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
Austria
17/02/2006
Denmark
Greece
Country
Date
Country
Date
Belgium
14/10/2005
Bulgaria
21/11/2005
14/10/2005
Finland
02/05/2006
France
14/10/2005
Hungary
25/10/2005
Ireland
Latvia
15/12/2005
Netherlands
13/10/2005
Portugal
22/05/2006
Romania
Sweden
14/10/2005
Switzerland
Country
Date
15/11/2005
06/06/2006
Czech
Republic
Germany
19/10/2005
Italy
05/01/2006
Norway
14/10/2006
Poland
14/10/2005
14/10/2005
Slovenia
06/12/2005
Spain
17/10/2005
14/10/2005
United
Kingdom
24/10/2005
13/10/2005
Total: 23
• Intentions to accept: list of countries and date
Intentions to accept the MoU
Country
Date
Country
Turkey
Total: 1
N/A
Date
Country
Date
Country
Date
● Other participants: (Institution Name, Country, Town)
Country
Date
Country
Date
Country
Date
Country
Date
Total: 0
Management Commitee
Chair
Dr. Miguel BANARES
CSIC - Instituto de Catalisis
Marie Curie, 2 E-28049
Madrid, Spain
[email protected]
Vice Chair
DC Rapporteur
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
[email protected]
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
[email protected]
Svetlana VOINOVA
COST Office
+32 2 533 38 48
[email protected]
• 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
[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
[email protected]
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]
France
Professor Jacques FRAISSARD
Laboratoire de Physique Quantique
- ESPCI
10 rue du Vauquelin
Paris FR
[email protected]
Professor Christian FERNANDEZ
UMR 6506
Université de Caen
LCS - CNRS
6 boulevard du Maréchal Juin
Caen FR
[email protected]
Germany
Professor Franz-Peter MONTFORTS
Institut für Organische Chemie
Universität Bremen
Leobener Straße NW 2
Postfach 33 04 40
Bremen 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
[email protected]
Hungary
Professor András ERDOHELYI
Institute of Solid State and Radiochemistry
University of Szeged
POB 168
Szeged HU
[email protected]
Ireland
Dr. James SULLIVAN
School of Chemistry & Chemical Biology
University College Dublin
Belfield
Dublin IE
[email protected]
Italy
Dr. Anna Maria VENEZIA
ISMN CNR
Via Ugo La Malfa 153
Palermo IT
[email protected]
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]
Dr. Klaus D. SCHIERBAUM
Institut für Physik der kondensierten Materie
Heinrich-Heine-Universität Düsseldorf
Universitätsstr. 1
Geb. 25.23
Düsseldorf DE
[email protected]
Professor Soghomon BOGHOSIAN
Chemical Technology and Applied Physical Chemistry
University of Patras
Patras GR
[email protected]
Professor Lászlň GUCZI
Institute of Isotopes and Surface Chemistry
Hungarian Academy of Sciences
P.O. Box 77
Budapest HU
[email protected]
Professor Julian R.H. ROSS
College of sciences
University of Limerick
Limerick IE
[email protected]
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
[email protected]
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
[email protected]
Mr. Ioan SANDULESCU
Faculty of Chemistry
University of Bucharest
36-46, M. Kogalniceanu Bd, Sector 5
Bucharest RO
[email protected]
Slovenia
Professor Karin STANA-KLEINSCHEK
Faculty of Mechanical Engineering
University of Maribor
Maribor SI
[email protected]
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
[email protected]
Dr. Wendy BROWN
University College London
20 Gordon Street
London UK
