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
Professor Robert SCHOONHEYDT
Centre for Surface Chemistry and CatalysisFLTBWCatholic University of Leuven Kardinal Mercierlaan 92 3001
Louvain Belgium
[email protected] uven.ac.be
Professor Vasile PARVULESCU Department of Chemical Technology & CatalysisFaculty of Chemistry University of Bucharest B-dul Regina Elisabeta 4-12 030016 Bucharest Romania
Contacts
MC Chair Science Officer: Administrative Officer:
Dr. Miguel BANARES Tel. +34 91 585 4788 Fax. +34 91 585 4760 [email protected]
Javier CALDENTEY COST Office +32 2 533 38 17
Svetlana VOINOVA COST Office +32 2 533 38 48
• 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
[email protected] Belgium
Professor Eric GAIGNEAUX
Faculté d'ingénieurie Biologique, Agronomique et Environementale Université Catholique de Louvain
Croix du Sud 2/17 Louvain-la-Neuve BE [email protected] Bulgaria
Professor Donka ANDREEVA Institute of Catalysis
Bulgarian Academy of Sciences Acad. G. Bonchev” str., bl. 11 Sofia BG
[email protected] Czech Republic
Professor Hynek BIEDERMAN Mathematics & Physics Faculty Charles University
VXO. Holešovickách 2 Prague 8 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
[email protected] Denmark
Professor Preben J. MØLLER University of Copenhagen Universitetsparken 5 Copenhagen DK [email protected] Finland
Dr. Sanna AIRAKSINEN
Laboratory of Industrial Chemistry Helsinki University of Technology FI-02015 TKK FI
France
Professor Jacques FRAISSARD Laboratoire de Physique Quantique - ESPCI
10 rue du Vauquelin Paris FR
Professor Christian FERNANDEZ UMR 6506
Université de Caen LCS - CNRS
6 boulevard du Maréchal Juin Caen 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
[email protected] Germany
Professor Franz-Peter MONTFORTS Institut für Organische Chemie Universität Bremen
Leobener Straße NW 2 Postfach 33 04 40 Bremen DE
Dr. Klaus D. SCHIERBAUM
Institut für Physik der kondensierten Materie Heinrich-Heine-Universität Düsseldorf Universitätsstr. 1
Geb. 25.23 Düsseldorf DE
[email protected] 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
Professor Soghomon BOGHOSIAN
Chemical Technology and Applied Physical Chemistry University of Patras
Patras GR
Hungary
Professor András ERDOHELYI
Institute of Solid State and Radiochemistry University of Szeged
POB 168 Szeged HU
Professor Lászlň GUCZI
Institute of Isotopes and Surface Chemistry Hungarian Academy of Sciences
P.O. Box 77 Budapest HU
[email protected] Ireland
Dr. James SULLIVAN
School of Chemistry & Chemical Biology University College Dublin
Belfield Dublin IE
Professor Julian R.H. ROSS College of sciences
University of Limerick Limerick IE
Italy
Dr. Anna Maria VENEZIA ISMN CNR
Via Ugo La Malfa 153 Palermo IT
Latvia
Dr. Ludmila LEITE
Laboratory of Catalytic Synthesis Latvian Institute of Organic Synthesis Aizkraukles iela 21
Riga LV [email protected] Netherlands
Professor Guido MUL Faculty of Applid Sciences Delft University of Technology Julianalaan 136
NL
Professor Bert WECKHUYSEN Debye Instituut
Utrecht University Sorbonnelaan 16 Utrecht NL
[email protected] Norway
Dr. Gisle ŘYE
Norwegian University of Science and Technology - NTNU Ugelstad Laboratory
TRONDHEIM NO [email protected] Poland
Professor Maria ZIOLEK Faculty of Chemistry Adam Mickiewicz University 6 Grunwaldzka Str.
