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Perovskites and Related Mixed Oxides

Concepts and Applications

Edited by Pascal Granger, Vasile I. Parvulescu,
Serge Kaliaguine, and Wilfrid Prellier

Wiley Logo

List of Contributors

Houshang Alamdari

Laval University

Department of Mining, Metallurgical and Materials Engineering

1065 avenue de la médecine

Quebec City, QC G1V 0A6

Canada

Andre Luiz Alberton

Federal University of Rio de Janeiro/COPPE

Department of Chemical Engineering/NUCAT

Av.Horacio Macedo 2030

CEP 21941-972

Centro de Tecnologia Bl.G – 121

Cidade Universitária

Rio de Janeiro Brazil

Matteo Ardit

University of Ferrara

Department of Physics and Earth Sciences

Via Saragat 144122 Ferrara

Italy

Carmela Aruta

National Research Council

CNR-SPIN

Via del Politecnico 1

00133 Rome

Italy

Catherine Batiot-Dupeyrat

Université de Poitiers

Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP)

ENSIP, UMR CNRS 7285

1 rue Marcel Doré, TSA 41105

86073 Poitiers Cedex 9

France

Alexandre Bayart

Université d'Artois

Faculté des Sciences Jean Perrin

Unité de Catalyse et de Chimie du Solide (UCCS)

CNRS UMR 8181

Rue Jean Souvraz – SP 18

62307 Lens

France

Gregory Biausque

Université Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon

(IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Nicolas Bion

Université de Poitiers

Institut de Chimie des Milieux et

Matériaux de Poitiers (IC2MP)

CNRS UMR 7285

4 rue Michel Brunet, TSA 51106

86073 Poitiers Cedex 9

France

Sourav Biswas

University of Connecticut

Departments of Chemistry and Chemical Engineering and Institute of Materials Science

U-3060, 55 North Eagleville Road

Storrs, CT 06269

USA

Luis F. Bobadilla

Institute of Chemical Research of Catalonia

Heterogeneous catalysis and In Situ/Operando Spectroscopy

Avda. Països Catalans, 16

43007 Tarragona

Spain

Rodrigo Brackmann

Federal University of Rio de

Janeiro/COPPE

Department of Chemical

Engineering/NUCAT

Av. Horacio Macedo 2030

CEP 21941-972

Centro de Tecnologia Bl.G – 121

Cidade Universitária

Rio de Janeiro

Brazil

Oliver Brunko

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Agustín Bueno-López

University of Alicante

Department of Inorganic Chemistry

Carretera de San Vicente s/n

03080 Alicante

Spain

Dariusz Burnat

Swiss Federal Laboratories for

Materials Science and Technology (Empa)

Materials for Energy Conversion

Überlandstrasse 129

8600 Dübendorf

Switzerland

and

University of Applied Sciences (ZHAW)

School of Engineering

Institute of Materials and Process

Engineering (IMPE)

Technikumstrasse 9,

8600 Winterthur

Switzerland

Miguel Angel Centeno

Centro mixto CSIC-Universidad de Sevilla

Instituto de Ciencia de Materiales de Sevilla

Avda. Americo Vespucio 49

41092 Sevilla

Spain

Steven S.C. Chuang

The University of Akron

Department of Polymer Science

FirstEnergy Advanced Energy Research Center

170 University Avenue

Akron, OH 44325-3909

USA

Bogdan Cojocaru

University of Bucharest

Faculty of Chemistry

Department of Organic Chemistry, Biochemistry and Catalysis

Bd. Regina Elisabeta 4–12

030018 Bucharest

Romania

Juan C. Colmenares

Polish Academy of Sciences

Institute of Physical Chemistry

ul. Kasprzaka 44/52

01-224 Warsaw

Poland

Giuseppe Cruciani

University of Ferrara

Department of Physics and Earth Sciences

via Saragat 144122 Ferrara

Italy

Jean-Philippe Dacquin

Université Lille 1, Sciences et Technologies

Unité de Catalyse et de Chimie du Solide – UMR 8181

Bâtiment C3

59650 Villeneuve d'Ascq Cedex

France

Ana Raquel de la Osa

Universidad de Castilla-La Mancha

Facultad de Ciencias y Tecnologías Químicas

Departamento de Ingeniería Química

Avenida de Camilo José Cela, 12

13071 Ciudad Real

Spain

Rachel Desfeux

Université d'Artois

Faculté des Sciences Jean Perrin

Unité de Catalyse et de Chimie du Solide (UCCS)

