride). The highest dispersion of gold was obtained on the carbon support. The nature of the active sites of prepared materials was tested by acetonylacetone cyclisation (acid-base test reaction) and methanol oxidation. Methanol oxidation is a good test reaction for redox properties (formaldehyde formation) and an identification of basicity and acidity. Activity and selectivity is not related to the number of acidic centres. It is a structure sensitive reaction. Furthermore, the introduction of V and/or Nb together with Au into MCM-41 diminishes the basicity of AuMCM-41. Carbon supports give rise to a high gold dispersion, whereas alumina and niobia lead to the formation of big Au crystalites.Au supported on carbons is selective towards formaldehyde in MeOH oxidation, but the catalysts are easily deactivated. Development of operando techniques for analysis of liquid phase processes ATR and Raman spectroscopy of glycerol oxidation Liquid phase processes have to be carried out under very well controlled conditions. Many features influence Raman spectra recorded under the reaction conditions (Operando technique). These are stirring rate, the presence of catalyst particles, bubble formation, and temperature. The conditions of

ATR and Raman spectra were compared. Comparison of ATR and Raman systems lead to the following conclusions:

- ATR • concentrations as low as ~0.05 Mol/L can be detected accurately • High time resolution (data point every minute)

- Raman • concentration of about ~1 Mol/L necessary • Low time resolution (data point every 7 minutes)

The liquid phase oxidation of glycerol using Vanadium containing catalysts was analyzed by ATR spectroscopy. Vanadium catalysts cannot be applied in this liquid phase reaction because of very easy leaching of vanadium into the solution, as determined by on-line monitoring.

Achievements in molecular modeling

Modeling the structure of (V, Nb,Ta) modified zeolites Frederik Tielens undertook theoretical studies of the insertion of group five elements (V, Nb,Ta) into a zeolite structure. He built a model of zeolites based on the sodalite structure. The calculation of energies allowed him to indicate that vanadium in the zeolite framework is preferentially as V4+, whereas niobium and tantalum as M5+. Moreover, the energy preference for the species present in the zeolite structure differ depending on the nature of the transition metal. For vanadium it is V=O, niobium exist in two forms, Nb=O and Nb-OH, whereas tantalum is present as Ta-OH. The reducibility of T(V)/T(IV) increases from Ta to V. These calculations are in agreement with the experimental data obtained in Ziolek’s group and described in literature. Unexpectedly, he found that the possibility of framework substitution of group 5 elements increases from vanadium to tantalum. This statement is confirmed by the experimental results for mesoporous molecular sieves from Ziolek’s group which showed much easier incorporation of niobium than vanadium. The theoretical result for Ta requires further research efforts. DFT studies for the formation of carbonates on zirconia surfaces Satu demonstrated a realistic model of monoclinic zirconia on which adsorption of water and formation of formates and carbonates were considered. It was found that at low coverages water is chemisorbed dissociatively and forms hydroxyl groups on the surface. The preferred form is 1-fold coordinated OH. An increase of the temperature decreases the OH coverage. Adsorption of CO and CO2 leads to the formation of formate and carbonate species. Various types of these species were considered. Finally, it was stated that the most stable are formates and bidentate carbonates. Reaction paths for methanol oxidation on supported vanadium oxide Methanol adsorption as well as adsorption of water and formation of formates and carbonates were studied by theory on supported vanadium oxide (M. Catalayud) and on zirconia surfaces (S. Korhonen), respectively. The energies of methanol adsorption and hydrogen, water, formaldehyde formation for vanadia supported on titania were calculated. Moreover, energies of hydrogen and methanol adsorption on V2O5/TiO2 doped with alkali metals were calculated. Interestingly, the results showed a volcanic curve depending on the nature of the alkali metal, in agreement with the experimental data obtained in Banares’s group. Reactivity studies Polymerisation of glycerol Two directions of glycerol transformation were studied, etherification towards di- and triglycerols (A. Ruppert – Weckhuysen’s group) and ammoxidation to acrylonitrile (O. Guerrero-Perez – Banares group). The first reaction occurs on catalysts containing both Lewis acid and basic sites. Successfully, CaO was applied for that purpose. The surface area and the strength of Lewis acid and basic sites matter and the catalyst with the right balance of basicity and acidity exhibits the highest glycerol etherification activity. Ca-O based catalyst can be prepared with an activity comparable with that of the most basic alkaline earth metal oxide, i.e. BaO.

Glycerol etherification at 220 ºC in the absence of solvent represents rather harsh experimental conditions for a heterogeneous catalyst material. As a result, depending on the preparation and treatment conditions the catalyst can defragment and form colloidal CaO particles of about 50-100 nm during the reaction. Their amount gradually increased with the reaction time. It causes the increase of glycerol conversion. Catalytic testing of these CaO colloids, after isolation from the reaction medium, revealed a very high etherification activity, which may become of practical interest after finding a suitable way of immobilisation since such supported colloidal system would take advantage of both their hetero- and homogeneous nature. Ammoxidation of glycerol The ammoxidation of glycerol was performed on vanadium, niobium, and antimony supported on alumina. The preliminary results are very promising. Sb/Alumina catalyst gives rise to low glycerol conversion and selectivity to acetonitrile near 20%. The V/Alumina system is highly active in glycerol conversion but not selective – a mixture of compounds (1,2 propanodiol, propanal, ethane, ethene, propane, propene) is formed. V,Sb/alumina catalyst exhibits high glycerol conversion (70-80 %) and acetonitrile is the main reaction product (55-60 % selectivity). The additional doping of the catalyst with niobium (V,Sb,Nb/alumina) increases both glycerol conversion and acetonitrile selectivity. The disadvantage of the proposed catalysts is their relatively fast deactivation by the deposition of polyaromatic compounds (side reaction products). Future work will concentrate on the elimination of these disadvantages. Scientific results as reported in the working group meeting held in Delft 14 – 15 November, 2008 Achievements established in the second half of the year 2008, including data from various STSMs, were reported in the fourth working group meeting, which was held 14th/15th November 2008, at the Delft University of Technology, The Netherlands. Ten lectures were presented during the meeting. Below a short summary of the achievements is provided, again separated in the tasks of our group, i.e. i) preparation and characterisation of catalysts; ii) on-line reaction monitoring; iii) theoretical studies of the location of active species on catalyst surfaces and their interaction with alcohols; and iv) reactivity studies of the (amm)oxidation and polymerisation of methanol and glycerol. Catalyst preparation and characterization Metal Organic Frameworks (MOFs) M.D. Hernandez gave an overview of activities of the Delft laboratory in the synthesis of Metal Organic Framework (MOF) materials based on ZnO, and spectroscopic evaluation of the photo-catalytic activity. Different organic antenna molecules can be incorporated in the structure. When changing the organic antenna molecule in the MOF structure, the absorption spectrum and bandgap changes dramatically. The catalysts were found active in the photo-catalytic oxidation of propene. Modeling of the materials, will be conducted in Paris. Gold loaded on porous carbons New carbon supported Au catalysts were prepared. In particular Au systems based on MCM-41, and carbon analogues of SBA-15 (carbon replica) prepared by glucose impregnation and carbonization were discussed. A reference catalyst based on a commercial carbon support was also prepared and analyzed. Carbon supports give rise to a high gold dispersion. The catalysts were found active in the methanol oxidation and the special attractiveness of the gold modified carbon replica of SBA-15 was emphasised. Ordered mesoporous materials with chromium Cr-catalysts were prepared on ordered mesoporous materials using CrO3 solutions and characterized by reaction of probe molecules, including the conversion of Acetonyl Acetone (AA) to methyl cyclopentenone (MCP) and dimethylfurane (DMF). Chromium species prepared via wetness impregnation with CrO3 solutions into mesoporous silicas consist of Cr6+ species, whereas SiO2, Cr3+

was identified. The implications for the performance of these catalysts in the formation of methanethiol in the reaction of H2S with MeOH were discussed. Alkali promoted vanadate catalysts The effect of alkali addition on the redox properties of supported vanadate catalysts was analyzed. In particular the trend in reduction temperatures, as a function of the nature of the alkali, was discussed. The experimental data determined by H2-TPR were found to be in good agreement with theoretical calculations performed in Paris. One of the issues was the data on the very large alkali ions, which seemed to deviate from the trend. This requires further investigation. Development of operando techniques for analysis of liquid phase processes ATR and Microreactor technology Adsorption properties of ketones and alcohols on TiO2 surfaces were analyzed using the combination of microreactors, allowing rapid switching of two different solvents in a microchannel, and ATR (infrared) spectroscopy allowing to probe the TiO2-liquid interface. The results were very promising: when a gas bubble was used, liquid switching was achieved at switching times in the second time range. It was demonstrated that the coating slowed down the rate of solvent switching, and the effect of the coating thickness will be further investigated in future experiments. Interaction with various molecules and TiO2 surfaces are very easy to model. The models could predict the wavenumbers of certain adsorbed states on TiO2 surfaces, which will be conducted in the coming year. Achievements in molecular modeling Structure of group V elements on modeled silica surfaces DFT measurements on the interaction of Vanadia on modeled silica surfaces were performed. In particular the pathways and changes of the structure of the vanadate site as a function of the degree of hydration were presented. The conclusion was that in many stages hydroxyl groups associated with the vanadia site should be present. The predicted vibrational frequency of the V-OH bonds was also presented. Besides Vanadia, also the interaction of the surface with AuCl3 was modeled. Methanol Dissociation on Isolated Vanadate Groups DFT modeling on the dissociation of methanol over isolated vanadate groups was also conducted. In particular the nature of the active oxygen was discussed (which is typically considered to be the V-O-support bond), as well as the energetically most favorable intermediates in the pathway. It was confirmed by the calculations that indeed the formation of an alkoxide bond by opening of the V-O-Support bond was the most favorable, at least in the case of a TiO2 support, also resulting in the formation of a Ti-O-H group. Basicity and Lewis acidity of alkaline earth metal oxides It was proven that the presence of both strong basic sites and Lewis acid sites is necessary for the etherification of glycerol over alkaline earth metal oxides. Glycerol adsorption on MO (001) surfaces involves the interaction with acid-base surface sites. The basicity of lattice oxygen is correlated to the adsorption energy: BaO (-3.02 eV) > SrO (-2.85 eV) > CaO (-2.05 eV) > MgO (-1.35 eV). The more basic the character of the oxide, the more exothermic is the energy 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-Ogly distances correlate with the crystal lattice parameter. Regarding the adsorption modes, MgO shows preference for top adsorption sites, while CaO, SrO and BaO stabilize bridging modes between two surface metal sites, due to the larger M-Olattice distances. Overall, the obtained results nicely correspond with experimental data and confirm earlier observations that the strength of the basic sites on the oxide surface is the main factor deciding about the activity of the material in glycerol etherification, which confirms that deprotonation of a glycerol OH group is a key factor in the reaction. The empirical glycerol conversion and the calculated tendency of glycerol

