Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry

NATO ASI Series Advanced Science Institutes Series

A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.

The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division

A LHe Sciences B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences IG Ecological Sciences H Cell Biology

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

Series C: Mathematical and Physical Sciences - Vol. 320

Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry edited by

C. Gutierrez Instituto de Qufmica Ffsica "Rocasolano", C.S.I.C., Madrid, Spain

and

C. Melendres Argonne National Laboratory, Argonne, Illinois, U.S.A.

Springer Science+Business Media, B.V.

Proceedings of the NATO Advanced Study Institute an Spectroc:opic and Diffraction Techniques in Interfaaal Electrochemistry Puerta de la Cruz, Tenerife, Spain July 3-15,1988

Ubrary of Congress Cataloglng-in~Publlcation Data NATO Advanced Stuay Institute on SpectroscoplC and Dlffractlon

Technlques In InlerfaClz1 Electroche.,s t ry 11 968 Puerto de la Cru2. Can,ry !sllnds)

Spectroscop'C 'nd dlffr~CI'on tachnlqu es In In terflc l a l electroche",stry I edlted Oy C. Gu t llrrez and C. Melendres.

p. C • . -- (NATO ASI serles. Ser les C. Matheutlc,l and physlcal sClences ; o .

-Proceedlngs of Ihe NATO Advanced Study Institute on SplctrO$coplC and Dlffractlen Technlques In !nterhclal EleCtrocheMlstry. Puerte de la Cruz, hnerlfr. Sp"n, 3-15 ..July 1988."

Includes blbl,o!iraphlcal referlnces ana IndeK.

1 . i:lectrochu,stry- -Con!iresses. 2 . Surface chellstry­-Congresses. 3. Spectrul a nalysls--Cen!iresse s. 4. Olffrac t ion-- Congresses. 1. Gut,errez. C. (Claudlo). 1942- Il . Melendres. C. (Cules). 1939- III. T,tle. IV. Tltle, InterfiClil e lectrocne .. ,stry. V. Ser les . 00551.N36 1988 541.3·7- -oc20 90-5353

ISBN 978-94-010-5684-7

Printed on acid-free paper

AII Rights Reserved © 1990 Springer Science+Busincss Media Dordrecht Origina11y published by Kluwer Academic Publishers in 1990 Softcover reprint of the hardcover 1 st edition 1990 No part 01 the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo­copying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

ISBN 978-94-010-5684-7 ISBN 978-94-011-3782-9 (eBook)

fdfffhj320e)fISBN 978-94-011-3782-9 (eBook)

DOI 10.1007/978-94-011-3782-9

CONTENTS

Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

List of Participants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................... ix

List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .xv

The Advancing Frontier in the Knowledge of the Structure of Interphases J. O'M. Bockris and A. Gonzalez Martin ................................. 1

Some Recent Spectroscopic Approaches to the Solid-Solution Interface J. O'M. Bockris and M. Gamboa Aldeco .................................. 55

Application to Electrocatalysis of EMIRS (Electrochemically Modulated Infrared Reflectance Spectroscopy) and Related Techniques B. Beden ...................................................... 103

Photoacoustic Spectroscopy and the In-Situ Characterization of the Electrochemical Interface C. E. Vallet .................................................... 133

Raman Spectroscopic Techniques in Interfacial Electrochemistry R K. Chang .................................................... 155

Laser Raman Spectroscopy in Studies of Corrosion and Electrocatalysis C. A. Melendres .................................................. 181

UV -Visible Reflectance Spectroscopy in Electrochemistry W. Plieth ...................................................... 223

Study of Anodic Oxides by UV-Visible Potential-Modulated Reflectance Spectroscopy C. Gutierrez .................................................... 261

vi

Nonlinear Optical Techniques for Surface Studies Y. R. Shen ..................................................... 281

X-Ray Diffraction at the Electrode-Solution Interface J. Robinson ..................................................... 313

X-Ray Reflectivity and Surface Roughness B. M. Ocko ..................................................... 343

Surface Structural Investigations by Electron Diffraction Techniques D.M. Kolb, G. Lehmpfuhl and M. S. Zei ................................. 361

Auger Electron Spectroscopy and the Electrochemical Interface D. J. Aberdam .................................................. 383

Photoelectron Spectroscopy (xpS and UPS) of Electrode Surfaces R. Katz ....................................................... 409