CNRS UMR 8181

Rue Jean Souvraz – SP 18

62307 Lens

France

Michele Dondi

Institute of Science and Technology for Ceramics

CNR-ISTEC

via Granarolo 64

48018 Faenza

Italy

Christophe Dujardin

Université Lille 1, Sciences et Technologies

Unité de Catalyse et de Chimie du Solide – UMR 8181

Bâtiment C3

59650 Villeneuve d'Ascq Cedex

France

Daniel Duprez

Université de Poitiers

Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP)

CNRS UMR 7285

4 rue Michel Brunet, TSA 51106

86073 Poitiers Cedex 9

France

Angelos M. Efstathiou

University of Cyprus

Chemistry Department

Heterogeneous Catalysis Laboratory

1 University Avenue, University Campus

1678 Nicosia

Cyprus

Florence Epron

Université de Poitiers

Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP)

CNRS UMR 7285

4 rue Michel Brunet, TSA 51106

86073 Poitiers Cedex 9

France

David Farrusseng

Université Lyon 1

Institut de recherches sur la catalyse

et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Davide Ferri

Paul Scherrer Institut (PSI)

5232 Villigen

Switzerland

Fausto Gallucci

Eindhoven University of Technology,

Department of Chemical

Engineering and Chemistry,

Chemical Process Intensification

P.O. Box 513, STE 038

5612 AZ Eindhoven,

The Netherlands

Nuria García-Moncada

Universidad de Sevilla e Instituto de

Ciencias de Materiales de Sevilla

Centro mixto US-CSIC

Departamento de Química Inorgánica

Avda. Américo Vespucio 49

41092 Seville

Spain

Jesús Manuel Garcia-Vargas

Université Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Sonia Gil

Université Lyon 1

Institut de recherches sur la catalyse

et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Anne Giroir-Fendler

Université Claude Bernard Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69622 Villeurbanne Cedex

France

Pascal Granger

University of Lille

Unité de Catalyse et de Chimie du Solide

UMR CNRS 8181

Batiment C3

59655 Villeneuve d'Ascq Cedex

France

Andre Heel

Swiss Federal Laboratories for

Materials Science and Technology (Empa)

Materials for Energy Conversion

Überlandstrasse 129

8600 Dübendorf

Switzerl

and

University of Applied Sciences (ZHAW)

School of Engineering

Institute of Materials and Process

Engineering (IMPE)

Technikumstrasse 9,

8600 Winterthur

Switzerland

Willinton Y. Hernández

Ghent University

Department of Inorganic and Physical Chemistry

Krijgslaan 281, S3

9000 Ghent

Belgium

Svetlana Ivanova

Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla

Centro mixto US-CSIC

Departamento de Química Inorgánica

Avda. Américo Vespucio 49

41092 Seville

Spain

Randy Jalem

Kyoto University

Unit of Elements Strategy Initiative for Catalysts & Batteries (ESICB)

Katsura, Saikyo-ku

Kyoto 615-8520

Japan

and

Nagoya Institute of Technology

Department of Materials Science and Engineering

Gokiso, Showa, Nagoya

Aichi 466-8555

Japan

Serge Kaliaguine

Université Laval

Department of Chemical Engineering

1065, Avenue de la médecine

Quebec City, QC G1V 0A6

Canada

Vijayanandhini Kannan

GITAM University

GITAM School of Technology

Department of Physics

Hyderabad 502329

Telangana

India

Lassi Karvonen

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Alain Kiennemann

ICPEES

Group “Energie et Carburants pour un Environnement Durable”

CNRS UMR 7515

25, rue Becquerel

67087 Strasbourg

France

Evgenii V. Kondratenko

Catalyst Discovery and Reaction EngineeringLeibniz-Institut für Katalyse e.V. an der Universität Rostock

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Michalis Konsolakis

Technical University of Crete

School of Production Engineering and ManagementUniversity Campus, Kounoupidiana

73100 Chania, Crete

Greece

Athanasios Ladavos

University of PatrasDepartment of Business Administration of Food and Agricultural Enterprises G. Seferi 2