deprotonation follow the same pattern (MgO < CaO < SrO < BaO), for the surface models used in our calculations. MgO, which we proved to be not basic enough to effectively deprotonate glycerol, is indeed the least active. During the deprotonation the OH groups are formed on the surface, and the highest number of those groups is observed on BaO (all three glycerol groups are deprotonated), this could be as well connected with the partial hydration of the oxide which was observed during the reaction – the highest tendency was observed in the case of BaO. Interaction of gold clusters with amorphous silica The interaction of gold clusters on amorphous silica surfaces in the presence of chloride using the First Principle Calculation method was analyzed. The adsorption of Au-Cl on silica, and silica modified with chloride (1, 2 and 3 Cl atoms) were studied and the results show that if the number of gold atoms increases, the adsorption energy for chlorine decreases. Moreover, if the number of chloride ions increases the adsorption energy decreases. The most desirable adsorption for charged gold clusters occurred on silica without or with low content (1Cl) of chloride. The results achieved from the calculations indicate that metallic gold interacts very weakly with Silica surface contrary to Au+ or AuCl which interacts well with Silica. The second conclusion is that AuCl prefers to interact with only 1 surface silanol group or one Si-Cl group. Moreover, it can be concluded that interaction with more than one silanol or Si-Cl group simultaneously is energetically unfavorable. The important conclusion is statement that adsorption of AuCl on silanol groups is better than on Si-Cl groups. The results of this work demand further investigation, i.e. analysis of the models with bigger gold clusters and higher amounts of chloride (AuCl2, AuCl3), and the investigation of the vibrational frequencies. This could help in better understanding of the experimental results. The results of this work will be presented in EuropaCat 2009 conference and they will be compared to the former experimental ones in the form of published paper. Reactivity studies Heterogeneous liquid-phase ammoxidation of glycerol The conversion of glycerol under microwave radiation in the presence of various V and Sb catalysts supported on Al2O3 was achieved. The formation of acrolein, as well as the reaction of glycerol to acrylonitril in the presence of NH4OH in solution, were discussed. A very significant effect of the microwave radiation on conversion was noticed, while the catalyst affected the selectivity of the reactions. Alcohol conversions over Fe-Mo catalysts Fe-Mo catalysts were evaluated in the conversion of methanol to formaldehyde. Closing the mass balance in the reaction is problematic, in view of the difficulties in quantitative analysis of formaldehyde. The distribution of the active phase over the support had a significant influence on the performance. In particular an Egg-shell catalyst was compared with other confirmations. Besides redox properties, the catalysts appeared to have acid base properties, in view of the observed formation of dimethylether. Conclusions A large variety of catalysts has been synthesized, with promising characteristics for alcohol conversions. In particular the acid-base properties and nature of the surface sites have been well characterized. The catalysts can be divided in three categories, i.e. CaO and related materials, supported metal oxides (Fe-Mo, Cr, (alkali promoted) V-Sb, and Nb), and catalysts based on Au. Extensive DFT modelling has been conducted to reveal the structure of a variety of these systems, as well as the interaction with alcohols and the modes of reduction. CaO was found a promising catalyst for the target reaction of the conversion of glycerol, yielding etherification. Combinations of V and Sb were found very active in the ammoxidation of glycerol, in particular in the combination with the use of microwaves. Fe-Mo catalysts have to be further evaluated for the conversion of glycerol, as well as

the Cr, and Au-catalysts. Tool development has focused on the analysis of liquid phase processes, and includes the evaluation of Raman spectroscopy and ATR in combination with microreactors, which appears an ideal combination for transient experiments. Many activities are planned for 2009, in particular focusing on extending the work in the combination of operando analyses, reactivity evaluation, and DFT modelling of the conversion of glycerol in particular, and alcohols in general.

WG D36-007-06 GIRAULT Molecular Catalysis and Photocatalysis at Soft Interfaces: Experiment and Modelling H. Girault, WG coordinator This working group started its activities in June 2006. After a first meeting in Lausanne in October 2006, the WG met twice in 2007. In June in Budapest, and in November in Prague. Also, H. Girault visited the HUT group after the COST D36 symposium in Helsinki, and the LIMSAG group in different occasions. Partners also met at different conferences, and in particular Z. Samec presented some of the group results at the International Society of Electrochemistry annual meeting in September in Banff Canada, and H. Girault both at the Rubinstein symposium in Namur and at the annual meeting of the Electrochemical Society of China in YangZhou in October. The different tasks of the project are:

Molecular catalysis of oxygen reduction at ITIES Synthesis of surface-active bi-metallic complexes Computer simulation of ITIES Artificial photosynthesis

Molecular catalysis of oxygen reduction at ITIES Oxygen reduction was studied at polarized liquid-liquid interfaces in the presence and absence of tetraphenylporphyrins (TPP). We had shown in 2006, that CoTPP dissolved in the organic phase gave rise to very large catalytic currents associated with the reduction of oxygen by decamethylferrocene. In 2007, many different metal TPPs and OEPs (e.g. Zn, Ni,Cu, Pd) were synthetised and their catalytic activities were tested. The major surprise was the observation that free base TPP could also catalyse the reaction. This result is surprising as most mechanisms known so far involves the presence of a metal atom such as cobalt. This was presented and thoroughly discussed at the Prague meeting. We have also studied the adsorption of the different porphyrins at the interface by surface tension and capacitance measurements. Indeed, an important aspect of the present project is to investigate if adsorbed porphyrins do form catalytic aggregates whose properties differ from that of molecules in the bulk. The third line of research has been to study the interfacial protonation properties of porphyrins. It was shown in 2006 that electrochemistry could be used to measure the protonation constants of TPPs that possess two protonation sites. Another major surprise in 2007 was the observation that it is possible to protonate twice CoTPP. To unravel this phenomenon, we have undertaken a screening program of the UV-vis absorption and emission of the different porphyrins. The key questions remaining to elucidate are:

- The locus of the reaction vis à vis the interface - The influence of the pH - The number of electrons involved. Either two electrons with the generation of hydrogen

peroxide or four electrons with the production of water. - The influence of the metal atom in TPP.

TPP OEP AP

Figure 1: Abbreviation of the different porphyrins synthetised Synthesis of surface active bi-metallic complexes As discussed above, all the synthetic effort has been dedicated to the synthesis of different TPPs, OEPs and APs that are very surface active, validating the hypothesis that a pendant amino group was an efficient to achieve surface activity. The synthesis of bifacial porphyrins is in progress. Computer simulation of ITIES Two aspects have been addressed in 2007. First, we have studied the influence of oxygen molecules in molecular dynamics. Also, we have developed a new method to characterize the surface roughness of liquid-liquid interfaces, and an application of this method for the air-water interface has been published (see attached manuscript, L.B. Partay et al., J. Comp. Chem., available on line). The next step is to apply this method to porphyrin adsorption. Artificial photosynthesis This task was not addressed yet. However, we dedicated a lot of effort to unravel what would appear to be the generation of hydrogen at polarized liquid-liquid interface associated with the direct oxidation of decamethylferrocene by acid solutions. Dissemination 1. “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. B. Partay, G. Hantal, P. Jedlovszky, A Vincze, G. Horvai, Journal of Computacional Chemistry , in press (2007)

2. Few manuscripts are now in preparation. 3. Invited Plenary Lecture H. Girault, at 14th annual meeting of the Chinese Electrochemical

Society, Xiamen, China on 7-9, Nov., 2007 4. WIKI SITE January-December 2008 Summary: In 2008, the main achievements of the working group have been: - the synthesis of hydrogen peroxide in biphasic systems using decamethylferrocene as an oxygen

ligand. The reaction is controlled by the proton pump reaction from aqueous to the organic phase. - the demonstration that free base porphyrins such as H2TPP can activate oxygen to catalyse its

reduction. - The design, synthesis and characterisation of highly efficient amphiphilic porphyrins for oxygen

reduction - The development of new computational techniques to study the structure of liquid-liquid interface

by molecular dynamics. Report The general goal of this project is to study a novel electrocatalytic approach for oxygen reduction based on molecular catalysts at a soft interface such as a liquid-liquid interface. The long-term objective is the design of a novel class of “chemical fuel cells” based on a soft interface. The strategy is to combine groups from five institutions with expertise in the synthesis of molecular catalysts and with expertise in experimental and theoretical electrochemistry, photoelectrochemistry at liquid-liquid interfaces:

EPFL – Ecole Polytechnique Fédérale de Lausanne JHIPC – J. Heyrovský Institute of Physical Chemistry TKK – Helsinki University of Technology BUTE –Budapest University of Technology ICMUB (LIMRES) – Université de Bourgogne

The first objective that has been planned is to study the molecular catalysis of oxygen reduction at the liquid-liquid interface. This part of work was in fact our major research effort in the past two years. And all of five groups from EPFL, JHIPC, TKK, BUTE and ICMUB (LIMRES) have been keeping good collaborations to move the work forward. Considering the research expertise and experimental facilities, the groups from EPFL and JHIPC have been working on the electrochemical aspects of oxygen reduction at the liquid-liquid interface, including classical four-electrode electrochemistry, surface tension measurements and modelling of the electrochemical processes. Both the fundamental oxygen reduction reaction, i.e., oxygen reduction by decamethylferrocene (DMFc), and the catalytic oxygen reduction by a series of porphyrin catalysts including free base porphyrins and cobalt porphyrins with monomeric and dimeric structures, as well as the surface characterization of porphyrin catalysts, have been studied. All these porphyrin catalysts have been prepared by the ICMUB (LIMRES), since this group has a long experience in the synthesis of macrocyclic compounds. The group in BUTE has been working on the computer simulations on the interfacial microscopic structure and roughness. Regarding the oxygen reduction at the liquid-liquid interface, they have calculated the properties of oxygen at the interface. Although the group in TKK has not received any financial support for this project from Academy of Finland, the group has contributed to the project by providing computing resources at the Centre for Scientific Computing for the BUTE collaborators and actively participated all the COST workshops at their own costs.