[email protected]
IC. Overview activities and expenditure
Action D36 - budget from 24-Feb-2006 to 31-Dec-2008
Meetings
Meeting Type
Date
Place
Paid part
Management Committee 24-Feb-2006 Brussels (BE)
Management Committee 25-Sep-2006 Brussels (BE)
Management Committee 02-Oct-2006 Brussels (BE)
Working Group
19-Nov-2006 Prague (CZ)
Working Group
24-Nov-2006 Bruckmuhl (DE)
Working Group
30-Nov-2006 Lausanne (CH)
Working Group
01-Dec-2006 Warwick (uk)
01-Dec-2006 Palermo (IT)
Working Group
Working Group
08-Dec-2006 Barcelona (ES)
Working Group
17-May-2007Coimbra (PT)
In conjunction with Workshop/Conference
01-Sep-2007 Espoo (FI)
Working Group
05-Oct-2007 Stockholm (SE)
Working Group
16-Nov-2007 Prague (CZ)
Working Group
26-Nov-2007 Arcavacata di Rende (IT)
Working Group
16-Dec-2007 Burgos (ES)
Working Group
04-Apr-2008 Dijon (FR)
10-May-2008Poznan (PL)
Working Group
Working Group
15-May-2008Graz (AT)
In conjunction with Workshop/Conference
04-Sep-2008 Dublin (IE)
Working Group
26-Sep-2008 Villars (CH)
Working Group
24-Oct-2008 Nice (FR)
Working Group
14-Nov-2008 Delft (NL)
Working Group
28-Nov-2008 Leiden (NL)
Working Group
11-Dec-2008 Rome (IT)
29
4
28
4
8
4
8
7
11
10
41
8
5
10
6
5
7
6
28
4
14
8
5
10
Cost
Total
17930.14
1833.59
15255.57
1978.31
3473.28
2859.43
4226.86
5916.26
8385.23
8798.08
32030.3
7065.89
2719.79
7401.25
3326.08
3125.15
4376.94
7340.41
19402.76
2655.7
12644.27
5336.46
2361.52
8000
188443.3
STSM
Beneficiary
Date
From
To
Mr Jianjun Zhao
03-Dec-2006 Berne (CH)
Coventry (uk)
20-Dec-2006 Paris (FR)
Madrid (ES)
Dr Monica Calatayud
Mr Akintayo Adisa
05-Mar-2007 Manchester (uk)
Burgos (ES)
Ms Jana Bulickova
02-May-2007Prague (CZ)
Dresden (DE)
Ms Ilaria Degano
07-May-2007PISA (IT)
Prague (CZ)
14-May-2007FI-02015 TKK (FI)
75252 Paris (FR)
Ms Satu Korhonen
Mr Jan Fiedler
16-May-2007Prague (CZ)
10125 Torino (IT)
Dr. Izabela Sobczak
01-May-2007Poznan (PL)
Delft (NL)
Dr Maciej Trejda
01-May-2007Poznan (PL)
Delft (NL)
05-May-20071050 Bruxelles (BE) 90146 Palermo (IT)
Mr Gérôme Melaet
Dr Michèle Salmain
24-Sep-2007 Paris 75005 (FR)
Prague 8 (CZ)
Dr Viorel Chihaia
01-Oct-2007 Bucharest (RO)
Budapest (HU)
Ms Diana Costa
15-Sep-2007 3004-535 Coimbra (PT)
Graz (AT)
Ms Satu Korhonen
01-Oct-2007 FI-02015 TKK (FI)
Paris (FR)
Pr Björn Lindman
03-Jan-2008 Lund (SE)
Maribor (SI)
Mr Alberto Martinez
02-Feb-2008 Burgos (ES)
Manchester (uk)
Mr Edgar Ventosa
03-Feb-2008 Burgos (ES)
Coventry (uk)
Ms Nika Veronovski
01-Mar-2008 2000 Maribor (SI)
00185 Roma (IT)
Mr Ivan Ivanov
14-Apr-2008 1113 Sofia (CZ)
90146 Palermo (IT)
Dr Anna Elzbieta LEWANDOWSKA
18-May-2008MADRID (ES)
UTRECHT (NL)
Ms Tímea Benkó
24-May-2008Budapest (HU)
Palermo (IT)
Dr Filipe Antunes
17-May-2008Coimbra (PT)
Rome (IT)
Ms Tina Tkavc
01-Apr-2008 Maribor (SI)
Lund (SI)
Dr Romana Sokolova
23-Jun-2008 Prague (EE)
Pisa (IT)
Mr Germán Soldano
15-Jun-2008 D89069 Ulm (DE)
Leiden (NL)
Dr Agnieszka RUPPERT03-Aug-2008 Utrecht (NL)
Paris (FR)
Ms Anna Wojtaszek
05-Nov-2008 60-780 Poznań Paris
(PL) (FR)
Ms Hanna Golinska
05-Nov-2008 60-780 Poznan (PL) E-28049 Madrid (ES)
Cost
Total
1280
627
2440
852
1200
1100
1550
2470
2470
2450
1500
2000
2500
2500
1400
2500
2500
2500
2100
1470
1410
2280
2500
1380
2500
1560
2500
2500
54,039
Workshops
Title
Date
Place
Cost
Total
WG 01 meeting: Redox activity
19-Nov-2006
of host-guest.
