MODERN ASPECTS OFELECTROCHEMISTRY

No. 36

Modern Aspects ofElectrochemistryModern Aspects of Electrochemistry, No. 35:

Impedance spectroscopy with specific applications to electrodeprocesses involving hydrogen.Fundamentals and contemporary applications of electroless metaldeposition.The development of computational electrochemistry and itsapplication to electrochemical kinetics.Transition of properties of molten salts to those of aqueoussolutions.Limitations of the Born Theory in applications to solventpolarization by ions and its extensions to treatment of kinetics ofionic reactions.

Modern Aspects of Electrochemistry, No. 34:

Additivity principles in behavior of redox couples and corrosionprocesses.Foundation of voltaic measurements at liquid interfaces.Direct methanol fuel cells: current progress and emergingtechnology.Dynamics of processes in molten salts.Electrochemical techniques and microbially influenced corrosion(MIC).

Modern Aspects of Electrochemistry, No. 33:

A review of the literature on the potential-of-zero charge.Review and discussion on nonequilibrium fluctuations in corrosionprocesses.Conducting polymers, their electrochemistry and biomimickingprocesses.Microwave photoelectrochemistry; from its origins to currentresearch problems.New fluorine cell design from model development through pilotplant tests.The rapidly developing field of electrochemistry of electronicallyconducting polymers and their applications.

MODERN ASPECTS OFELECTROCHEMISTRY

No. 36

Edited by

C. G. VAYENASUniversity of Patras

Patras, Greece

B. E. CONWAYUniversity of Ottawa

Ottawa, Ontario, Canada

RALPH E. WHITEUniversity of South Carolina

Columbia, South Carolina

and

MARIA E. GAMBOA-ADELCOManaging Editor

Superior, Colorado

KLUWER ACADEMIC PUBLISHERSNEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW

eBook ISBN: 0-306-47927-3Print ISBN: 0-306-47492-1

©2004 Kluwer Academic PublishersNew York, Boston, Dordrecht, London, Moscow

Print ©2003 Kluwer Academic/Plenum Publishers

All rights reserved

No part of this eBook may be reproduced or transmitted in any form or by any means, electronic,mechanical, recording, or otherwise, without written consent from the Publisher

Created in the United States of America

Visit Kluwer Online at: http://kluweronline.comand Kluwer's eBookstore at: http://ebooks.kluweronline.com

New York

LIST OF CONTRIBUTORS

PANAKKATTU K. BABUDepartment of ChemistryUniversity of Illinois at Urbana-ChampaignUrbana, Illinois 61801, USA

PANOS NIKITASLaboratory of Physical ChemistryDepartment of ChemistryAristotle University of Thessaloniki54124 Thessaloniki, Greece

IVAN BOLZONELLAUnit of Electrochemical EngineeringInstitute of Chemical and BiologicalProcess ScienceSchool of Basic SciencesSwiss Federal Institute of TechnologyCH-1015 Lausanne, Switzerland

ERIC OLDFIELDDepartment of ChemistryUniversity of Illinois at Urbana-ChampaignUrbana, Illinois 61801, USA

CHRISTOS COMNINELLISUnit of Electrochemical EngineeringInstitute of Chemical and BiologicalProcess ScienceSchool of Basic SciencesSwiss Federal Institute of TechnologyCH-1015 Lausanne, Switzerland

SU-IL PYUNDepartment of Materials Scienceand EngineeringKorea Advanced Institute of Scienceand Technology373-1 Guseong-dong, Yuseong-gu,Daejeon305-701 Republic of Korea

GYÖRGY FÓTIUnit of Electrochemical EngineeringInstitute of Chemical and BiologicalProcess ScienceSchool of Basic SciencesSwiss Federal Institute of TechnologyCH-1015 Lausanne, Switzerland

HEON-CHEOL SHINDepartment of Materials Scienceand EngineeringKorea Advanced Institute of Scienceand Technology373-1 Guseong-dong, Yuseong-gu,Daejeon305-701 Republic of Korea

MARC T. M. KOPERSchuit Institute of CatalysisLaboratory for Inorganic Chemistry andCatalysisEindhoven University of Technology5600 MG Eindhoven, The Netherlands

ANDRZEJ WIECKOWSKIDepartment of ChemistryUniversity of Illinois at Urbana-ChampaignUrbana, Illinois 61801, USA

A Continuation Order Plan is available for this series. A continuation order will bring deliveryof each new volume immediately upon publication. Volumes are billed only upon actualshipment. For further information please contact the publisher.

