Fuel cell catalysis: a surface science approach

709 Pages·2009·26.1 MB·English

by  Andrzej Wieckowski

FUEL CELL CATALYSIS
WILEY SERIES ON ELECTROCATALYSIS
AND ELECTROCHEMISTRY
AndrzejWieckowski,SeriesEditor
FuelCellCatalysis:ASurfaceScienceApproach,EditedbyMarcT.M.Koper
ElectrochemistryofFunctionalSupramolecularSystems,MargheritaVenturi,
PaolaCeroni,andAlbertoCredi
CatalysisinElectrochemistry:FromFundamentalstoStrategiesforFuelCell
Development,ElizabethSantosandWolfgangSchmickler
FuelCellScience:Theory,Fundamentals,andBiocatalysis,AndrzejWieckowski
andJensNorskov
FUEL CELL CATALYSIS
A SURFACE SCIENCE APPROACH
Edited by
Marc T. M. Koper
The Wiley Series on Electrocatalysis and Electrochemistry
Copyright#2009byJohnWiley&Sons,Inc.Allrightsreserved
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LibraryofCongressCataloging-in-PublicationData:
Fuelcellcatalysis:asurfacescienceapproach/editedbyMarcKoper.
p.cm.—(TheWileyseriesonelectrocatalysisand
electrochemistry)
Includesindex.
ISBN978-0-470-13116-9(cloth)
1.Electrocatalysis. 2.Fuelcells. 3.Solid-liquidinterfaces. I.
Koper,Marc.
QD569.F84 2009
621.3102429—dc22
2009004193
CoverimagecourtesyofMatthewNeurock
PrintedintheUnitedStatesofAmerica
10 9 8 7 6 5 4 3 2 1
&CONTENTS
Preface to the Wiley Series on Electrocatalysis and
Electrochemistry vii
Preface ix
List of Contributors xi
1. ElectrocatalysisofOxygenReductioninPolymer
ElectrolyteFuelCells:ABriefHistoryandaCritical
ExaminationofPresentTheoryandDiagnostics 1
ShimshonGottesfeld
2. ElectrochemicalElectronTransfer:
FromMarcusTheorytoElectrocatalysis 31
E.SantosandW.Schmickler
3. ElectrocatalysisandCatalystScreeningfromDensity
FunctionalTheoryCalculations 57
J.Rossmeisl,J.Greeley,andG.S.Karlberg
4. First-PrinciplesSimulationoftheActiveSitesandReaction
EnvironmentinElectrocatalysis 93
MichaelJ.Janik,SallyA.Wasileski,ChristopherD.Taylor,
andMatthewNeurock
5. AbInitioAtomisticThermodynamicsforFuelCellCatalysis 129
TimoJacob
6. MechanismsoftheOxidationofCarbonMonoxideand
SmallOrganicMoleculesatMetalElectrodes 159
MarcT.M.Koper,StanleyC.S.Lai,andEnriqueHerrero
7. CluesfortheMolecular-LevelUnderstandingofElectrocatalysison
Single-CrystalPlatinumSurfacesModifiedbyp-BlockAdatoms 209
V.Climent,N.Garc´ıa-Ara´ez,andJ.M.Feliu
8. ElectrochemistryatWell-CharacterizedBimetallicSurfaces 245
VojislavR.StamenkovicandNenadM.Markovic
v
vi CONTENTS
9. RecentDevelopmentsintheElectrocatalysisoftheO
2
ReductionReaction 271
YeXu,MinhuaShao,ManosMavrikakis,andRadoslavR.Adzic
10. ElectrocatalysisatPlatinumandBimetallicAlloys 317
MasahiroWatanabeandHiroyukiUchida
11. ElectrocatalysisfortheDirectAlcoholFuelCell 343
J.-M.Leger,C.Coutanceau,andC.Lamy
12. BroadbandSumFrequencyGenerationStudiesofSurface
IntermediatesInvolvedinFuelCellElectrocatalysis 375
G.Q.Lu,A.Lagutchev,T.Takeshita,R.L.Behrens,DanaD.Dlott,
andA.Wieckowski
13. Methanol,Formaldehyde,andFormicAcidAdsorption/Oxidation
onaCarbon-SupportedPtNanoparticleFuelCellCatalyst:
AComparativeQuantitativeDEMSStudy 411
Z.JusysandR.J.Behm
14. TheEffectofStructurallyWell-DefinedPtModification
ontheElectrochemicalandElectrocatalyticProperties
ofRu(0001)Electrodes 465
H.E.HosterandR.J.Behm
15. SizeEffectsinElectrocatalysisofFuelCellReactions
onSupportedMetalNanoparticles 507