Prague (CZ)
organometallic and molecular structures at electrode
545
interfaces
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 meeting
17-May-2007Coimbra (PT)
730
Annual Workshop and MC
01-Sep-2007
meeting 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
26-Nov-2007
based surfactants
Arcavacata– di
stabilisation
Rende (IT) and functionalisation of particles
650 and surfaces
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
04-Sep-2008
meeting
Dublin (IE)
2,222
COST WG D36/07 meeting
26-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
SCHOOL_STUDENTS
Date
Place
24-Nov-2008 Leiden (NL)
Honoraria
Title
Date
Expert
title
Cost
Total
D36 TRAINING SCHOOL on ELECTROCATALYSIS
9000
at NANOSCALE techn
9000
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.
th
PLENARY LECTURE - “Niobium as a promoter for oxidation catalysts”, 6 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 symposiumhas 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 2cyclohexen-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 168173, 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. OC2007-1457 “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 gammacyclodextrin, 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
NH4+
NH3
CD-C60-CD
2e-
2e-
N2H4
CD-NH4+
2-
2e-
N2H2
CD-C60-CD
N2
C60
+ CD
Mechanism of electrocatalytic conversion of
nitrogen to ammonia
3
current / µ A
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.
2
1
0
10
15
20
time / s
Helquats are unique three-dimensional condensed
Current oscillations on dropping Hg
polyaromatics, which fill the gap between helicenes
electrode originating from the cationic
and poly-viologenes. They are designed as models
catalysis of nitro-aromatic radical reduction
of screw–shaped biomolecules or as new materials
reduction.
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
Spiral-shaped di-quarternary
resulted in 1 publication and 9 other papers reported
polycondensated aromatic molecule of
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
(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 OH 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
3+
3+
supported on CeO2 doped by lanthanides ions, by Al and Y 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
3+
different dopant ions, Me . 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 FTreactor (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 PdCl42- 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 Indoped 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 PLLnanoparticle 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.
a
b
c
Figure 3. Transmission electron microscopy of (a) Pt-deposits within zeolite Y membranes – scale bar = 5 nm, (b) phosphinestabilised 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)
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+,
5+
whereas niobium and tantalum as M . 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,
th
th
were reported in the fourth working group meeting, which was held 14 /15 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
6+
3+
impregnation with CrO3 solutions into mesoporous silicas consist of Cr species, whereas SiO2, Cr
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-Osupport 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-OSupport 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
Figure 1: Abbreviation of the different porphyrins synthetised
AP
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.
NH N
N HN
N
Co
N N
H2TPP
CoTPP
N
N HN
N
Co
N
N
N
NH2
H2AP
F
NH2
CoAP
CoOEP
H2OEP
F
N
H
N
N
H
N
N
Co
N N
N
NH N
F
F
F
F
F F
F
F
F F
N
F
H N
N
H
N
F
H2FAP
F
NH2
F
F
F
F
F
F
F F
F
F
F F
N
F
N Co N
N
F
F
NH2
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 oxygencobalt 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)
-
-
-
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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.
-
-
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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).
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-
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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 Lysinebased 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, LusoPortugal, 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.SIID 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.
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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
5
microbead-based immunoassay using an (η -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) 48694874.
4. L. Pospíšil, J. Fiedler, M. Hromadová, M. Gál, M.Valášek, J. Pecka, J. Michl “Search for a OneElectron Reduction of the Cation Radical of an "Extended Viologen", p-Phenylene-bis-4,4'-(1-Aryl2,6-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(µtppz)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) 37363742.
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 oniumand 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 goldpalladium 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
3+
CO over gold catalysts based on doped by Me (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 LópezPalacios, 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) 209213
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 MCM41 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, 4950.
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 precondensation with an amino acid-based cationic amphiphile. A viable approach for liposomebased 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.). WileyVCH, 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.);WileyBlackwell, 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.SIID 11320854]