Agrinio 30100

Greece

Oscar H. Laguna

Centro mixto CSIC-Universidad de Sevilla

Instituto de Ciencia de Materiales de Sevilla

Avda. Americo Vespucio 49

41092 Sevilla

Spain

Leonarda F. Liotta

Université per Lo Studio dei Materiali Nanostrutturati (ISMN)-CNR

via Ugo La Malfa 153

90146 Palermo

Italy

Paweł Lisowski

Polish Academy of Sciences

Institute of Physical Chemistry

ul. Kasprzaka 44/52

01-224 Warsaw

Poland

Agnieszka Magdziarz

Polish Academy of Sciences

Institute of Physical Chemistry

ul. Kasprzaka 44/52

01-224 Warsaw

Poland

Yongtao Meng

University of Connecticut

Departments of Chemistry and Chemical Engineering and Institute of Materials Science

U-3060, 55 North Eagleville Road

Storrs, CT 06269

USA

Mahesh Muraleedharan Nair

Université Laval

Department of Chemistry

1065, avenue de la médecine

Quebec City, QC G1V 0A6

Canada

Masanobu Nakayama

Kyoto University

Unit of Elements Strategy Initiative for Catalysts & Batteries (ESICB)

Katsura, Saikyo-ku

Kyoto 615-8520

Japan

and

Nagoya Institute of Technology

Department of Materials Science and Engineering

Gokiso, Showa, Nagoya

Aichi 466-8555

Japan

and

Japan Science and Technology Agency

PRESTO

4-1-8 Honcho Kawaguchi

Saitama 332-0012

Japan

Lori Nalbandian

Center for Research and Technology – Hellas (CERTH)

Chemical Process and Energy Resources Institute (CPERI)

Laboratory of Inorganic Materials

6th km Charilaou–Thermi Road

57001 Thessaloniki

Greece

José Antonio Odriozola

Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla

Centro mixto US-CSIC

Departamento de Química Inorgánica

Avda. Américo Vespucio 49

41092 Seville

Spain

Vasile I. Parvulescu

University of Bucharest

The Department of Organic Chemistry, Biochemistry and Catalysis

4–12 Regina Elisabeta Bvd.

030018 Bucharest

Romania

Viorica Parvulescu

Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy

Department of Surface Chemistry and Catalysis

Spl. Independentei 202

060021 Bucharest

Romania

Marc Pera-Titus

Eco-Efficient Products and Processes Laboratory (E2P2L)

UMR 3464 CNRS – Solvay

3966, Jin Du Road

Xin Zhuang Industrial Zone

Shanghai 201108

China

Caroline Pirovano

Ecole Nationale Supérieure de Chimie de LilleUnité de Catalyse et de Chimie du Solide (UCCS)CNRS UMR 8181Cité Scientifique, Bâtiment C7, CS 9010859652 Villeneuve d'Ascq CedexFrance

Philippos Pomonis

University of Ioannina

Department of Chemistry, University of Ioannina, Ioannina 45110, Greece

Sascha Populoh

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Altug S. Poyraz

University of Connecticut

Departments of Chemistry and Chemical Engineering and Institute of Materials Science

U-3060, 55 North Eagleville Road

Storrs, CT 06269

USA

Ranjith Ramadurai

Indian Institute of Technology Hyderabad

Department of Materials Science and Metallurgical Engineering

Kandi, Sangareddy 502285

Telangana

India

Tomás Ramirez-Reina

Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla

Centro mixto US-CSIC

Departamento de Química Inorgánica

Avda. Américo Vespucio 49

41092 Seville

Spain

Vicente Rives

Universidad de Salamanca

Departamento de Química Inorgánica

GIR-QUESCAT

37008 Salamanca

Spain

Marie Rochoux

Université Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Uwe Rodemerck

Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str.29a, D-18059 Rostock, Germany

Anne-Cécile Roger

ICPEES

Group “Energie et Carburants pour un Environnement Durable”

CNRS UMR 7515

25, rue Becquerel

67087 Strasbourg

France

Aurélie Rolle

Ecole Nationale Supérieure de

Chimie de Lille

Unité de Catalyse et de Chimie du

Solide (UCCS)

CNRS UMR 8181

Cité Scientifique, Bâtiment C7, CS 90108

59652 Villeneuve d'Ascq Cedex

France

Pascal Roussel

Ecole Nationale Supérieure de

Chimie de Lille

Unité de Catalyse et de Chimie du

Solide (UCCS)