Poznan PL [email protected]
Professor Barbara GRZYBOWSKA-SWIERKOSZ Institute of the Catalysis and Surface Chemistry Polish Academy of Sciences
8 Niezapominajek str.
Kraków PL
[email protected] Portugal
Professor Luisa Maria ABRANTES Faculdade de Ciencias
Universidade de Lisboa R. Ernesto Vasconcelos, Ed.C8 Lisboa PT
[email protected] 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
Mr. Ioan SANDULESCU Faculty of Chemistry University of Bucharest
36-46, M. Kogalniceanu Bd, Sector 5 Bucharest RO
Slovenia
Professor Karin STANA-KLEINSCHEK Faculty of Mechanical Engineering University of Maribor
Maribor SI
Professor Venceslav KAUCIC National Institute of Chemistry University of Ljublijana Hajdrihova 19
PO Box 660 Ljubljana SI [email protected] Spain
Dr. Maria Rosa INFANTE
Instituto de Investigaciones Quimicas y Ambientales CSIC
Jordi Girena Salgado 18-26 Barcelona ES
[email protected] Sweden
Professor Sven Gunnar JARAS Division of Chemical Technology Royal Institute of Technology - KTH Teknikringen 42
Stockholm SE [email protected]
Dr. Magali BOUTONNET Division of Chemical Technology Royal Institute of Technology - KTH Teknikringen 42
Stockholm SE [email protected] 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 [email protected] United Kingdom
Professor Robert JONES School of chemistry University of Nottingham Nottingam UK
Dr. Wendy BROWN University College London 20 Gordon Street
London UK
IC. Overview activities and expenditure
Action D36 - budget from 24-Feb-2006 to 31-Dec-2008
Meetings
Meeting Type Date Place Paid part Cost Total
Management Committee 24-Feb-2006 Brussels (BE) 29 17930.14
Management Committee 25-Sep-2006 Brussels (BE) 4 1833.59
Management Committee 02-Oct-2006 Brussels (BE) 28 15255.57
Working Group 19-Nov-2006 Prague (CZ) 4 1978.31
Working Group 24-Nov-2006 Bruckmuhl (DE) 8 3473.28
Working Group 30-Nov-2006 Lausanne (CH) 4 2859.43
Working Group 01-Dec-2006 Warwick (uk) 8 4226.86
Working Group 01-Dec-2006 Palermo (IT) 7 5916.26
Working Group 08-Dec-2006 Barcelona (ES) 11 8385.23
Working Group 17-May-2007Coimbra (PT) 10 8798.08
In conjunction with Workshop/Conference01-Sep-2007 Espoo (FI) 41 32030.3
Working Group 05-Oct-2007 Stockholm (SE) 8 7065.89
Working Group 16-Nov-2007 Prague (CZ) 5 2719.79
Working Group 26-Nov-2007 Arcavacata di Rende (IT) 10 7401.25
Working Group 16-Dec-2007 Burgos (ES) 6 3326.08
Working Group 04-Apr-2008 Dijon (FR) 5 3125.15
Working Group 10-May-2008Poznan (PL) 7 4376.94
Working Group 15-May-2008Graz (AT) 6 7340.41
In conjunction with Workshop/Conference04-Sep-2008 Dublin (IE) 28 19402.76
Working Group 26-Sep-2008 Villars (CH) 4 2655.7
Working Group 24-Oct-2008 Nice (FR) 14 12644.27
Working Group 14-Nov-2008 Delft (NL) 8 5336.46
Working Group 28-Nov-2008 Leiden (NL) 5 2361.52
Working Group 11-Dec-2008 Rome (IT) 10 8000
188443.3
STSM
Beneficiary Date From To Cost Total
Mr Jianjun Zhao 03-Dec-2006 Berne (CH) Coventry (uk) 1280
Dr Monica Calatayud 20-Dec-2006 Paris (FR) Madrid (ES) 627
Mr Akintayo Adisa 05-Mar-2007 Manchester (uk) Burgos (ES) 2440
Ms Jana Bulickova 02-May-2007Prague (CZ) Dresden (DE) 852
Ms Ilaria Degano 07-May-2007PISA (IT) Prague (CZ) 1200