Rutherford Backscattering Spectroscopy of Electrode Surfaces R. Katz ....................................................... 439

Electrochemical Applications of Scanning Tunneling Microscopy A. J. Arvia ..................................................... 449

Subject index ................................................... .471

PREFACE

Electrochemistry is one of the oldest branches of Physical Chemistry. Having its foundations in the work of Faraday, Arrhenius and others, it evolved from the study of transport in electrolyte solutions to that of electrode kinetics. Kinetic methods are inherently unable to identify unequivocally the species involved in a reaction. Therefore, beginning in the 70s many spectroscopic and diffraction techniques were applied to the study of the electrode-electrolyte interface, in order to identify intermediary reaction species, and even the spatial arrangement of atoms or molecules at the interface. In order to disseminate these techniques, a NATO Advanced Sutdy Institute was held at Puerto de la Cruz, Tenerife (Canary Islands, Spain) from July 2 to 15, 1988. The Institute consisted of tutorial type lecutures, poster sessions, and round-table discussions. It was attended by over 65 participants from NATO-member countries, and others from Argentina and Japan.

In the present volume most of the lectures presented at the Institute have been collected. At least one chapter is devoted to each technique. Emphasis has been made on case studies, rather than theory, which can be found in textbooks and other publications. Our purpose in this book is to help the electrochemists uninitiated in spectroscopic methods to decide which techniques would be suitable for application to their particular problems.

We thank all the lecturers who contributed to this volume, and even those UHPs (Unrepentant Habitual Procrastinators) who did not in spite of our urgings to do so. We greatly appreciate the many hours they spent in preparing their lectures and in after-hours discussions with the participants. We owe a great deal of gratitude to our local co-director, Prof. Arevalo, for his excellent organization of the local arrangements.

It was our pleasure to have as company participants from so many lands. Finally, we thank the Scientific Affairs Division of NATO for their financial support.

C. Gutierrez and C. A. Melendres

vii

LIST OF PARTICIPANTS

ALBARELLI, Michael J. Baker Laboratory, Department of Chemistry, Cornell University, Ithaca, NY 14853, U.S.A.

ANDERSON, Mark R. Department of Chemistry, University of Utah, Salt Lake City, UT 84112, U.S.A.

ANDREU, Rafael. Depto. de QUimica Fisica, Fac. de Quimica, Universidad de Sevilla, 41012-Sevilla. Spain.

BEREKET, Gozen. Dept. of Chemistry, Faculty of Arts and SCience, University of Anatolia, Turkey.

CASADO GIMENEZ, Juan. Dept. of Physical Chemistry, Universidad Aut6noma de Barcelona, Bellaterra, Barcelona, Spain.

CELDRAN, Raquel. Universidad Aut6noma de Madrid, F.3.cultad de Ciencias, Depto. Quimica, C-II, 28049 Madrid, Spain.

CROUIGNEAU, Pierre. Laboratoire de Chimie I, UER Sciences, Universite de POitiers, 86022 Poitiers Cedex, France.

DA SILVA, Rui. Faculdade de Engenharia, Universidade do Porto, 4000 Porto, Portugal

EPPEL, Steve Department of Physics, Case Western Reserve University, Cleveland, OH 44106, U.S.A.

ERBOLUKBAS, Aysen. Istanbul Universitesi Fen Fakultesi Fizik Bolumu, Vezneciler Istanbul, Turkey.

ESKIKAYA, Tulay. Chemistry Dept., Istanbul Technical Uni~rersity, 82060 Istanbul, Turkey

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x

FERNANDES, Joao. Instituto Superior Tecnico, Lab. Electroquimica, Universidade Tecnica de Lisboa, 1096 Lisboa Codex, Portugal.

FERREIRA, Mario G.S. Depto. de Eng. Quimica, Instituto Superior Tecnica, Universidade Tecnica de Lisboa, 1096 Lisboa Codex, Portugal.

FONSECA, Ines. Dept. of Chem., Faculty of Science of Lisbon, CECUL, R. da Escola Pol1teenica 58-1293 Lisboa Codex, Portugal.

FONTANESI, Claudio. University of Modena, Dept. of Chemistry, Via Campi 183, 41100 Modena, Italy.

GIORDANO, Cristina. INIFTA, Casilla de Correo 16, Sucursal 4, (1900) La Plata, Argentina.

