Catalysis in Electrochemistry E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: The Wiley Series on Electrocatalysis and Electrochemistry
• Sprache: Englisch

Seitenzahl: 952

Veröffentlichungsjahr: 2011

Beschreibung

Catalysis in Electrochemistry: From Fundamental Aspects to Strategies for Fuel Cell Development is a modern, comprehensive reference work on catalysis in electrochemistry, including principles, methods, strategies, and applications. It points out differences between catalysis at gas/surfaces and electrochemical interfaces, along with the future possibilities and impact of electrochemical science on energy problems. This book contributes both to fundamental science; experience in the design, preparation, and characterization of electrocatalytic materials; and the industrial application of electrocatalytic materials for electrochemical reactions. This is an essential resource for scientists globally in academia, industry, and government institutions.

Leseprobe

Contents

Cover

Wiley Series on Electrocatalysis and Electrochemistry

Title Page

Copyright

Dedication

Preface

Interview with Wolf Vielstich

Preface to the Wiley Series on Electrocatalysis and Electrochemistry

Contributors

Chapter 1: Volcano Curves in Electrochemistry

1.1 Introduction

1.2 Volcano Curves in Heterogeneous Catalysis

1.3 Attempts to Explain Effects of Nature of Electrode on Hydrogen Evolution

1.4 Electrochemical Volcano Curve

References

Chapter 2: Electrocatalysis: A Survey of Fundamental Concepts

2.1 Introductory aspects to fuel cell electrocatalysis

2.2 Electrochemical energy conversion

2.3 Phenomenology of electrochemical reactions

2.4 Other variables influencing electrochemical rate process

2.5 Electrocatalyst Surface

Acknowledgment

References

Chapter 3: Dynamics and Stability of Surface Structures

3.1 Introduction

3.2 Structure and Stability of Electrode Surfaces

3.3 Mass Transport on Electrode Surfaces: Dynamics and Energetics of Defects

3.4 Influence of Adsorbates

3.5 Concluding Remarks

References

Chapter 4: Electrocatalytic Properties of Stepped Surfaces

4.1 Introduction

4.2 Phenomenological Description of Stepped Surfaces

4.3 Electronic Properties of Step Sites

4.4 Adsorption on Step Sites and Step Decoration: Adatoms Adsorption

4.5 Reactivity of Stepped Surfaces

References

Chapter 5: Computational Chemistry Applied to Reactions in Electrocatalysis

5.1 Introduction

5.2 Theoretical foundations

5.3 Water–metal interface in the absence of external fields

5.4 Water–metal interface in the presence of external fields and/or varying electrode potentials

5.5 Conclusions

References

Chapter 6: Catalysis of Electron Transfer at Metal Electrodes

6.1 Introduction

6.2 Adiabatic Outer Sphere Reactions

6.3 Catalysis of Simple Electron Transfer

6.4 Bond-Breaking Electron Transfer

6.5 Hydrogen Catalysis

6.6 Outlook

Appendix: Schmickler–Koper–Santos Hamiltonian

Acknowledgments

References

Chapter 7: Combining Vibrational Spectroscopy and Density Functional Theory for Probing Electrosorption and Electrocatalytic Reactions

7.1 Introduction

7.2 Theory of Vibrational Sprectoscopy of Adsorbed Molecules and Electric Field Effects

7.3 Selected Examples

7.4 Conclusions

References

Chapter 8: Electrochemical Catalysts: From Electrocatalysis to Bioelectrocatalysis

8.1 Introductory Remarks

8.2 Some Typical Electrocatalysts

8.3 Bioelectrocatalysis and Bioelectrodes

Acknowledgment

References

Chapter 9: Electrocatalysis at Bimetallic Surfaces Obtained by Surface Decoration

9.1 Introduction: Ways of Action of Cocatalysts

9.2 Experimental Techniques

9.3 Preparation of Bimetallic Model Surfaces

9.4 Case Studies

References

Chapter 10: CO Adsorption on Platinum Electrodes

10.1 Introduction

10.2 Brief Historical Perspective

10.3 Fundamental Aspects of CO Adsorption on Pt Electrodes

10.4 CO Poisoning of Pt-Based Electrodes in Relation with Fuel Cell Technologies

10.5 Summary and Conclusions

References

Chapter 11: Exploring Metal Oxides: A Theoretical Approach

11.1 Introduction

11.2 Describing Oxides by Quantum Chemistry

11.3 Metal Oxide Surfaces

11.4 Case Studies

11.5 Conclusions and Perspectives

Acknowledgments

References

Chapter 12: Electrocatalysis at Liquid–Liquid Interfaces

12.1 Introduction to Electrochemistry at Liquid-Liquid Interfaces

12.2 Molecular Electrocatalysis at Functionalized ITIES

12.3 Biocatalysis at Functionalized ITIES

12.4 Nanoparticle Electrocatalysis and Photocatalysis at ITIES

12.5 Supported ITIES Electrocatalysis

12.6 Outlook

References

Chapter 13: Platinum-Based Supported Nanocatalysts for Oxidation of Methanol and Ethanol