Ms Satu Korhonen 14-May-2007FI-02015 TKK (FI) 75252 Paris (FR) 1100
Mr Jan Fiedler 16-May-2007Prague (CZ) 10125 Torino (IT) 1550
Dr. Izabela Sobczak 01-May-2007Poznan (PL) Delft (NL) 2470
Dr Maciej Trejda 01-May-2007Poznan (PL) Delft (NL) 2470
Mr Gérôme Melaet 05-May-20071050 Bruxelles (BE) 90146 Palermo (IT) 2450 Dr Michèle Salmain 24-Sep-2007 Paris 75005 (FR) Prague 8 (CZ) 1500
Dr Viorel Chihaia 01-Oct-2007 Bucharest (RO) Budapest (HU) 2000
Ms Diana Costa 15-Sep-2007 3004-535 Coimbra (PT)Graz (AT) 2500
Ms Satu Korhonen 01-Oct-2007 FI-02015 TKK (FI) Paris (FR) 2500
Pr Björn Lindman 03-Jan-2008 Lund (SE) Maribor (SI) 1400
Mr Alberto Martinez 02-Feb-2008 Burgos (ES) Manchester (uk) 2500
Mr Edgar Ventosa 03-Feb-2008 Burgos (ES) Coventry (uk) 2500
Ms Nika Veronovski 01-Mar-2008 2000 Maribor (SI) 00185 Roma (IT) 2500 Mr Ivan Ivanov 14-Apr-2008 1113 Sofia (CZ) 90146 Palermo (IT) 2100 Dr Anna Elzbieta LEWANDOWSKA18-May-2008MADRID (ES) UTRECHT (NL) 1470
Ms Tímea Benkó 24-May-2008Budapest (HU) Palermo (IT) 1410
Dr Filipe Antunes 17-May-2008Coimbra (PT) Rome (IT) 2280
Ms Tina Tkavc 01-Apr-2008 Maribor (SI) Lund (SI) 2500
Dr Romana Sokolova 23-Jun-2008 Prague (EE) Pisa (IT) 1380
Mr Germán Soldano 15-Jun-2008 D89069 Ulm (DE) Leiden (NL) 2500
Dr Agnieszka RUPPERT03-Aug-2008 Utrecht (NL) Paris (FR) 1560
Ms Anna Wojtaszek 05-Nov-2008 60-780 Poznań (PL)Paris (FR) 2500 Ms Hanna Golinska 05-Nov-2008 60-780 Poznan (PL) E-28049 Madrid (ES) 2500
54,039
Workshops
Title Date Place Cost Total
WG 01 meeting: Redox activity of host-guest. organometallic and molecular structures at electrode interfaces19-Nov-2006 Prague (CZ) 545
WG D38-06-06 meeting 24-Nov-2006 Bruckmuhl (DE) 600
WG D36-003-06 meeting 01-Dec-2006 Palermo (IT) 700
WG D36-008-06 meeting 08-Dec-2006 Barcelona (ES) 700
Action D36 WG 008 meeting17-May-2007Coimbra (PT) 730
Annual Workshop and MC meeting01-Sep-2007 Espoo (FI) 3,426
D36 WG06 meeting 03-Sep-2007 Espoo (FI) 329
WG 003-06 meeting 05-Oct-2007 Stockholm (SE) 573
WG D36/007-06 meeting 16-Nov-2007 Prague (CZ) 445
WG D36/0008/06 Biopolymer based surfactants – stabilisation and functionalisation of particles and surfaces26-Nov-2007 Arcavacata di Rende (IT) 650
WG D36/05/06 meeting 15-Dec-2007 Burgos (ES) 600
WG D36/007-06 meeting 04-Apr-2008 Dijon (FR) 445
WG D36/006/06 meeting 10-May-2008Poznan (PL) 650
WG D36/008 meeting 15-May-2008Graz (AT) 520
COST D36 Annual Workshop+MC meeting04-Sep-2008 Dublin (IE) 2,222
COST WG D36/07 meeting26-Sep-2008 Villars (CH) 200
WG D36/03 meeting 24-Oct-2008 Nice (FR) 1,324
WG D36/06-06 meeting 14-Nov-2008 Delft (NL) 284
WG D37/005-06 meeting 28-Nov-2008 Leiden (NL) 360
15,303
General Support Grants
Title Date Cost Total
0
Schools
Type Date Place title Cost Total
SCHOOL_STUDENTS 24-Nov-2008 Leiden (NL) D36 TRAINING SCHOOL on ELECTROCATALYSIS at NANOSCALE techniques and applications9000 9000
Honoraria
Title Date Expert Cost Total
0
Grant
Grant 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-CD 2- CD-C60-CD
2-
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 20
0 1 2 3
current /µµµµA
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).