Figure 1. Illustration of proton-coupled oxygen reduction by decamethylferrocene at the water-1,2-dichloroethane interface. In more details, the group in EPFL has been concentrating on the biphasic system of oxygen reduction by decamethylferrocene (DMFc). To better understand the reaction mechanism, the reduction of oxygen by DMFc in 1,2-dichloroethane (DCE), in contact with an aqueous solution of sulfuric acid, was first investigated and hydrogen peroxide was found to be produced in this biphasic system. The interface under polarization functions as a proton pump to drive the transfer of aqueous protons to the organic phase to participate the oxygen reduction by DMFc in DCE, as shown in Figure 1. This reaction pathway has been evaluated by various experimental protocols, such as electrochemistry, common-ion controlled electrolysis, in-situ scanning electrochemical microscopy measurement and so on. Evaluation by quantum calculations is currently undergoing by an internal collarboration in EPFL with Prof. Corminboeuf. The group in ICMUB (LIMRES) will be performing electron spin resonance studies of the oxygenated solution of decamethylferrocene in DCE at ambient or lower temperatures to detect the intermediate species indicated by the quantum calculations.

Figure 2. Molecular number density profile of DCE (solid line), water (dotted line) and O2 (filled squares) along the interface normal axis Z of the water/DCE system simulated using the Nosé–Hoover thermostat. The O2 density profile obtained with the Berendsen thermostat (open squares) is also shown for comparison. The DCE profile is magnified by a factor of four for clarity. The scale on the left refers to the water and DCE, whereas that on the right to the O2 profiles. Considering that we observed the oxygen reduction at the water-dichloroethane interface, we have been curious to know whether the solvation and reactivity of molecular oxygen at the interface are different from those in the bulk phases. Therefore, the group in BUTE has performed molecular dynamics simulations of oxygen solvated at the vicinity of water-1,2-dichloroethane interface. In particular, the distribution of oxygen along the interface normal has been evaluated. The results, as displayed in Figure 2, show that the choice of the algorithm used to keep the temperature of the system constant has a non-negligible effect on this distribution, the Nosé–Hoover thermostat being superior over the Berendsen thermostat in this respect. No adsorption of oxygen at the interface has been observed. In this calculation, the molecular scale roughness of the interface has been taken into account by means of the novel method for identification of truly interfacial molecules, based on the ideal of dropping a probe sphere perpendicular to the plane of the interface. With the list of molecules identified as truly interfacial ones, two measures of the molecular scale roughness of the surface have been proposed, and the dependence of the method on various parameters, in particular, on the size of the probe sphere has been discussed in detail.

NN

N NCo

NNH

N HN

H2TPP CoTPP

NNH

N HN

NN

N NCo

H2OEP CoOEP

NNH

NHN

NH2

NN

NN

Co

NH2

H2AP CoAP

NNHN HN

NH2

FF

FF

F FF F

FF

FF

F FF

NN

NN

NH2

FF

FF

F FF F

FF

FF

F FF

Co

H2FAP CoFAP Figure 3. Illustration of porphyrin catalysts that have been studied.

On the basis of above work, the catalytic effects of various porphyrins compounds prepared by ICMUB (LIMRES), both free-base and metalated porphyrins (with structure shown in Figure 3), on the oxygen reduction by DMFc have been studied. Conventional cobalt porphyrins, such as cobalt tetraphenylporphyrin (CoTPP) and cobalt octaethylporphyrin (CoOEP), have found to function only as

the redox catalyst. Further derivatization of the conventional cobalt porphyrin by a benzoamino group at the meso position (for example, the one so called CoAP) significantly increases the interfacial affinity of the catalyst, and thus a much stronger catalytic activity. In the course of this work, the group in ICMUB (LIMRES) has contributed a lot by commenting the efficiency of different porphyrins towards the electron reduction of dioxygen, particularly the role of protonation of the intermediate oxygen-cobalt porphyrin complex versus oxygen-oxygen bond cleavage. More importantly, the groups in JHIPC and EPFL have found that the free base porphyrins, such as tetraphenylporphyrin (H2TPP), octaethylporphyrin (H2OEP) and fluorinated tetraphenylporphyrin (H2FAP) could also catalyze the oxygen reduction by DMFc, which was supported by the electrochemical data, stopped-flow spectrophotometry and density functional theory calculations. This striking effect may change the understanding of the mechanism of porphyrin catalyzed oxygen reduction reaction, as usually only metalated porphyrins demonstrate catalytic ability.

Figure 4. Illustration of photoelectrochemical oxygen reduction in thin film system: A = O2.

In addition, the group in EPFL has also performed photo-electrochemical oxygen reduction in thin film system with a structure illustrated in Figure 4, even it is not clearly proposed in the proposal. Several types of thin film structures have been investigated. The first one is based on the layer-by-layer alternative deposition method to fabricate a thin aqueous film on solid supports, such as porous carbon material and gold electrodes. This thin aqueous layer can be sensitized by incorporation of dyes or semiconducting nanoparticles, such as CdSe nanoparticles, which behave as homogeneous porous photo-electrodes. Immersing this aqueous layer into an organic solution forms a solid electrode supported liquid|liquid interface. The second one is porphyrin sensitized titanium oxide (Ti(O)) xerogel film prepared by the sol-gel technique. The photoreduction of oxygen (A = O2 in Figure 4) in these thin film structures have been observed and analyzed using a theoretical model. In the future, our five groups will be keeping interaction on this project. In the workshop meeting held on 26th September in Villars-Switzerland, we have formulated a future plan and distributed the research work for next few months. Basically, the groups in EPFL and JHIPC will be continuing on the molecular oxygen reduction catalyzed by various porphyrins and cyclams. The following several aspects will be concentrated on, further understanding the reaction mechanism by theoretical calculations and scanning electrochemical microscopy, the thermodynamic analysis the oxygen reduction in the organic phase, investigating of adsorption of catalysts at the liquid/liquid interface by electrochemical methodologies and surface tension measurements, and extending the project to carbon dioxide reduction catalyzed by cobalt porphyrins and cyclams at the liquid-liquid interface by photoelectrochemical techniques. The ICMUB (LIMRES) group will work on the synthesis of cofacial biscobalt bisporphyrins and saturated tetraazamacrocycles, cyclam and N-substituted cyclam derivatives, which not only demonstrate catalysis on oxygen reduction but also carbon dioxide reduction and will be the studied at a liquid-liquid interface by groups in EPFL and JHIPC. The group will also, as mentioned above, perform electron spin resonance studies of oxygenated solutions of decamethylferrocene in organic solvents in order to evidence an eventual formation of a dioxygen complex of decamethylferrocene indicated by the theoretical calculations. Finally, the group in BUTE will be working on the molecular dynamic and Monte Carlo simulations on the proton structure and activity at the liquid-liquid interface, as well as the catalytic role of porphyrin catalysts at the liquid-liquid interface. During this year, four top notch publications have been made, vide Annex. Visibility

Prof. Hubert H. Girault was invited to visit different universities in Japan in October 2008, and gave a

seminar entitled: “Redox catalysis at soft interfaces” to the present the WG activities at Kyoto

University, Kyoto Institute of Technology, Osaka University, Kobe University and Nagasaki University.

Prof. Hubert H. Girault was invited as a guest professor at Beijing University in November 2008, and

gave a seminar entitled: “Redox catalysis at soft interfaces” to the present the WG activities.

WG D36-008-06 INFANTE Biopolymer based surfactants – stabilization and functionalization of particles and surfaces M. R. Infnte, WG coordinator WG meetings During 2007 two WG meetings have been carried out: first in Coimbra, 17-18 May 2007 Portugal and the second in Acquafredda di Maratea (Italy) for the period of 26-27 November 2007. Short stays of students Neus Lozano (Barcelona) in Rome Giacomo Gente (Roma) in Barcelona Patrizia Andreozzi (Rome) in Barcelona. Carmen Moran (Coimbra) in Barcelona Eduardo F. Marques (Porto) went as a Visiting Professor to Rome. Eduardo Marques (Porto) as visiting professor to Barcelona Rodrigo Brito (Porto) in Barcelona Bruno Silva (Oporto) in Sweden Rodrigo Brito (Oporto) in Sweden Cooperation Rome/Calabria (Italy) - Andreozzi, P.; La Mesa, C.; Masci, G.; Suber, L “Formation and physical-chemical

characterisation of silica-based blackberry-like nano particles capped by polysaccharides”, J. PHYS. CHEM. C, (2007), 11, 18030

- Muzzalupo, R.; Tavano, L.; Trombino, S.; La Mesa, C.;Nicotera, I.; Oliviero Rossi, C “N, N’- HEXADECANOYL- L -2 -DIAMINOMETHYL- 18- CROWN- 6 SURFACTANT: SYNTHESIS AND AGGREGATIONPROPERTIES IN AQUEOUS SOLUTIONS.., COLLOIDS SURF. B, DOI:10.1016/J.COLSURFB.2007.07.001, IN PRESS.

- Calabresi, M.; Andreozzi, P.; La Mesa, C “Polymorphic Behaviour And Supramolecular Association Systems Containing Bile Acid Salts..”, Molecules,(2007), 12(8), 1731-1754. REVIEW ARTICLE.

- ., La Mesa, C.,Proietti, C., Risuleo, G., “A Biophysical Investigation On The Binding And Controlled Dna Release In A Ctab-Sos Cat-Anioni Vesicle System. Bonincontro, A” Biomacromolecules, (2007), 81824-1829.

Cooperation Rome (Italy)/ Barcelona (Spain) - R.Muzzalupo, MR Infante,L Pérez, A Pinazo, E. F. Marques, M.L. Antonelli, C.Strinati and Camillo

La Mesa.Interactions Between Gemini Surfactants And Polymers: Thermodynamic Studies. Langmuir 2007, 23, 5963-5970

- Two more papers are in preparation Cooperation Calabria (Italy)/ Barcelona (Spain)

- C. Moran, M.R. Infante, L. Perez, A. Pinazo, M.Youssry, I.Nicotera And L. Coppola, Lyotropic Phase Behaviour Of 1,2-Dilaurolyl-Glycerol-3-O-(N_-Acetyl-L-Arginine).Submmited

- M.C. Morán, A.Pinazo, Infante, Mr. L. Coppola, R.Pons. Structure Of Semi Synthetic Membranes Formed With Dppc/Diacylglycerol Tyrosine Conjugates: Dppc/1212yac Interaction. In Preparation.