Preface

This volume of Modern Aspects contains a remarkable spread of topicscovered in an authoritative manner by some internationally renownedspecialists. In a seminal chapter Drs. Babu, Oldfield and Wieckowskidemonstrate eloquently the strength of electrochemical nuclear magneticresonance (EC-NMR) to study in situ both sides of the electrochemicalinterface via the simultaneous use of and This powerfulnon-invasive technique brings new insights to both fundamental andpractical key aspects of electrocatalysis, including the design of betteranodes for PEM fuel cells.

The recent impressive advances in the use of rigorous ab initioquantum chemical calculations in electrochemistry are described in aremarkable chapter by Marc Koper, one of the leading protagonists in thisfascinating area. This lucid chapter is addressed to all electrochemists,including those with very little prior exposure to quantum chemistry, anddemonstrates the usefulness of ab initio calculations, including densityfunctional theory (DFT) methods, to understand several key aspects offuel cell electrocatalysis at the molecular level.

The most important macroscopic and statistical thermodynamicmodels developed to describe adsorption phenomena on electrodes arepresented critically in a concise and authoritative chapter by PanosNikitas. The reader is guided through the seminal contributions ofFrumkin, Butler, Bockris, Guidelli and others, to the current state of theart adsorption isotherms, which are both rigorous, and in good agreementwith experiment.

Electrochemical promotion (i.e., the use of electrochemistry toactivate and in situ tune the catalytic activity and selectivity of metal andmetal oxide catalysts interfaced with solid electrolytes) is discussed in aremarkable chapter by Drs. György Fóti, Ivan Bolzonella and Christos

vii

viii Preface

Comninellis, who discuss both the fundamentals of this new excitingapplication of electrochemistry as well as recent advances includingnovel monolithic designs, for its practical utilization.

Lithium transport through transition metal oxides and carbonaceousmaterials is of paramount importance in rechargeable lithium batteries.The chapter by Drs. H. -C. Shin and Su-Il Pyun from KAIST, Korea,examines critically the “diffusion control” models, used routinely forcurrent transients (CT) analysis, and demonstrates that, quite frequently,the cell current is controlled by the total cell impedance and not by lithiumdiffusion alone. This interesting chapter, rich in new experimental data,also provides a new method for CT analysis and an explanation for theexisting discrepancy in Li diffusivity values obtained by the diffusioncontrol CT analysis and other methods.

B. E. ConwayUniversity of OttawaOttawa, Ontario, Canada

C. G. VayenasUniversity of PatrasPatras, Greece

R. E. WhiteUniversity of South CarolinaColumbia, South Carolina

Contents

Chapter 1

NANOPARTICLE SURFACES STUDIEDBY ELECTROCHEMICAL NMR

P. K. Babu, E. Oldfield, and A. Wieckowski

I. Introduction 14557

9

II. ExperimentalIII. Results and Discussion

1.2.3.

4.

Selected Topics inOther Pt Nanoparticles (Unsupported and Supported)Correlation Between the Shift andAdsorbates ElectronegativitySpatially-Resolved Oscillation of the in a PtCatalyst 14

17171820

22

25

27

2937

IV. NMR at the Electrochemical Interface1.2.3.4.

5.

6.

7.

8.

NMR Knight ShiftEC-NMR Under Potential ControlCorrelation of NMR to FTIR DataCorrelation Between Clean Surface ofMetals and the Adsorbate Knight ShiftNMR Comparison of CO Adsorbed on Pt-Black fromDifferent SourcesEffect of Surface Charge on the Chemisorption Bond:CO Chemisorption on PdPt Electrodes Modified by Ruthenium: A Study inToleranceEC-NMR of Pt/Ru Alloy Nanoparticles

ix

x Contents

V. Summary and Conclusions 404248

AppendixReferences

Chapter 2

AB INITIO QUANTUM-CHEMICALCALCULATIONS IN ELECTROCHEMISTRY

Marc T. M. Koper

I. Introduction 5154

5456576061616364646567

78

8898

II. Ab Initio Quantum Chemistry1.

2.3.4.5.6.7.