CNRS UMR 8181

Cité Scientifique, Bâtiment C7, CS 90108

59652 Villeneuve d'Ascq Cedex

France

Sébastien Royer

Université de Poitiers

CNRS UMR 7285, IC2MP

4 Rue Michel Brunet, TSA 51106

86073 Poitiers Cedex 9

France

Masahiro Sadakane

Hiroshima University

Graduate School of Engineering

Department of Applied Chemistry

1-4-1 Kagamiyama

Higashi-Hiroshima 739-8527

Japan

Leyre Sagarna

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Sébastien Saitzek

Université d'Artois

Faculté des Sciences Jean Perrin

Unité de Catalyse et de Chimie du Solide (UCCS)

CNRS UMR 8181

Rue Jean Souvraz – SP 18

62307 Lens

France

José Luis Santos

Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla

Centro mixto US-CSIC

Departamento de Química Inorgánica

Avda. Américo Vespucio 49

41092 Seville

Spain

Gesine Saucke

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Ricardo Scheunemann

Federal University of Rio de Janeiro/COPPE

Department of Chemical Engineering/NUCAT

Av.Horacio Macedo 2030

CEP 21941-972

Centro de Tecnologia Bl.G – 121

Cidade Universitária

Rio de Janeiro

Brazil

Martin Schmal

Federal University of Rio de Janeiro/COPPE

Department of Chemical Engineering/NUCAT

Av.Horacio Macedo 2030CEP 21941-972

Centro de Tecnologia Bl.G – 121

Cidade Universitária

Rio de Janeiro

Brazil

Yves Schuurman

Université Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

ZhenMian Shao

Université d'Artois

Faculté des Sciences Jean Perrin

Unité de Catalyse et de Chimie du Solide (UCCS)

CNRS UMR 8181

Rue Jean Souvraz – SP 18

62307 Lens

France

Vasilis N. Stathopoulos

Technological Educational Institute of Sterea Ellada

School of Technological Applications

34400 Psahna, Evia

Greece

Steven L. Suib

University of Connecticut

Departments of Chemistry and Chemical Engineering and Institute of Materials Science

U-3060, 55 North Eagleville Road

Storrs, CT 06269

USA

Antonello Tebano

University of Roma Tor Vergata

CNR-SPIN and Department DICII

Via del Politecnico 1

00133 Rome

Italy

Philipp Thiel

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Matthias Trottmann

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Wataru Ueda

Kanagawa University

Faculty of Engineering

Rokkakubashi, Kanagawa-ku, Yokohama-shi

Kanagawa 221-8686

Japan

Jose Luis Valverde

Universidad de Castilla-La Mancha

Facultad de Ciencias y Tecnologías Químicas

Departamento de Ingeniería Química

Avenida de Camilo José Cela, 12

13071 Ciudad Real

Spain

Rose-Noëlle Vannier

Ecole Nationale Supérieure de

Chimie de Lille

Unité de Catalyse et de Chimie du Solide (UCCS)

CNRS UMR 8181

Cité Scientifique, Bâtiment C7, CS 90108

59652 Villeneuve d'Ascq Cedex

France

Philippe Vernoux

Université Lyon 1

Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON)

CNRS UMR 5256

2 avenue Albert Einstein

69626 Villeurbanne Cedex

France

Nina Vogel-Schäuble

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

Anke Weidenkaff

Swiss Federal Laboratories for Materials Science and Technology (Empa)

Laboratory for Solid State Chemistry and Catalysis

Überlandstrasse 129

8600 Dübendorf

Switzerland

and

University of Stuttgart

Institute for Materials Science

Heisenbergstr. 370569 Stuttgart

Germany

Ioannis V. Yentekakis

Technical University of Crete

School of Environmental Engineering

Laboratory of Physical Chemistry & Chemical ProcessesUniversity Campus, Kounoupidiana

73100 Chania, Crete

Greece

Chiara Zanelli

Institute of Science and Technology for Ceramics

CNR-ISTEC

via Granarolo 64

48018 Faenza

Italy

Vassilis Zaspalis

Center for Research and Technology – Hellas (CERTH)

Chemical Process and Energy Resources Institute (CPERI)