Cooperation Coimbra (Portugal)/ Lund (Sweden) Barcelona (Spain) 1. Mónica Rosa, María Del Carmen Morán, Maria Da Graça Miguel And Björn Lindman. The

Association Of Dna And Stable Catanionic Amino Acid-Based Vesicles..Colloids And Surfaces A, 2007, 301 (1-3), 361-375.

Dr. O. Soderman interacts with with Ramon Pons on the question of titration of an acid functionality at a charged interface. No manuscript has come out of this. He is also running a co-operation with Artur Valente in Coimbra on inclusion complexes formed by cyclodextrin and surfactants, using both NMR methods and calorimetric approaches. No papers published 2007, but a manuscript is in preparation. Cooperation Porto (Portugal)/ Barcelona (Spain) During the year 2007, collaborations involved a short visit of E.F. Marques to the CSIC for discussions and a seminar (March 07). This was followed by a short stay of Rodrigo Brito (PhD student, Univ. Porto) in CSIC and Univ. Barcelona in order to carry out toxicological and SAXS studies with novel amphiphiles derived from amino acids. - R.O. Brito; E.F. Marques; P. Gomes, M.J. Araújo; O. Söderman; M.R. Infante, M.T. Garcia; I.

Ribosa; P. Vinardell; M. Mitjans, “Spontaneous Vesicle Formation In A Catanionic Mixture With A Lysine-Derived Surfactant: Phase Behaviour, Structural And Toxicity Studies”, M. Book Of Proceedings Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 129-140, University Of Coimbra, 2007.

- Brito, R.O.; Marques, E.F.; Gomes, P.; Araújo, M.J.; Söderman, O.; Infante, M.R.; Garcia, M.T.; Ribosa, I., Vinardell, P.; Mitjans, M. Spontaneous Vesicle Formation In A Catanionic Mixture With A Lysine-Derived Surfactant: Phase Behaviour, Structural And Toxicity Studies, Book Of Abstracts Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 21, UNIVERSITY OF COIMBRA, 2007.

- Brito, R.O.; Marques, E.F.; Gomes, P.; Araújo, M.J.; Söderman, O.; Infante, M.R.; J. P. Douliez; Garcia, M.T.; Ribosa, I., Vinardell, P.; Mitjans, M. From Nanotubes To Spontaneous Vesicles In A Lysine-Based Surfactant: Phase Behavior, Microstructure And Toxicity Studies, Book Of Abstracts Of The 21st Conference Of The European Colloid And Interface Society, Geneva, Sept 10-14, P 1.A.43, P.187, 2007.

Univ. Porto/Lund University (with Björn Lindman, Ulf Olsson and Olle Söderman). The collaborations involved work in polymer-vesicle interactions (gels and mechanism of vesicle deformation), self-assembly of catanionic surfactants and vesicle formation in mixtures of novel amino acid-based surfactants. This collaboration involved short stays in Lund by Porto PhD students Bruno Silva (host: U. Olsson) and Rodrigo Brito (host: O. Söderman). - Antunes F. E., Brito R.O., Marques E. F., Lindman B., Miguel M. G., Mechanisms Behind The

Faceting Of Catanionic Vesicles By Polycations: Chain Crystallization And Segregation J. Phys. Chem. B, 2007, 111, 116-123.

- B.F.B. Silva; E.F. Marques, U. Olsson, Miscibility Gap In A Catanionic Lamellar Phase, Book Of Proceedings Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 331-339, University Of Coimbra, 2007.

- Silva, B.F.B; Marques, E. F.; Olsson, U. Lamellar Miscibility Gap In A Binary Catanionic Surfactant-Water System. J Phys. Chem B, 2007, 111, 13520-13526.

Comunications in conferences: ORAL - Marques, E.F.; Brito, R.O.; Gomes, P., Araújo, M.J.; Douliez, J.P.; Söderman, O. Novel Lysine-

based surfactants: from self-assembled tubes to spontaneous liposomes. Abstract Book of the 8th

Congress of Physical Chemistry of the Portuguese Society of Chemistry, p. 29, FC5, Luso-Portugal, 21-22 June, 2007.

- Brito, R.O.; Marques, E.F.; Gomes, P.; Araújo, M.J.; Söderman, O.; Infante, M.R.; Garcia, M.T.; Ribosa, I., Vinardell, P.; Mitjans, M. Spontaneous vesicle formation in a catanionic mixture with a lysine-derived surfactant: phase behaviour, structural and toxicity studies, Book of Abstracts of the 2nd Iberic Meeting of Colloids and Interfaces - RICI2, p. 21, University of Coimbra, 2007.

- Silva, B.F.B.; Marques, E.F.; Olsson, U., Miscibility gap in a catanionic lamellar phase, Book of Abstracts of the 2nd Iberic Meeting of Colloids and Interfaces - RICI2, p. 36, University of Coimbra, 2007.

- Silva, B.F.B.; Marques, E.F.; Olsson U., Self-Assembly in an asymmetric catanionic surfactant: unusual lamellar-lamellar coexistence and vesicle-micelle transition, Book of Abstracts of the 21st Conference of the European Colloid and Interface Society, Geneva, Sept 10-14, CL6.3.3, p. 91, 2007.

Univ. Porto/Sapienza Roma University (with C. La Mesa). The collaborations involved a short stay by E.F. Marques as a visiting professor in Roma University for one month (Oct 07) for the development of work on bile salt/gemini surfactant mixtures, fluorocarbon/hydrocarbon surfactant mixtures with spontaneous vesicle formation and polymer-vesicle interactions. E.F. Marques also presented two seminars in the local Dept Chemistry. • Muzzalupo, R.; Infante, M. R.; Perez, L.; Pinazo, A.; Marques, E. F.; Antonelli, M. L.; Strinati, C.;

La Mesa, C. Interactions between Gemini Surfactants and Polymers: Thermodynamic Studies, Langmuir, 2007, 23, 5963-5970.

Univ. Porto/Calabria University (with Luigi Coppola) The collaborations involved work on the rheological and self-diffusion NMR characterization of the extended isotropic solutions formed by mixtures of bile salt with cationic surfactant didodecyldimethylammonium bromide. • M. Youssry, L. Coppola, E. F. Marques and I. Nicotera. The microstructure of the L1-phase of the

DDAB/STDC/water system: Rheology and PGSE-NMR study, manuscript submitted. Cooperation Maribor (Slovenia) with Graz (Austria) • FRAS, Lidija, STENIUS, Peer, LAINE, Janne, STANA-KLEINSCHEK, Karin. Topochemical

modification of cotton fibres with carboxymethyl cellulose. Cellulose (Dordr., Online), Published online 27 September 2007, 7

• HRIBERNIK, Silvo, SFILIGOJ-SMOLE, Majda, STANA-KLEINSCHEK, Karin, BELE, Marjan, JAMNIK, Janko, GABERŠČEK, Miran. Flame retardant activity of SiO[sub]2-coated regenerated cellulose fibres. Polym. degrad. stab.. [Print ed.], 2007, vol. 92, no. 11, str. 1957-1965. JCR IF (2006): 2.174, SE (14/75), polymer science, x: 1.42

Published Scientific Conference Contribution Abstract • REISCHL, Martin, STANA-KLEINSCHEK, Karin, RIBITSCH, Volker. Physico-chemical

characterization of cellulose polymers. V: 12. Österrechische Chemietage : September 10-13, 2007, Klagenfurt, Austria : book of abstracts. [Vienna]: Gesellschaft Österreichische Chemiker, 2007, str. MS-31. [COBISS.SI-ID 11646998]

• REISCHL, Martin, KUZMA, Bojan, BRUMEN, Milan, ŽEROVNIK, Janez, STANA-KLEINSCHEK, Karin, RIBITSCH, Volker. Modelling adsorption kinetics of dye molecules in cellulose fibres. V: 12. Österrechische Chemietage : September 10-13, 2007, Klagenfurt, Austria : book of abstracts. [Vienna]: Gesellschaft Österreichische Chemiker, 2007, str. MS-36.

• FRAS, Lidija, STANA-KLEINSCHEK, Karin, STENIUS, Peer. Influence of adsorbed carboxymethyl cellulose on the cotton fibre adsorption capacity for cationic surfactant. V: 12. Österrechische Chemietage : September 10-13, 2007, Klagenfurt, Austria : book of abstracts. [Vienna]: Gesellschaft Österreichische Chemiker, 2007, str. MS-37.

• GAAL, Denise, REISCHL, Martin, FRAS, Lidija, KÖSTLER, Stefan, STANA-KLEINSCHEK, Karin, RIBITSCH, Volker. Interaction of functional polysaccharides with cellulosic surfaces for medical applications. V: 12. Österrechische Chemietage : September 10-13, 2007, Klagenfurt, Austria : book of abstracts. [Vienna]: Gesellschaft Österreichische Chemiker, 2007, str. MS-38.

Patent Application • FRAS, Lidija, BUT, Igor, STANA-KLEINSCHEK, Karin, RIBITSCH, Volker, ŠAUPERL, Olivera,

ZABRET, Andrej. Tampon, ki vsebuje pH regulirajočo ter antibakterijsko in antimikotično aktivno formulacijo, in postopek njegove izdelave : zahteva za podelitev patenta [Uradu Republike Slovenije za intelektualno lastnino] : št. prijave P-200600138, datum vložitve prijave 05.06.2006. Ljubljana: Urad Republike Slovenije za intelektualno lastnino, 2006. 23 f

• STRNAD, Simona, INDEST, Tea, LAINE, Janne, STANA-KLEINSCHEK, Karin, VESEL, Alenka, DWORCZAK, Renate. Poliestrski biomaterial s površino, ki ima antitrombotične lastnosti, in postopek njegove izdelave : zahteva za podelitev patenta, št. prijave 200700097 z dne 19.04.2007. Ljubljana: Urad Republike Slovenije za intelektualno lastnino, 2007. 1 f. [COBISS.SI-ID 11320854]

Articles in preparation with Belgique collaboration • Thermodynamic characterization of xylan films. Effect of the incorporation of organically modified

clay nanoparticles and Inulin. • Study of the adsorption of Inulin onto organic modified clay particles. Selective ion adsorption. Cooperation Lund (Sweden)/ Coimbra (PORTUGAL) 1. Publications • “The association of DNA and stable catanionic amino acid-based vesicles“, M. Rosa, M. C. Morán,

M. G. Miguel, B. Lindman Colloids Surf. A: Physicochem. Eng. Aspects, 301, 361, 2007. • “DNA encapsulation by biocompatible catanionic vesicles”, M.Rosa, M. G. Miguel, B. Lindman J.