General Aspects of Quantum Chemistry andElectronic Structure CalculationsWave-Function-Based MethodsDensity Functional Theory MethodsBasis Sets and Effective PotentialsStructure, Energetics, and Vibrational FrequenciesMethods of AnalysisAb Initio Molecular Dynamics

III. Selected Applications1.2.3.4.

5.

6.7.

8.

Clusters and SlabsHow to Model the Electrode PotentialChemisorption of Halogens and HalidesChemisorption of Carbon Monoxide on Metals andAlloysField Dependent Chemisorption and the InterfacialStark Effect: General RelationshipsField-Dependent Chemisorption of Carbon MonoxideChemisorption of Water and Water DissociationProducts 106

115125127

Ab Initio Approaches to Modeling ElectrodeReactions

IV. OutlookReferences

Contents xi

Chapter 3

MACROSCOPIC AND MOLECULAR MODELS OFADSORPTION PHENOMENA ON ELECTRODE SURFACES

P. Nikitas

I. Introduction 131132136136138140140145153153161164166171

177182184185

II. Features of Electrosorption and Factors Affecting ThemIII. Macroscopic Models

1.2.

PC ApproachSTE Approach

IV. Molecular Models1.2.

Guidealli’s ApproachModels Based on the LBS Approach

V. Complicated Adsorption Phenomena1.2.3.4.

Co-Adsorption and ReorientationPolylayer FormationSurface SegregationPhase Transitions

VI. Polarization Catastrophe and Other ArtifactsVII. The Role of the Metal Electrode—The Case of Solid

ElectrodesVIII. Computer Simulation

IX. ConclusionsReferences

Chapter 4

ELECTROCHEMICAL PROMOTION OF CATALYSIS

György Fóti, Ivan Bolzonella, and Christos Comninellis

I. Introduction 191193

194

II. The Phenomenon of Electrochemical Promotion1. Description of a Typical Electrochemical Promotion

Experiment

xii Contents

2.3.

The Mechanism of Electrochemical Promotion 197203207207209

212216219224228

230233236236241244248250252

Promotional TransientsIII. Fundamental Studies of Electrochemical Promotion

1.2.3.

4.5.6.7.8.

9.

Catalytic Model SystemsExperimental AspectsElectrochemical Characterization of the Single-PelletCellCyclic VoltammetryFast-Galvanostatic TransientsPermanent Electrochemical PromotionElectrochemical Activation of a CatalystElectrochemical Promotion and Catalyst-SupportInteractionsWork Function Measurements

IV. Cell Development for Electrochemical Promotion1.2.3.4.

Bipolar Con guration for Electrochemical PromotionRing-Shaped Electrochemical CellMultiple-Channel Electrochemical CellPerspectives

V. ConclusionsReferences

Chapter 5

MECHANISMS OF LITHIUM TRANSPORTTHROUGH TRANSITION METAL OXIDES

AND CARBONACEOUS MATERIALS

Heon-Cheol Shin and Su-Il Pyun

I. Introduction 255

257259260261

II. Bird’s Eye View of the Models for Current Transients inLithium Intercalation Systems: Diffusion ControlledLithium Transport1.2.3.

The Geometry of the Electrode SurfaceThe Growth of a New Phase in the ElectrodeThe Electric Field in the Electrode

Contents xiii

III. General Perspective on Current Transients fromTransition Metal Oxides and Graphite 261

264

267268273273

273

278

283283

284

286

294297298

303

1.

2.

3.4.

Non-Cottrell behavior throughout the LithiumIntercalation/DeintercalationIntersection of Anodic and Cathodic CurrentTransients(Quasi-)Current PlateauDepression of the Initial Current Value

IV. Physical Origin of the Current Transients1.

2.

Linear Relation Between Current and ElectrodePotentialComparison of Cell Resistances Determined by theCurrent Transient Technique and by ElectrochemicalImpedance Spectroscopy

V. Theoretical Description of Cell-Impedance ControlledLithium Transport1.2.

3.

4.

Governing Equation and Boundary ConditionCalculation Procedure of the Cell-ImpedanceControlled Current TransientsTheoretical Current Transients and their Comparisonwith Experimental Current TransientsSome Model Parameters Affecting the Shape andMagnitude of the Cell-Impedance Controlled CurrentTransients

VI. Concluding RemarksReferences

INDEX