13.1 Preparation Methods of Dispersed Electrocatalysts

13.2 Characterization Using X-ray and Other Physical Techniques

13.3 Characterization Using Electrochemical Techniques

13.4 Performance for Methanol Oxidation Reaction and Ethanol Oxidation Reaction

13.5 Single-Cell Tests

References

Chapter 14: Impact of Electrochemical Science on Energy Problems

References

Index

Wiley Series on Electrocatalysis and Electrochemistry

Andrzej Wieckowski, Series Editor

Fuel Cell Catalysis: A Surface Science Approach, Marc T. M. Koper

Electrochemistry of Functional Supramolecular Systems, Margherita Venturi, Paola Ceroni, and Alberto Credi

Fuel Cell Science: Theory, Fundamentals, and Biocatalysis, Andrzej Wieckowski and Jens Nørskov

Catalysis in Electrochemistry: From Fundamentals to Strategies for Fuel Cell Development, Elizabeth Santos and Wolfgang Schmickler

Copyright © 2011 John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Santos, Elizabeth

Catalysis in electrochemistry: from fundamentals to strategies for fuel cell development / edited by Elizabeth Santos and Wolfgang Schmickler

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-40690-8 (cloth)

eBook ISBN: 978-0-470-92941-4

oBook ISBN: 978-0-470-92942-1

ePub ISBN: 978-0-470-93473-9

To Cristina Giordano and Wolf Vielstich,Our Mentors and Parents in Science

E.S. and W.S.

Preface

By many, Professor Wolf Vielstich is considered to be the father of modern fuel cell research. His originally German textbook Brennstoffelemente, which appeared in 1965, was quickly translated into Russian, English (Fuel Cells, Wiley, 1970), and Spanish and is a classic. Even today, it is an excellent source for the scientific background behind electrochemical energy conversion. In total, Professor Vielstich has been active in fuel cell research for more than 50 years, and only a few years ago he began to edit, together with A. Lamm, H. Yokokawa, and H. Gasteiger, the Handbook of Fuel Cells—Fundamentals, Technology, Applications, whose last volumes have just been published. We interviewed him electronically at his home in Salta, Argentina.

Interview with Wolf Vielstich

What made you become interested in fuel cells as early as the 1950s?

During the early 1950s, when I was still a student, I worked at the Ruhrchemie-Oberhausen during vacations. There, in cooperation with Professor Justi, Braunschweig, experiments on high-temperature FCs were in progress, while I worked on alkaline H2/O2 cells at low temperatures. Then, in the 1960s, it was a good idea to choose H2/O2 cells, with liquid reactants, for electric power and water supply (from the cell reaction) for the NASA Apollo programm. The Wernher von Braun organization asked my advice about introducing a 1- to 2-kW FC unit, and I suggested Dr. Jose Giner from our Electrochemistry Department at Bonn University to do the job. It was a success, and NASA is still using this alkaline FC today.

Since that time there has been an ebb and flow in fuel cell activities. What are the perspectives at present?

During the last 10 years, the automobile industry, including General Motors and Daimler, has been optimistic about developing an acid-type H2–air unit for application in electric cars. But up to now, costs of production are still too high, and in addition the supply of hydrogen in the form of gas or liquid is an unsolved problem.

What is the most promising fuel for fuel cells: hydrogen, methanol, something else?

While power density and energy capacity are satisfactory in the case of H2/O2 cells, as has been demonstrated by their recent use in motorgliders (DLR-Motorsegler Antares), this is not at all the case for methanol or ethanol.

At present, there is much activity in fuel cell research. What are the challenges for fundamental science in this area today?

Nowadays, much fundamental fuel cell research is focused on the catalysis of methanol and ethanol oxidation at temperatures below 80°C. Theoretically, with oxidation to CO2, methanol can deliver six e− per molecule; at present, commercial cells deliver 250 mA cm−2 and a cell voltage of 400 mV at 60°C, and the six e− per molecule is almost attained. But for application in electric cars a factor of at least 4 to 5 in power density would be necessary. Using ethanol, present-day catalysts show an even lower energy density than with methanol and offer no more than 2–3 electrons per molecule, while the complete oxidation to CO2 involves 12 electrons. A catalyst breaking the C–C bond has still to be found.