Colloid Int. Sci., 312, 87, 2007. • “DNA pre-condensation with an amino acid-based cationic amphiphile. A viable approach for

liposome-based gene delivery”, M.Rosa, N. Penacho, S. Simoes, M. C. P. Lima, B. Lindman, M. G. Miguel Molecular Membrane Biology, accepted, 2007.

• “DNA gel particles: particle preparation and release characteristics”, M.C. Morán, M.G. Miguel, B. Lindman, Langmuir, 23, 6478, 2007.

• “Manipulation of DNA with surfactants and lipids: Compaction and decompaction”, B. Lindman, M. C. Morán, D. Costa, R. Dias, M. Miguel, Polymer Preprints, Japan, 56, 49, 2007.

• “Effect of additives on swelling of covalent DNA gels”, D. Costa, M. G.Miguel, B. LIndman, J. Phys. Chem. B, 111, 8444, 2007

• “Responsive Polymer Gels: Double-Stranded versus Single-Stranded DNA, D. Costa, M. G. Miguel, B. Lindman, J. Phys. Chem. B, 111, 10886, 2007

• “Surfactant-DNA Gel particles: formation and release characteristics”, M. C. Morán, M. G. Miguel, B. Lindman. Biomacromolecules, 8, 3886, 2007.

• “Effect of headgroup on DNA-cationic surfactant interactions” A. Dasgupta, P. K. Das, R. S. Dias, M. G. Miguel, B. Lindman, M. Gnanamani, M. Ganguli, S. Maiti. J. Phys. Chem. B, 111, 8502, 2007.

• “Viscoelasticity of a non ionic lamellar phase”, B. Medronho, M. G. Miguel, U. Olsson.Langmuir, 23, 5270, 2007.

• “How does a non-ionic hydrophobically modified polymer interact with a nonionic vesicle? Rheological aspects”, T. dos Santos, B. Medronho, F. E. Antunes, B. Lindman, M.G. Miguel. Colloids and Surfaces A: Physicochem. Eng. Aspects, In press, 2007.

• “New PVA–DNA cryogels: characterization, swelling and transport studies”, A. Papancea, A.J.M. Valente, S. Patachia, M.G. Miguel, B. Lindman, Langmuir, accepted, 2007.

• “DNA folding: observing details of the conformational behavior “, M. C. Morán, A.A.C.C. Pais, S. Gawęda, R. S. Dias, K. Schillén, B. Lindman, M. G. MMguel, Biomacromolecules, submitted, 2007.

• “Cationic Fluorene Based Conjugated Polyelectrolyte: Induced Compaction in DNA”, M.L. Davies, M.G. Miguel, M.C. Morán, H.D. Burrows, B. Lindman, P. Douglas.

• Manuscript in preparation. January-December 2008

During the second full year of activity, efforts have been made to get significant collaboration between the group members of the project with an excellent scientific production. Lund/Coimbra Adsorption of bio-surfactants (protein and sugar derived -surfactants) on surfaces and particles in particular DNA encapsulation. The results are reflected in 23 contributions (vide Annex on publications): Rome/Barcelona Collaboration dealt with interactions between Gemini surfactants and homo-polymers, to find rational explanation on the interactions between such association colloids and macromolecules. The work deals essentially with the thermodynamic properties of the above mixtures. In another research line, surface coverage of nano-particles by Gemini surfactants was experienced. On this purpose, DLS and NMR were used in combination. In a third project, still under completion, the relations between size and thermodynamic stability of vesicles made of common lipids and arginine-based surfactants was performed. Experiments were performed by DLS, electro-phoretic mobility and TEM. The results are reflected in 4 contributions to literature (vide Annex on publications)

Rome-Calabria

Collaboration dealt with interactions between new synthetic surfactants (forming micelles or vesicles and niosomes), to find rational explanation to the observed behavior. The work deals essentially with the structural and thermnodynamic properties of the above mixtures. Another project, still under completion, deals with the synthesis and physic-chemical properties off synthetic lipids with sugar as polar head groups. The results are disseminated in four publications (vide Annex on publications) Rome-Maribor The work in collaboration dealt with the stabilization of Titania nano-particles mediated by adsorption of surfactants. Investigation dealt with DLS and electro-phoretic mobility. It is planned to extend the collaboration. The results are bein reflected in this article in preparation:

Use of Surfactants to Stabilise TiO2 P25 Colloidal Dispersions N. Veronovski, P. Andreozzi, C.

La Mesa,, M. Sfiligoj-Smole, K. Stana-Kleinschek, submitted.

Rome-Porto The work in collaboration dealt with the interactions between Gemini and polymers, as formerly indicated in the collaboration with Barcelona’s group. Another project, still under completion, deals with the characterization of vesicular dispersions made by oppositely charged surfactants (under completion). Investigation dealt with DLS and electrophoretic mobility. A relevant article is listed in Annex on publications. Rome-Coimbra The work in collaboration dealt with thermal gelation of hydrophobically modified polysaccharides, such as EHEC or similar macromolecules, and on the effect that cyclodextrines have in controlling thermal gelation. The results were unconclusive.

ANNEX 2: JOINT PAPERS, PATENTS

COST ACTION D36

Action-related publications (136)

WG D36/001/06 POSPISIL 1. P. Mořkovská., M.Hromadová, L. Pospíšil, S. Giannarelli “Double Layer Effects and Distance

Dependence of Electron Transfer in Reduction of Nitro Aromatic Radical Anion.” Langmuir, 22 (2006) 1896.

2. M. Hromadová, M. Salmain, N. Fischer-Durand, L. Pospíšil, G. Jaouen, “Electrochemical microbead-based immunoassay using an (η5-cyclopentadienyl) tricarbonylmanganese redox marker bound to bovine serum albumine.”, Langmuir, 22 (2006) 506-511.

3. M. Hromadová, R. Sokolová, L. Pospíšil, N. Fanelli , “Surface Interactions of s-Triazine-Type Pesticides. An Electrochemical Impedance Study”, J. Phys. Chem. B, 2006, 110 (2006) 4869-4874.

4. L. Pospíšil, J. Fiedler, M. Hromadová, M. Gál, M.Valášek, J. Pecka, J. Michl “Search for a One-Electron Reduction of the Cation Radical of an "Extended Viologen", p-Phenylene-bis-4,4'-(1-Aryl-2,6-Diphenylpyridinium)”, J. Electrochem. Soc., 153 (2006) E179.

5. S. Ghumaan, B. Sarkar, N. Chanda, M. Sieger, J. Fiedler, W. Kaim and G. K. Lahiri 2,2/-Dipyridylketone (dpk) as Ancillary Acceptor and Reporter Ligand in Complexes [(dpk)(Cl)Ru(µ-tppz)Ru(Cl)(dpk)]n+ Where tppz = 2,3,5,6-Tetrakis(2-pyridyl)pyrazine. Inorg. Chem. 45 (2006) 7955.

6. L. PospĂ-ĹĄil, N. Varaksa, T. F. Magnera, T. Brotin, J. Michl, “Adsorption of tentacled tetragonal star connectors, C4R4-Co-Cp(HgS)5, on mercury. Langmuir, 23 (2007) 930-935.

7. L. RulĂ-ĹĄek, O. Exner, L. Cwiklik, P. Jungwirth, I. StarĂ˝, L. PospĂ-ĹĄil, Z. Havlas, “On the Convergence of the Physico-Chemical Properties of [n]Helicenes. J. Phys. Chem. C, 111 ( 2007) 14948-14955.

8. M. Koley, B. Sarkar, S. Ghumaan, E. Bulak, J. Fiedler, W. Kaim, and G. Kumar Lahiri “Probing Mixed-Valence in a New tppz-Bridged Diruthenium (III,II) Complex {(tppz)[Ru(bik)Cl]2}3+ (tppz=2,3,5,6-Tetrakis(2- pyridyl)pyrazine, bik = 2,2/-Bis(1-methylimidazolyl) ketone): EPR Silence, Intervalence Absorption, and mueCO Line Broadening. Inorg. Chem., 46 (2007) 3736-3742.

9. E. Bulak, M. Leboschka, B. Schwederski, O. Sarper, T. Varnali, J. Fiedler, F. Lissner, T. Schleid, and W. Kaim, “Reversibly Reducible cis-Dichloroplatinum(II) and cis- Dichloropalladium(II) Complexes of Bis(1-methylimidazol-2-yl) glyoxal. Inorg. Chem., 46 (2007) 5562-5566.

10. S. Kar, B. Sarkar, S. Ghumaan, M. Leboschka, J. Fiedler, W. Kaim, and G. Kumar Lahir, “Ancillary ligand determination of the spin location in both oxidized and reduced forms of diruthenium complexes bridged by bis-bidentate 1,4-bis(2-phenolato)-1,4-diazabutadiene. Dalton Trans., 2007, 1934-1938.

11. L. Pospíšil, M. Hromadová, M. Gál, J. Bulíčková, R. Sokolová, N. Fanelli, “Electrochemical impedance of nitrogen fixation mediated by fullerene-cyclodextrin complex”, Electrochim. Acta, 53 (2008) 7445

12. L. Pospíšil, M. Hromadová, R. Sokolová, J. Bulíčková, N. Fanelli, “Cationic Catalysis and Hidden Negative Differential Resistance in Reduction of Radical Anion of nitrobenzene”, Electrochim. Acta, 53 (2008) 4852.

13. R. Sokolová, M. Hromadová, J. Fiedler, L. Pospíšil, S. Giannarelli, M. Valášek, “Reduction of substituted benzonitrile pesticides”, J. Electroanal. Chem., 622 (2008) 211

14. S. Samanta, P. Singh, J. Fiedler, S. Záliš, W. Kaim, ”Singlet diradical complexes of ruthenium and osmium: Geometrical and electronic structures and their unexpected changes on oxidation”, Inorg. Chem., 47 (2008) 1625.

WG D36/003/06 VENEZIA 15. A. M. Venezia, F. L. Liotta, G. Pantaleo, A. Beck, A. Horváth, O. Geszti, A. Kocsonya and L.