GOMEZ, Mercedes Depto. de Quimica, Facultad de Ciencias, C-II, Universidad Aut6noma de Madrid, 28049 Madrid, Spain.

GOSLICH, Roland. Insttitut fUr Solarenergieforschung GmbH, Sokelant StraSe 5, D-3000 Hannover 1, West Germany.

HANSEN, Galen J. Physics Dept., UMC 4415, Utah State University, I-ogan, UT 84322. USA.

JAEGERMANN, Wolfram. Hahn-Meitner Institut, Glienicker Str. 100, D-1000 Berlin 39, West Germany.

JEHOULET. Laboratoire des Surfaces et Interfaces, 13 rue de Toul, 59046 Lille Cedex, France.

JIMENEZ FERRER, M. Isabel. Dpto. Fisiea Aplicada, Facultad de Ciencias, Ciudad Universitaria de Cantoblanco, 28049 Madrid. Spain.

JUSTO, Maria Julia. L.N.E.T.!., Az. Lameiros, Est. Paco Lumiar, 1600 Lisboa, Portugal.

KAUTEK, W.M. Laboratory for Chemical Surface Technologies, Federal Insitute for Materia.l;; Research, Unter den Eichen 87, D-1000 Berlin 45, West Germany

KESSEL, Robert. Inst. of Physical Chemistry, Universitat Dusseldorf, D-4000 Dusseldorf, Universitatsstrasse I, Gebaude 26.32, West Germany.

LARRAMONA, Gerardo Instituto de Quimica Fisica "Rocasolano", tSIC, Serrano, 119, 28006-Madrid, Spain.

LA UERMANN, Iver. Institut fur Solarenergieforschung, SokelantstraBe 5, D-3000 Hannover I, West Germany.

MAKKY, Wagih. Dept. of Electrical Engineering, University of Illinois, Chicago, IL 60680, U.S.A.

MARASSI, Roberto. Dept. of Chemistry, University of Camerino, Via S. Agostino I, Italy.

MARCO SANZ. Jose F. Instituto de Quimica Fisica "Rocasolano", CSIC, Serrano. 119, 28006-Madrid, Spain.

MARTIN NEVSKAIA, Daniela. Dpto. Fisica Aplicada. Facultad de Ciencias, Ciudad Un1vers1tar1a de Cantoblanco, 28049 Madrid. Spain.

McMAHON, John J. Dept. of Chemistry, Fordham University, Bronx, N.Y. 10458, U.S.A.

MEISSNER, Dieter. Inst1tut fur Solarenergiesforschung, Sokelantstrasse 5, D-3000 Hannover 1, West Germany.

MONTEIRO, Fernando J. Depto. de Engenharia Metalurgica, Universidade do Porto, Rua dos Bragas, 4099 Porto Codex, Portugal.

MuLLER JEVENOIS, Carlos. Dpto. Quimica Fisica. Universidad de Barcelona, Marti i Franques I, 08028 Barcelona, Spain.

OLLIER, Nathalie. Laboratoire d'Electrochimie Interfaciale (LEI), CNRS, 1, Place Aristide Briand, 92195 Meudon Principal Cedex, France.

OZSAVASCI, Cenglz. Gazi Universitesi, Fen-Edebiyat Fakultesi, Kimya Boliimu, 06500 Teknikokullar, Ankara. Turkey.

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xii

PALITEIRO, Carlos. Department of Chemistry, University of C01mbra, 3049-C01mbra, Portugal.

PEjA, Maria Jesus. Depto. de Quimica, Facultad de Ciencias, C-II, Universidad Aut6noma de Madrid, 28049-Madrid, Spain.

PEREIRA, M. Isabel S. CECUL, Fac. de Ciencias, R. Da Escola Politecn1ca, 1200 Lisboa, Portugal. PH ILPOTT, }If .R. IBM Almaden Research Center, 650 Harry Road, San Jose, CA 95120-6099, U.S.A.

PIAZZA, Giuseppe. Dipart1mento Chimico "G. CiamicianM , Via Selmi, 2, 40127 Bologna, Italy.

PIMENTA, Gervasio. ICEN-LNETI, Depto. de Quimica, P-2686 Sacavem Codex, Portugal.