This year, the first commercial all-electric cars, heavily subsidized, have been marketed in Japan. Are they just a marketing hype or are they already a viable alternative to conventional cars?

All-electric cars, using Li ion batteries, still have a problem. Due to the high costs, only small cars with limited power and energy capacity are being built. Hybrid systems, as produced by Toyota today, use only small battery sets; this makes sense in this particular application.

What role will electric cars play in 20 years time? Which technologies will they use: fuel cells, batteries, or a combination of both?

Without a marked change in the availability of gas and/or oil, even in 20 years time all-electric cars, using fuel cells or batteries, will make only a small contribution, mainly due to the high production costs.

E. Santos

W. Schmickler

Preface to the Wiley Series on Electrocatalysis and Electrochemistry

The Wiley Series on Electrocatalysis and Electrochemistry covers recent advances in electrocatalysis and electrochemistry and depicts prospects for their contribution to the industrial world. The series illustrates the transition of electrochemical sciences from its beginnings in physical electrochemistry (covering mainly electron transfer reactions, concepts of electrode potentials, and structure of the electrical double layer) to a filed in which electrochemical reactivity is shown as a unique aspect of heterogeneous catalysis, is supported by high-level theory, connects to other areas of science, and focuses on electrode surface structure, reaction environments, and interfacial spectroscopy.

The scope of this series ranges from electrocatalysis (practice, theory, relevance to fuel cell science and technology) to electrochemical charge transfer reactions, biocatalysis and photoelectrochemistry. While individual volumes may appear quite diverse, the series promises up-to-date and synergistic reports on insights to further the understanding of properties of electrified solid/liquid systems. Readers of the series will also find strong refernce to theoretical approaches for predicting electrocatalytic reactivity by high-level theories such as DFT. Beyond the theoretical perspective, further vehicles for growth are provided by the sound experimental background and demonstration of the significance of such topics as energy storage, syntheses of catalytic materials via rational design, nanometer-scale technologies, prospects in electrosynthesis, new research instrumentation, surface modifications in basic research on charge transfer and related interfacial reactivity. In this context, one might notice that new methods that are being developed for one specific field are readily adapted for application in another.

Electrochemistry has benefited from numerous monographs and review articles due to its applicability in the practical world. Electrocatalysis has also been the subject of individual reviews and compilations. The Wiley Series on Electrocatalysis and Electrochemistry hopes to address the current activity in both of these complementary fields by containing volumes that individually focus on topics of current and potential interest and application. At the same time, the chapters intend to demonstrate the connections of electrochemistry to areas in addition to chemistry and physics, such as chemical engineering, quantum mechanics, chemical physics, surface science, biochemistry, and biology, and thereby bring together a vast range of literature that covers each topic. While the title of each volume informs of the specific concentration chosen by the volume editors and chapter authors, the integral outcome of the series aims is to offer a broad-based analysis of the total development of the field. The progress of the series will provide a global definition of what electrocatalysis and electrochemistry are concerned with now and how these fields will evolve overtime. The purpose is twofold; to provide a modern reference for graduate instruction and for active researchers in the two disciplines, and to document that electrocatalysis and electrochemistry are dynamic fields that are ever-expanding and ever-changing in their scientific profiles.

Creation of each volume required the editor involvement, vision, enthusiasm and time. The Series Editor thanks all the individual volume editors who graciously accepted the invitations. Special thanks are for Ms. Anita Lekhwani, the Series Acquisitions Editor, who extended the invitation to the Series Editor and is a wonderful help in the assembling process of the series.

Andrzej Wieckowski

Series Editor

Contributors

Antolini, Ermete Scuola Scienza Materiali, Via 25 Aprile 22, 16016 Cogoleto (Genova), Italy

Arvia, Alejandro Jorge Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata (UNLP), Consejo Nacional de Investigaciones Científicas y Técnológicas (CONICET), Diagonal 113 y Calle 64, CC16, Suc. 4, 1900 La Plata, Argentina

Baltruschat, Helmut Abteilung Elektrochemie, Universität Bonn, Römerstr. 164, D-53117 Bonn, Germany

Beltramo, Guillermo Jülich Forschungzentrum, Institute of Complex Systems, D-52425 Jülich, Germany