Guczi, Effect of Ti (IV) loading on CO oxidation activity of gold on titania doped silica, Appl. Catal. A., 310, 114 (2006).

16. L. Guczi, Z. Pászti, K. Frey, A. Beck, G. Pető, Cs. S. Daróczy, Modeling gold/iron oxide interface system, Topics in Catalysis, 39, 137 (2006).

17. Krisztina Frey, Andrea Beck, Gábor Petõ, Gy. Molnár and László Guczi, Activity of TiO2 Overlayer Deposited on Au/SiO2/Si(100) Model System, Catal. Commun., 7, 64 (2006).

18. Anita Horváth, Andrea Beck, Antal Sárkány, Györgyi Stefler, Zsolt Varga, Olga Geszti, Lajos Tóth and László Guczi, Silica supported Au nanoparticles decorated by TiO2: formation, morphology and CO oxidation activity, J. Phys. Chem. B., 110, 15417 (2006).

19. László Guczi, Gold Catalyst Research at the Institute of Isotopes, Budapest. Gold Bulletin, 39, 121 (2006).

20. A.Beck, A. Horváth, A. Sárkány, L. Guczi, Building blocks of nanosized supported metals for catalysis: carbonyl clusters or colloids? Current Applied Physics, 6 (2): 200-204 (2006).

21. S. Leclerc, G. Trausch, B. Cordier, D. Grandclaude, A. Retournard, J. Fraissard, D. Canet, Chemical shift imaging (CSI) by precise object displacement, Magn. Reson. Chem., 44 (2006) 311-317.

22. A.Garsuch, W. Bohjimann, R. Sattler, J. Fraissard, O. Klopel, 129Xe NMR studies on carbon replies of Y zeolites, Carbon, 44(7) (2006) 1173-1179.

23. K. V. Romanenko, X. PY, J-B. D’Espinose de la caillerie, O.B. Lapina, J. Fraissard, 129Xe NMR study of pitch-based activated carbon modified by air oxidation/pyrolysis cycles: a new approach to probe the micropore size, The Journal of Physical Chemistry B, 110(7) (2006) 3055-3060.

24. Kovalvchuk, H. Sfihi, L. Kostenko, V. Zaitsev, Preparation, structure and thermal stability of onium- and amino-functionalized silicas for the use as catalysts supports. Journal of Colloid and Interface Science , 302 (2006) 214-229.

25. S. A. Alekseev,V. N. Zaitsev, J. Fraissard Organosilicas with covalently bonded groups under thermochemical treatment, Chem. Mater., 18 (2006) 1981-1987.

26. Ivan Ogurtsov, Iolanta Balan, Gabriel Munteanu, Multipole moments and polarizability of the molecular systems with D3h symmetry in orbitally degenerate electronic states, International Journal of Quantum Chemistry, 106 (2006), 1413-1418.

27. A. M. Venezia, R. Muraria, G. Pantaleo, G. Deganello , “Nature of cobalt active species in hydrodesulfurization catalysts: combined support and preparation method effects” , J. Mol. Catal, 271, 238-245, 2007.

28. A. M. Venezia, R. Murania, G. Pantaleo, G. Deganello, “Hydrodesulfurization Co based catalysts modified by Au”, Gold Bull. 40, 130-134, 40 (2007).

29. A. M. Venezia, R. Murania, G. Pantaleo, G. Deganello.”Pd and PdAu on mesoporous silica for methane oxidation: Effect of SO2.” J. Catal. 251, 94-102 (2007).

30. L. Ilieva, G. Pantaleo, I. Ivanov, A.M. Venezia, D. Andreeva, "NO reduction by CO in the presence of water over gold supported catalysts on CeO2-Al2O3 mixed support, prepared by mechanochemical activation", Appl. Catal. B: Env., 76, 107-114 (2007).

31. Beck, A. Horváth, Z. Schay, Gy. Stefler, Zs. Koppány, I. Sajó, O. Geszti, L. Guczi, Supported gold-palladium bimetallic catalysts. Structure and catalytic activity in CO oxidation, Topics in Catal., 44, 115 (2007).

32. László Guczi, Andrea Beck, Anita Horváth, Antal Sárkány, Györgyi Stefler, Olga Geszti, Novel Method for Preparation of Nanostructured Au/TO2 on SiO2 Support by Colloidal Synthesis, Studies Surf. Sci. Catal., 172, 221 (2007)

33. M. Petryk, S. Leclerc, D. Canet, J. Fraissard, Mathematical modeling and visualization of gas diffusion in a zeolite bed using a slice selection procedure, Diffusion Fundamentals 4 (2007) 11.1 - 11.23.

34. V. Gerda, K.I. Patrylak, YU.G. Voloshyna, J. Fraissard, Isomerization of Hexane on PtAuNanoparticles Supported on Zeolites. Catalysis Today , 122 (2007) 338-340.

35. V. K. Romanenko, J-B. D’Espinose De Lacaillerie, O. Lapina, J. Fraissard Is 129Xe NMR a useful technique for probing the pore structure and surface properties of carbonaceous solids? Microporous and Mesoporous Materials, 105 (2007) 118-123.

36. K. Romanenko, P.A. Simonov, A.G. Abrosimov, O. B. Lapina, A. Fonseca, J. B.Nagy, J.-B. D’Espinose and J. Fraissard 129Xe NMR study of the localization of PdCl2 supported on carbon nanotubes, React. Kinet. Catal. Lett., 90, N° 2, 355-364 (2007).

37. T. Kovalchuck, H. Sfihi, V. Zaitsev, J. Fraissard. Recyclable solid catalysts for epoxidation of alkenes: amino- and oniumsilica-immobilized [HPO4{W2O2(µ-O2)2(O2)2}]2- anion, J. Catal., 249 (2007) 1-14

38. Nassos S, Svensson EE, Boutonnet M, et al.The influence of Ni load and support material on catalysts for the selective catalytic oxidation of ammonia in gasified biomass Appl. Catalysis B, 74 (2007) 92-102.

39. Eriksson S, Rojas S, Boutonnet M, et al. Effect of Ce-doping on Rh/ZrO2 catalysts for partial oxidation of methane, Appl. Catal. A, 326 (2007) 8-16.

40. N. Kruse, J. Schweicher, A. Bundhoo, A. F. Frennet and T. Visart de Bocarmé, Topics in Catalysis, in press

41. L. Ilieva, G. Pantaleo, G. Munteanu, A.M. Venezia, D. Andreeva, "TPD of CO and NO over gold/ceria catalysts for NOx reduction", Rev. Roumaine Chim., in press.

42. L. Ilieva, G. Pantaleo, N. Mintcheva, I. Ivanov, A.M. Venezia, D. Andreeva, "Nano-structured gold catalysts supported on CeO2-Al2O3 for NOx reduction by CO: Effect of catalysts pretreatment and feed composition", Journal of Nanoscience & Nanotechnology (2007), in press.

43. 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. 44. M. 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., doi:10.1016/j.apcatb.2008.09.023. 45. L. Ilieva, G. Pantaleo, M. Kancheva, R. Nedyalkova, A.M. Venezia, D. Andreeva, “NO reduction by

CO over gold catalysts based on doped by Me3+

(Me=Al or lanthanides) ceria supports, prepared

by mechanochemical activation: effect of water in gas feed”, Appl. Catal. B: Environ., submitted. 46. Krisztina Frey, Viacheslav Iablokov, Gérôme Melaet, László Guczi, and N. Kruse, „CO oxidation

activity of Ag/TiO2 catalysts prepared via oxalate co-precipitation”, Catal. Lett. 124 (2008) 74-79 47. Beck, A. Horváth, Gy. Stefler, R. Katona, O. Geszti, Gy. Tolnai, L. Liotta, L. Guczi, ”Formation and

Structure of Au/TiO2 and Au/CeO2 Nanostructures in Mesoporous SBA-15”, Catalysis Today, 139 (2008) 180.

48. 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: Environ (2008) doi: 10.1016/j.acatb. 2008.10.023

WG D36/005/06 FERMIN 49. T.M. Day, P.R. Unwin and J.V. Macpherson, Factors Controlling the Electrodeposition of Metal

Nanoparticles on Pristine Single Walled Carbon Nanotubes, Nano Lett. 7 (2007) 51. 50. P. Bertoncello, M. Peruffo and P.R. Unwin, Formation and Evaluation of Electrochemically-Active

Ultra-Thin Palladium-Nafion Nanocomposite Films, Chem. Commun. (2007) 1597-1599 51. F. Li, I. Ciani, P. Bertoncello, P.R. Unwin, J. Zhao, C.R. Bradbury and D.J. Fermín, Scanning

Electrochemical Microscopy of Redox-Mediated Hydrogen Evolution Catalyzed by Two Dimensional Assemblies of Pd Nanoparticles, J. Phys. Chem. C submitted.

52. F.J.E.Scheijen, G.L.Beltramo, S.Hoeppener, T.H.M.Housmans, M.T.M.Koper, The Electrooxidation of Small Organic Molecules on Pt Nanoparticles Supported on Au: Influence of Pt Deposition Procedure, J. Solid State Electrochem. in press.

53. E. Santos and W. Schmickler, Electrocatalysis of Hydrogen Oxidation -- Theoretical Foundations, Ang. Chem. Int. Ed., 46 (2007) 8262.

54. E. Santos and W. Schmickler, Electronic Interactions Decreasing the Activation Barrier for the Hydrogen Electro-Oxidation Reaction, Electrochim. Acta in press.

55. A. Heras, A. Colina, J. López-Palacios, A.Kaskela, A. G. Nasibulin, V. Ruiz, Esko I. Kauppinen, Electrochemistry Communications, in press.

56. A. Martinez, A. Colina, R.A.W. Dryfe, V. Ruiz, submitted to Electrochimica Acta. 57. 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. 58. F.Li, P. Bertoncello, I. Ciani, G. Mantovani and P.R. Unwin, Adv. Func. Mat. 18 (2008) 1685 59. L. Hutton, M. E. Newton, P. R. Unwin and J. V. Macpherson, Anal. Chem. 2009, in press 60. Susana Palmero , Alvaro Colina, Emma Muñoz, Aránzazu Heras, Virginia Ruiz, Jesús López-

Palacios, Electrochemistry Communications 11 ( 2009) 122.

61. E. Santos, K. Pötting and W. Schmickler, On the catalysis of the hydrogen oxidation, Disc. Farad. Soc., 140 (2009) 209.