RADZ ISZEWSK I , J. G. Center for Structure and Reactivity, Department of Chemistry, The University of Texas at Austin, Austin, TX 78712-1167, U.S.A.

RANGEL, Carmen Mireya. LNE!I, Department of Materials Technology, Corrosion and Protection, 22 Paco do Lumiar, 1699 L1sboa Cedex, Portugal.

RIKMASCH, Jerk. Insti tut fur Solarenergieforschung, SokelantstraBe 5, D-3000 Hannover 1. West Germany.

ROBINSON, Jeanne K. Dept. of Chemistry, University of Oregon, Eugene, OR 97403, U.S.A.

SA, Carlos K. Depto. de Engenharia Metalurg1ca, Universidade do Porto, Rua dos Bragas, 4099 Porto Codex, Portugal.

SANTOS LOPES, Maria Irene. CECUL, Dep. Quimica, Faculdade de Ciencias, Rua da Escola Politecnica, 1200 Lisboa, Portugal.

SANZ, Fausto. Dpto. Quim1ca Fisica, Fac. Quimica, Universidad de Barcelona, Av. Diagonal 647, 08028 Barcelona, Spain.

SARAC, A. Sezai Technical University of Istanbul, Departmant of Chemistry, Maslak-Istanbul, Turkey

SHANNON, Curtis. Department of Chemistry, University of Texas, Austin, TX 78712, U.S.A.

TADJEDDINE, Abderrahmane. LEI du CNRS, 1 Plo Aristide Briand, F 92195 Meudon Ppl. Cedex, France.

YOSH IKA W A, Kozo. Takasago R&D Center, Mitsubishi Heavy Industries, Ltd., 2-1-1 Shinhama, Arai-Cho, Takasago, Hyogo Pret., 676 Japan.

xiii

LIST OF CONTRIBUTORS

ABERDAM, Daniel. Lab. de Spectrometrie Physique. Universite Joseph Fourier Grenoble I, BP87, F38402 St Martin d'Heres, France.

ARVIA, Alejandro J. Instituto de Investigaciones Fisicoquimicas Te6ricas y Aplicadas (INIFTA), Casilla de Correo 16, Sucursal 4, 1900-La Plata, Argentina.

BEDEll, Bernard. Lab. de Chimie I- Electrochimie et Interactions, U.A. au C.N.R.S. 350, Universite de Po1tiers, 86022 Po1tiers, France.

BOCKRIS, John O'M. Department of Chemistry, Texas A & M University, College Station, Texas 77843, U.S.A.

CHANG, Richard K. Section of Applied Physics and Center for Laser DiagnostiCS, Yale University, New Haven, CT 06520, U.S.A.

GUTIERREZ, Claudio Instituto de Quimica Fis1ca "Rocasolano", Consejo Superior de Investigaciones C1entificas, Serrano, 119, 28006-Madrid, Spain.

KOLB, Dieter M. Fritz-Haber-Institut der Max-Planck-Gesellschaft, D-1000 Berlin 33, West Germany.

KbTZ, Riidiger. ASEA Brown Boveri Corporate Research Center, CH 5405 Baden, Switzerland.

MEL ENDRES , Carlos. Materials Science and Chemical Technology Division, Argonne National Laboratory, Argonne, IL 60439, U.S .A.

OCKO, Benjamin Brookhaven National Laboratory, Bldg. 510B, Upton, N.Y. 11973, U.S.A.

PLIETH, Waldfried J. Institut fiir Physikalische und Theoretische Chemie, Freie Universitat Berlin, Takustrasse 3, D-1000 Berlin 33, West Germany.

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xvi

ROBINSON, James. Department of Physics, University of Warwick, Coventry CV4 7AL, United Kingdom.

SHEN, Y R. Department of Physics, University of California, Berkeley, CA 94720,U.S.A.

VALLET, Catherine E. Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, U.S.A.

LIST OF LECTURERS WHO FAILED TO SEND THEIR MANUSCRIPTS

BEWICK, Alan. Department of Chemistry, University of Southampton, Southampton S09 5NH, United Kingdom.

CAHAN, Boris D. Case Center for Electrochemical Studies and Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106, U.S.A.

HOFFMAN, Richard W. Department of Physics, Case Western Reserve University, Cleveland, OH 44106, U.S.A.

SASS, Jurgen K. Dept. of Surface Reactions, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-1000 Berlin 33/Dahlem, West Germany.