Laboratory of Inorganic Materials

6th km Charilaou–Thermi Road

57001 Thessaloniki

Greece

and

Aristotle University of Thessaloniki

Department of Chemical Engineering

Laboratory of Materials Technology

54124 Thessaloniki

Greece

Long Zhang

The University of Akron

Department of Polymer Science

FirstEnergy Advanced Energy Research Center

170 University Avenue

Akron, OH 44325-3909

USA

Jon Zuniga

TECNALIA

Energy and Environment Division

Mikeletegi Pasealekua 2

20009 San Sebastián-Donostia

Spain

Preface

Perovskites elicited an enormous interest in the past two decades and many practical applications have been investigated looking for their potential use in processes of interest. Perovskite-type structures and related mixed oxides highlighted their capacity to accommodate a wide range of transition metals sometimes in unusual oxidation states and with the possibility to stabilize high concentration of defective sites. All these electronic and structural features give rise to unexpected physicochemical properties, some of them being already exploited. Thus, the development of perovskite-based two-way catalysts at the beginning of the 1970s can be considered as one of the most prominent industrial achievements at that time. More recently, the car manufacturer Daihatsu installed novel post-combustion catalytic systems based on the so-called concept of self-regeneration mechanism with intelligent catalysts since it can recognize the atmosphere by itself and change its state automatically. Perovskite structures may also exhibit different physical properties such as ferroelectricity, ferromagnetism, superconductivity, and thermal conductivity.

These solids are often represented as a simple cubic structure. However, pioneering investigations revealed complex chemistry for those materials involving distortions and order–disorder phenomena. By way of illustration, the discovery of colossal magnetoresistance for this variety of mixed oxides stimulated the emergence of new concepts for understanding magnetotransport properties. Today, many research groups are involved in related problems of charge ordering, complex phase separation, and Jahn–Teller effect as crucial parameters for understanding those properties. Hence, one can take advantage of several key parameters that will govern the intrinsic properties of perovskites with a general formula ABO3, such as a wide variety of compositions by partial substitution of A and B sites preserving their structural properties, a well-defined structure that allows extensive bulk and surface characterization, valency and stoichiometry that can widely vary originating peculiar properties, and vast physical and chemical information already accumulated in the literature in the past two decades. Of course, one can play with those chemical and physical features for elaborating different strategies in order to improve their physicochemical properties and more particularly their catalytic performances. For instance, the selection of the B-site cation to get synergistic effects on the activity, the control of the valency and vacancy, the specific surface area enhancement or alternatively enhancement of the perovskite dispersion on a substrate, and finally the improvement of their properties by adding small amounts of noble metals remaining highly dispersed through the occurrence of strong interactions with the perovskite structure can be equally considered for improving the physicochemical properties of those solids.

For a long time, the poor control of their homogeneous composition with detrimental segregation of impurities has likely slow down their development and the introduction of novel preparation routes probably contributes to a growing practical interest that can justify a significant increase in publications and patents since 2000. Tremendous efforts led to the development of facile synthesis routes under mild conditions with unique physicochemical properties, especially their textural properties, and then widening their utilization to low-temperature applications. At the same time, the development of bulk and surface characterization typically under working conditions allows the characterization of complex surface reconstructions that facilitate the establishment of reliable structure–activity relationships. Today, a detailed nanoscopic characterization of surface processes, influencing the final design of active sites under working conditions, is of prime importance especially to rationalize the synthesis strategies.

The general objectives of this scientific book entitled Perovskites and Related Mixed Oxides are to highlight the most important achievements in the past two decades from the synthesis and related characterization methods to their practical applications especially in the field of environmental and sustainable physicochemical applications. A final part will be dedicated to new prospects of developments of those solids as carriers or catalysts. This book addresses more particularly the postgraduates and the Ph.D. students as well as the young qualified researchers starting on the subject. Today, scientists need to develop more rational approaches that consist in developing more efficient chemical and physical applications integrating atom economy and lower energy consumption. Hence, combined approaches including the rationalization of synthesis protocol perovskites to tune properly their structural and textural properties as well as a better integration of the solid in the reactor design may significantly contribute to a sustainable development.

Accordingly, this book will be divided into three parts. The first one will present the different progresses in synthesis methods from molten salts at high temperature to colloidal crystal template methods that allow a better control of the composition and textural properties with three-dimensionally ordered mesoporous solids. Physicochemical techniques currently used to characterize the functionalities of those materials will be depicted with principles of those techniques and relevant illustrations. Oxygen transport in perovskites and related mixed oxides has been the subject of a large number of publications based on the utilization of a wide range of techniques and led to various applications that will be examined. Their electric and magnetic properties will be extensively discussed. At the same time, oxygen diffusion of those materials has attracted the scientific community for the development of solid electrolyte membranes and electrochemical membrane reactors.

2xinterfacialsuprafacial

October 2015

Pascal Granger
Villeneuve d'Ascq, France

Vasile I. Parvulescu
Bucharest, Romania

Serge Kaliaguine
Quebec, Canada

Wilfrid Prellier
Caen, France