62. E. Santos, A. Lundin, K. Pötting, P. Quaino and W. Schmickler, Hydrogen evolution and oxidation -- a prototype for electrocatalytic reactions, J. Appl. Electrochem., available online.

WG D36/006/06 MUL 63. H. Si-Ahmed, M. Calatayud, C. Minot, E. Lozano Diz, A. E. Lewandowska and M. A. Bañares,

“Combining theoretical description with experimental in situ studies on the effect of potassium on the structure and reactivity of titania-supported vanadium oxide catalyst”, Catal. Today 126 (2007) 96-102

64. Mònica Calatayud, Anna E. Lewandowska, Enrique Lozano-Diz, Christian Minot y Miguel A. Bañares, “Combinando Descripción Teórica con Estudios in situ Raman del Efecto de Aditivos Alcalinos en la Estructura y Reactividad de Catalizadores de Óxido de Vanadio Soportado en Titania” V Congreso Argentino de Catálisis (2007) ISBN 978-950-34-0437-9

65. M. Trejda, A. Tuel, J. Kujawa, B. Kilos, M. Ziolek„Niobium rich SBA-15 materials – preparation, characterisation and catalytic activity”, Microp. Mesop. Mater., 110 (2008) 271-278

66. Lewandowska, A.E., Bañares, M.A., Ziolek, M., Khabibulin, D.F., Lapina, O.B., , “Structural and reactive relevance of V + Nb coverage on alumina of V-Nb-O/Al2O3 catalytic systems”, J. Catal. 255 (2008) 94-103

67. “Novel AuNbMCM-41 catalyst for methanol oxidation”, I. Sobczak, A. Kusior, J. Grams and M. Ziolek, Stud.Surf.Sci.Catal. 170 (2007) 1300, in preparation

68. Korhonen, S.T., Calatayud, M., Krause, A.O.I., “Stability of hydroxylated (1�11) and (1�01) surfaces of monoclinic zirconia: A combined study by DFT and infrared spectroscopy”, Journal of Physical Chemistry C 112 (2008) 6469-6476

69. Korhonen, S.T., Calatayud, M., Outi I Krause, A., “Structure and stability of formates and carbonates on monoclinic zirconia: A combined study by density functional theory and infrared spectroscopy“, Journal of Physical Chemistry C 112 (2008) 16096-16102

70. Lewandowska, A.E., Calatayud, M., Lozano-Diz, E., Minot, C., Bañares, M.A., “Combining theoretical description with experimental in situ studies on the effect of alkali additives on the structure and reactivity of vanadium oxide supported catalysts”, Catalysis Today 139 (2008) 209-213

71. Tielens, F., Trejda, M., Ziolek, M., Dzwigaj, S., “Nature of vanadium species in V substituted zeolites: A combined experimental and theoretical study”, Catalysis Today 139 (2008) 221-226

72. I. Sobczak, N. Kieronczyk, M. Trejda, M. Ziolek, “Gold, vanadium, and niobium containing MCM-41 matrials – catalytic properties in methanol oxidation”, Catal. Today, 139 (2008) 188-195

73. M. Trejda, J. Kujawa, M. Ziolek, J. Mrowiec – Bialon „Nb-containing mesoporous materials of MCF type – acidic and oxidative properties”, Catal. Today, 139 (2008) 196 – 201

74. F. Tielens, M. Trejda, M. Ziolek, S Dzwigaj, „ Nature of vanadium species in V substituted zeolites; a combined experimental and theoretical studies”, Catal. Today, 139 (2008) 221 – 226

75. 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, in press,

76. I. Sobczak, M. Ziolek, N. Kieronczyk, „Gold-vanadium-niobium catalysts in environmental protection – adsorption and interaction of NO, C3H6 and O2 – FTIR study” Adsorption, in press

77. D. Blasco-Jimenez, I. Sobczak, M. Ziolek, A.J.Lopez-Peinado, R.M. Martin-Aranda “The influence of chemical composition of MCM-41 support on the properties of amine-grafted materials”, J. Catal. Submitted

78. M.A. Bañares, G. Mestl, “In situ and Operando Raman Spectroscopy for the Structural Characterization of Operating Catalysts”, Advances in Catalysis 52 (2009) in press

WG D36/007/06 GIRAULT 79. “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. B.

Partay, G. Hantal, P. Jedlovszky, A Vincze, G. Horvai, Journal of Computacional Chemistry, in press (2007)

80. 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.

81. 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.

82. 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, accepted.

WG D36/008/06 INFANTE 83. Andreozzi, P.; La Mesa, C.; Masci, G.; Suber, L “Formation and physical-chemical

characterisation of silica-based blackberry-like nano particles capped by polysaccharides”, J. PHYS. CHEM. C, (2007), 11, 18030

84. Muzzalupo, R.; Tavano, L.; Trombino, S.; La Mesa, C.;Nicotera, I.; Oliviero Rossi, C “N, N’- HEXADECANOYL- L -2 -DIAMINOMETHYL- 18- CROWN- 6 SURFACTANT: SYNTHESIS AND AGGREGATIONPROPERTIES IN AQUEOUS SOLUTIONS, COLLOIDS SURF. B, DOI:10.1016/J.COLSURFB.2007.07.001, IN PRESS.

85. Calabresi, M.; Andreozzi, P.; La Mesa, C “Polymorphic Behaviour And Supramolecular Association Systems Containing Bile Acid Salts..”, Molecules,(2007), 12(8), 1731-1754. REVIEW ARTICLE.

86. ., La Mesa, C.,Proietti, C., Risuleo, G., “A Biophysical Investigation On The Binding And Controlled Dna Release In A Ctab-Sos Cat-Anioni Vesicle System. Bonincontro, A” Biomacromolecules, (2007), 81824-1829.

87. R.Muzzalupo, MR Infante,L Pérez, A Pinazo, E. F. Marques, M.L. Antonelli, C.Strinati and Camillo La Mesa.Interactions Between Gemini Surfactants And Polymers: Thermodynamic Studies. Langmuir 2007, 23, 5963-5970

88. C. Moran, M.R. Infante, L. Perez, A. Pinazo, L. Coppola, M.Youssry and I.Nicotera. Lyotropic Phase Behaviour of 1,2-dilaurolyl-glycerol-3-O-(N-acetyl-L-arginine). Paper-submitted to Colloids and Surfaces A

89. M.C. Morán, A.Pinazo, Infante, MR. L. Coppola, R.Pons. Structure Of Semi Synthetic Membranes Formed With DPPC/Diacylglycerol Tyrosine Conjugates: DPPC/1212YAc Interaction. Manuscript.

90. MÓNICA ROSA, MARÍA DEL CARMEN MORÁN, MARIA DA GRAÇA MIGUEL AND BJÖRN LINDMAN. THE ASSOCIATION OF DNA AND STABLE CATANIONIC AMINO ACID-BASED VESICLES..COLLOIDS AND SURFACES A, 2007, 301 (1-3), 361-375.

91. R.O. Brito; E.F. Marques; P. Gomes, M.J. Araújo; O. Söderman; M.R. Infante, M.T. Garcia; I. Ribosa; P. Vinardell; M. Mitjans, “Spontaneous Vesicle Formation In A Catanionic Mixture With A Lysine-Derived Surfactant: Phase Behaviour, Structural And Toxicity Studies”, M. Book Of Proceedings Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 129-140, University Of Coimbra, 2007.

92. Brito, R.O.; Marques, E.F.; Gomes, P.; Araújo, M.J.; Söderman, O.; Infante, M.R.; Garcia, M.T.; Ribosa, I., Vinardell, P.; Mitjans, M. Spontaneous Vesicle Formation In A Catanionic Mixture With A Lysine-Derived Surfactant: Phase Behaviour, Structural And Toxicity Studies, Book Of Abstracts Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 21, UNIVERSITY OF COIMBRA, 2007.

93. Brito, R.O.; Marques, E.F.; Gomes, P.; Araújo, M.J.; Söderman, O.; Infante, M.R.; J. P. Douliez; Garcia, M.T.; Ribosa, I., Vinardell, P.; Mitjans, M. From Nanotubes To Spontaneous Vesicles In A Lysine-Based Surfactant: Phase Behavior, Microstructure And Toxicity Studies, Book Of Abstracts Of The 21st Conference Of The European Colloid And Interface Society, Geneva, Sept 10-14, P 1.A.43, P.187, 2007.

94. Antunes F. E., Brito R.O., Marques E. F., Lindman B., Miguel M. G., Mechanisms Behind The Faceting Of Catanionic Vesicles By Polycations: Chain Crystallization And Segregation J. Phys. Chem. B, 2007, 111, 116-123.

95. B.F.B. Silva; E.F. Marques, U. Olsson, Miscibility Gap In A Catanionic Lamellar Phase, Book Of Proceedings Of The 2nd Iberic Meeting Of Colloids And Interfaces - RICI2, P. 331-339, University Of Coimbra, 2007.

96. Silva, B.F.B; Marques, E. F.; Olsson, U. Lamellar Miscibility Gap In A Binary Catanionic Surfactant-Water System. J Phys. Chem B, 2007, 111, 13520-13526.

97. FRAS, Lidija, STENIUS, Peer, LAINE, Janne, STANA-KLEINSCHEK, Karin. Topochemical modification of cotton fibres with carboxymethyl cellulose. Cellulose (Dordr., Online), Published online 27 September 2007, 7

98. HRIBERNIK, Silvo, SFILIGOJ-SMOLE, Majda, STANA-KLEINSCHEK, Karin, BELE, Marjan, JAMNIK, Janko, GABERŠČEK, Miran. Flame retardant activity of SiO[sub]2-coated regenerated cellulose fibres. Polym. degrad. stab.. [Print ed.], 2007, vol. 92, no. 11, str. 1957-1965. JCR IF (2006): 2.174, SE (14/75), polymer science, x: 1.42

99. M. Carmen Moran, M. Gracia Miguel, and Bjorn Lindman. DNA Gel Particles: Particle Preparation and Release Characteristics. Langmuir 2007, 23, 6478-6481.

100. Reischl M, Stana-Kleinschek K, Ribitsch V. Adsorption of surfactants on polymer surfaces investigated with a novel zeta-potential measurement system Materials Science Forum , 2006, 514-516, 1374-1378 Part 1-2

101. Monica Rosa, M. Rosa Infante, Maria da G. Miguel, Björn Lindman. Amino Acid-based Catanionic Surfactant Systems Spontaneous Vesicles, Cubosomes And Hexasomes. Langmuir 2006; 22(13); 5588-5596.