Bogolowski, Nicky Abteilung Elektrochemie, Universität Bonn, Römerstr. 164, D-53117 Bonn, Germany

Bolzán, Agustín Eduardo Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata (UNLP), Consejo Nacional de Investigaciones Científicas y Técnológicas (CONICET), Diagonal 113 y Calle 64, CC16, Suc. 4, 1900 La Plata, Argentina

Calatayud, Mónica UPMC Univ Paris 06, UMR 7616, Laboratoire de Chimie Théorique, F-75005, Paris, France; CNRS, UMR 7616, Laboratoire de Chimie Théorique, F-75005, Paris, France

Climent, Víctor Instituto de Electroquímica, Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain

Cuesta, Ángel Instituto de Química Física “Rocasolano,” CSIC, C. Serrano, 119, E-28006 Madrid, Spain

Ernst, Siegfried Abteilung Elektrochemie, Universität Bonn, Römerstr. 164, D-53117 Bonn, Germany

Feliú, Juan M. Instituto de Electroquímica, Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain

Giesen, Margret Jülich Forschungzentrum, Institute of Complex Systems, D-52425 Jülich, Germany

Girault, Hubert H. Laboratoire d’ Electrochimie Physique et Analytique, Ecole Polytechnique Fédérale de Lausanne, Station 6, CH-1015 Lausanne, Switzerland

González, Ernesto R. Instituto de Química de S.ao Carlos, Universidade de S.ao Paulo, 13560-970 S.ao Carlos, Brasil

Gross, Axel Institute of Theoretical Chemistry, Ulm University, Albert-Einstein- Allee 11, D-89069 Ulm, Germany

Gutiérrez, Claudio Instituto de Química Física “Rocasolano,” CSIC, C. Serrano, 119, E-28006 Madrid, Spain

Herrero, Enrique Instituto de Electroquímica, Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain

Koper, Marc T.M. Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands

Parsons, Roger 16 Thornhill Road, Bassett, Southampton 5016 TAT, United Kingdom

Pasquale, Miguel Ángel Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata (UNLP), Consejo Nacional de Investigaciones Científicas y Técnológicas (CONICET), Diagonal 113 y Calle 64, CC16, Suc. 4, 1900 La Plata, Argentina

Samec, Zdenk J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of Czech Republic, Dolejskova 3, 182 23, Prague 8, Czech Republic

Santos, Elizabeth Instituto de Física Enrique Gaviola (IFEG-CONICET), Facultad de Matemática, Astronomía y Física Universidad Nacional de Córdoba, Córdoba, Argentina and Institute of Theoretical Chemistry, Ulm University, Albert-Einstein- Allee 11, D-89069 Ulm, Germany

Schmickler, Wolfgang Institute of Theoretical Chemistry, Ulm University, Albert- Einstein-Allee 11, D-89069 Ulm, Germany

Schnur, Sebastian Institute of Theoretical Chemistry, Ulm University, Albert- Einstein-Allee 11, D-89069 Ulm, Germany

Su, Bin Laboratoire d’ Electrochimie Physique et Analytique, Ecole Polytechnique Fédérale de Lausanne, Station 6, CH-1015 Lausanne, Switzerland

Ticianelli, Edson A. Instituto de Química de S.ao Carlos, Universidade de S.ao Paulo, 13560-970 S.ao Carlos, Brasil

Tielens, Frederik UPMC Univ Paris 06, UMR 7609, Laboratoire de Réactivité de Surface, F-75005, Paris, France; CNRS, UMR 7609, Laboratoire de Réactivité de Surface, F-75005, Paris, France

Chapter 2

Electrocatalysis: A Survey of Fundamental Concepts

Alejandro Jorge Arvia, Agustìn Eduardo Bolzán and Miguel Ángel Pasquale

Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA), Universidad Nacional de La Plata (UNLP)1900 La Plata, Argentina

2.1 Introductory aspects to fuel cell electrocatalysis

A fuel cell is an electrochemical device in which electrochemical oxidation at the anode and a reduction reaction at the cathode take place and electrons that are released at the anode move to the cathode via the external circuit producing electrical work. This process is accompanied by the displacement of positive and negative ions through the conducting medium to the cathodic and anodic regions, respectively. The study of both the kinetics and mechanism of anodic and cathodic processes in either homogeneous or heterogeneous systems combines electrochemistry and catalysis knowledge [1–3]. Technical application of this knowledge to the development of fuel cells requires solving electrochemical engineering problems of design and optimization [4, 5]. The latter issue is beyond the scope of this chapter.