102. Gotchev G, Kolarov T, Levecke B, et al.Interaction forces in thin liquid films stabilized by hydrophobically modified inulin polymeric surfactant. 3. Influence of electrolyte type on emulsion films, Langmuir 23 (11): 6091-6094 MAY 22 2007

103. Thoren PEG, Soderman O, Engstrom S, et al. Interactions of novel, nonhemolytic surfactants with phospholipid vesicles. Langmuir 23 (13): 6956-6965 JUN 19 2007

104. Antunes FE, Coppola L, Gaudio D, Nicotera I, Oliviero C. Shear bheaviour of sodium oleate/water mixtures Colloids and Surfaces A (2007) 297:95.

105. Antunes, F. E.; Brito, R. O.; Marques, E. F.; Lindman, B.; Miguel, M. Mechanisms behind the faceting of catanionic vesicles by polycations: Chain crystallization and segregation.J. Phys. Chem. B 2007, 111, 116-123.

106. Costa, D.; Miguel, M. G.; Lindman, B. Responsive polymer gels: Double-stranded versus single-stranded DNA.J. Phys. Chem. B 2007, 111, 10886-10896.

107. Costa, D.; Miguel, M. G.; Lindman, B.Effect of additives on swelling of covalent DNA gels.J. Phys. Chem. B 2007, 111, 8444-8452.

108. Dasgupta, A.; Das, P. K.; Dias, R. S.; Miguel, M. G.; Lindman, B.”Effect of headgroup on DNA - Cationic surfactant interactions. J. Phys. Chem. B 2007, 111, 8502-8508.

109. Lindman, B.; Moran, M. C.; Costa, D.; Dias, R. S.; Miguel, M “Manipulation of DNA with surfactants and lipids: Compaction and decompaction Polymer Preprints, Japan 2007, 56, 49-50.

110. Moran, M. C.; Miguel, M. G.; Lindman, B. DNA gel particles: Particle preparation and release characteristics Langmuir 2007, 23, 6478-6481.

111. Moran, M. C.; Miguel, M. G.; Lindman, B.Surfactant-DNA gel particles: Formation and release characteristics.Biomacromolecules 2007, 8, 3886-3892

112. Rosa, M.; Miguel, M. D.; Lindman, B.DNA encapsulation by biocompatible catanionic vesicles.Colloid Interface Sci. 2007, 312, 87-97.

113. Rosa, M.; Moran, M. D.; Miguel, M. D.; Lindman, B.The association of DNA and stable catanionic amino acid-based vesicles.Colloid Surf. A 2007, 301, 361-375.

114. Costa, T.; Schillén, K.; Miguel, M.D.G; Lindman, B.; Melo, J. S. D. 
Association of a hydrophobically modified polyelectrolyte and a block copolymer studied with fluorescence techniques. In press

115. Dias, R.S.; Magno, L.M.; Valente, A.J.M.; Das, D.; Das, P.K.; Maiti, S.; Miguel, M.G.; Lindman, B.
Interaction between DNA and Cationic Surfactants with Different Headgroups. J. Phys. Chem. B. In press.

116. Gonzalez-Perez, A.; Dias, R.S.; Nylander, T.; Lindman, B.Cyclodextrin-surfactant complex: a new route in DNA decompaction. Biomacromolecules, 2008, 7, 772-775.

117. Jadhav, V.; Maiti, S.; Dasgupta, A; Das, P.K.; Dias, R.S.; Miguel, M.G.; Lindman, B. Effect of the head-group geometry of amino-acid based cationic surfactants on interaction with plasmid DNA Biomacromolecules, 2008, 9, 1852-1859.

118. Gawęda, S., Morán, M. C. , Pais, A. A. C. C., Dias, R. S., Schillén, K., Lindman, B., Miguel, M. G., Cationic agents for DNA compaction, J. Colloid Interface Sci., 2008, 323, 75-83.

119. Papancea, A.; Valente, A. J. M.; Patachia, S.; Miguel, M. G.; Lindman, B.IPVA-DNA cryogel membranes: Characterization, swelling, and transport studies¨Langmuir, 2008, 24, 273-279.

120. Rosa, M.; Penacho, N.; Simöes, S.; Lima, M. C. P.; Lindman, B.; Miguel, M.
DNA pre-condensation with an amino acid-based cationic amphiphile. A viable approach for liposome-based gene delivery”, Molecular Membrane Biology,, 2008, 25, 23-34.

121. DNA Interactions with polymers and surfactants Dias, R.S. and Lindman, B. (eds).Wiley. 2008. Dias, R.S.; Miguel, M.; Lindman, B. 
DNA as an amphiphilic polymer
In “DNA Interactions with polymers and surfactantsâ€, Dias, R.S. and Lindman, B. (eds). Wiley. 2008, pp 367-378.

122. Moran C. M.; Miguel, M. G.; Lindman, B.DNA gel particles: Particle preparation and release characteristics. In Colloids& Interfaces, RICI 2, A. Valente, J. S. Melo, Eds. Sociedade Portuguesa de Química, 2007, pp 179-186

123. Costa, D.; Miguel, M. G.; Lindman, B.Covalent DNA gels: Effect of DNA conformation In Colloids& Interfaces, RICI 2, A. Valente, J. S. Melo, Eds. Sociedade Portuguesa de QuÃmica, 2007, pp 215-220

124. Costa, M. C.; Morán, M. C.; Miguel, M. G. D.; Lindman, B. 
Cross-linked NAGels and Gel “Particles in “DNA Interactions with polymers and surfactants”, Dias, R.S. and Lindman, B. (eds). Wiley. 2008 pp 353-365.

125. Lindman, B.; Dias, R.S., Miguel, M.G.; Morán, M. C.; Costa, D.. Manipulation of DNA by Surfactants. In “Highlights in Colloid Scienceâ€, Platikanov, E., Exerowa, D. (eds.). Wiley-VCH, Weinheim, 2008, pp. 179-202.

126. Dias, R. S., Morán, M. C., Costa, D., Miguel, M. G., and Lindman, B.DNA-surfactant systems: Particles, gels and nanostructures in Nano-science:colloidal background, V. M. Starov, Ed.,. Taylor&Frances, 2008

127. Gemini Surfactant Binding onto Hydrophobically Modified Silica Nanoparticles. Andreozzi, P.; Pons, R.; Perez, L.; Infante, M.R.; Muzzalupo, R.; Suber, L.; La Mesa, C. J. Phys. Chem. C, (2008), 112, 12142.

128. Formation and Physical-Chemical Characterisation of Silica-Based Blackberry-like Nano Particles Capped by Polysaccharides. Andreozzi, P.; La Mesa, C.; Masci, G.; Suber, L. J. Phys. Chem. C, 2007, 111, 18030.

129. Interactions between Gemini Surfactants and Polymers: Thermodynamic Studies. Muzzalupo, R., Infante, M. R., Pérez, L., Pinazo, A., Marques, E. F., Antonelli, M. L., Strinati, C., La Mesa, C. Langmuir, 2007, 23, 5963.

130. Biocompatible catanionic vesicles formed in arginine glycerol-based surfactants - DPPA systemsN. Lozano, A. Pinazo, C. La Mesa, L. Pérez, P. Andreozzi, R. Pons, manuscript..

131. N,N’-hexadecanoyl- l-2-diaminomethyl-18-crown-6 Surfactant: Synthesis and Aggregation Properties in Aqueous Solutions. Muzzalupo, R.; Tavano, L.; Trombino, S.; La Mesa, C.; Nicotera, I.; Oliviero Rossi, C. Colloids Surf. B: Biointerfaces, 2008, 61, 30.

132. Preparation and Characterization of Bolaform Surfactant Vesicles. Muzzalupo, R.; Trombino, S.; Iemma, F.; Puoci, F.; La Mesa, C.; Picci, N. Colloids Surf. B:Biointerfaces, 2005, 46,78.

133. Interactions between Gemini Surfactants and Polymers: Thermodynamic Studies. Muzzalupo, R., Infante, M. R., Pérez, L., Pinazo, A., Marques, E. F., Antonelli, M. L., Strinati, C., La Mesa, C. Langmuir, 2007, 23, 5963.

134. Gemini Surfactant Binding onto Hydrophobically Modified Silica Nanoparticles. Andreozzi, P.; Pons, R.; Perez, L.; Infante, M.R.; Muzzalupo, R.; Suber,L.; La Mesa, C. J. Phys. Chem. C, (2008), 112, 12142.

135. Interactions between Gemini Surfactants and Polymers: Thermodynamic Studies. Muzzalupo, R., Infante, M. R., Pérez, L., Pinazo, A., Marques, E. F., Antonelli, M. L., Strinati, C., La Mesa, C. Langmuir, 2007, 23, 5963.

- In addition, several WG’s already possess draft versions of manuscripts that will be submitted

shortly.

Action Related Book Chapters (3) (WG D36/008/6 INFANTE) • 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, In press.

• 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, In press.

• Manipulation of DNA by Surfactants. B. Lindman, R.S. Dias, M. G.Miguel, M. C Morán D. Costa.

In The Best of Colloid Science; D. Platikanov, D. Exerowa (Eds.): Wiley-VCH, submitted.

Action Related Filed patents (2) (WG D36/008/06 INFANTE) • FRAS, Lidija, BUT, Igor, STANA-KLEINSCHEK, Karin, RIBITSCH, Volker, ŠAUPERL, Olivera,

ZABRET, Andrej. Tampon, ki vsebuje pH regulirajočo ter antibakterijsko in antimikotično aktivno formulacijo, in postopek njegove izdelave : zahteva za podelitev patenta [Uradu Republike Slovenije za intelektualno lastnino] : št. prijave P-200600138, datum vložitve prijave 05.06.2006. Ljubljana: Urad Republike Slovenije za intelektualno lastnino, 2006. 23 f

• STRNAD, Simona, INDEST, Tea, LAINE, Janne, STANA-KLEINSCHEK, Karin, VESEL, Alenka,

DWORCZAK, Renate. Poliestrski biomaterial s površino, ki ima antitrombotične lastnosti, in postopek njegove izdelave : zahteva za podelitev patenta, št. prijave 200700097 z dne 19.04.2007. Ljubljana: Urad Republike Slovenije za intelektualno lastnino, 2007. 1 f. [COBISS.SI-ID 11320854]