FredericMaillard,SergeyPronkin,andElenaR.Savinova
16. SupportandParticleSizeEffectsinElectrocatalysis 567
BrianE.HaydenandJens-PeterSuchsland
17. ElectrocatalysisforFuelCellsatEnzyme-ModifiedElectrodes 593
K.A.Vincent,S.C.Barton,G.W.Canters,andH.A.Heering
18. MetalloporphyrinCatalystsofOxygenReduction 637
RomanBoulatov
Index 695
&PREFACE to the Wiley Series on Electrocatalysis and
Electrochemistry
Thisseriescoversrecentadvancesinelectrocatalysisandelectrochemistryanddepicts
prospects fortheircontribution intothepresent andfutureof theindustrial world.It
illustratesthe transition of electrochemical sciences from a solid chapterof physical
electrochemistry (covering mainly electron transfer reactions, concepts of electrode
potentialsandstructureoftheelectricaldoublelayer)tothefieldinwhichelectroche-
micalreactivityisshownasauniquechapterofheterogeneouscatalysis,issupported
byhigh-leveltheory,connectstootherareas ofscience,andincludesfocusonelec-
trodesurfacestructure,reactionenvironment,andinterfacialspectroscopy.
Thescopeofthisseriesrangesfromelectrocatalysis(practice,theory,relevanceto
fuelcellscienceandtechnology)toelectrochemicalchargetransferreactions,bioca-
talysis,andphotoelectrochemistry.Whileindividualvolumesmaylookquitediverse,
the series promises updated and overall synergistic reports on insightsto further the
understandingofproperties ofelectrifiedsolid/liquid systems.Readers oftheseries
willalsofindstrongreferencetotheoreticalapproachesforpredictingelectrocatalytic
reactivity by such high-level theories as DFT. Beyond the theoretical perspective,
furthervehiclesforgrowtharethesoundexperimentalbackgroundanddemonstration
of significance of such topics as energystorage, syntheses of catalytic materials via
rational design, nanometer-scale technologies, prospects in electrosynthesis, new
instrumentation,surfacemodificationsinbasicresearchonchargetransfer,andrelated
interfacial reactivity. In this context, readers will notice that new methods that are
beingdevelopedforaspecificfieldmaybereadilyadaptedforapplicationinothers.
Electrochemistryhasbenefitedfromnumerousmonographsandreviewarticlesdue
toitsuniquecharacterandsignificanceinthepracticalworld(includingelectroanaly-
sis).Electrocatalysishasalsobeenthesubjectofindividualreviewsandcompilations.
TheWileySeries onElectrocatalysisandElectrochemistryisdedicated tobecomp-
lementarywithrespecttothecurrentactivitybyfocusingeachvolumeonaspecific
topic of choice. The chapters also demonstrate electrochemistry’s connections to
other areas of chemistry and physics, such as biochemistry, chemical engineering,
quantummechanics,chemicalphysics,surfacescience,andtobiology,andillustrate
the wide range of literature that each topic contains. While the title of each volume
informs of the specific focus chosen by the volume editors and chapterauthors, the
integraloutcomeoffersabroad-basedanalysisofthetotaldevelopment ofthefield.
The progress of the series will provide a global definition of what electrocatalysis
and electrochemistry are concerned with now and how they evolve with time.
vii
viii PREFACE TO THE WILEY SERIES ON ELECTROCATALYSIS AND ELECTROCHEMISTRY
Thepurposeismanifold,mainlytoprovideamodernreferenceforgraduateinstruc-
tionandforactiveresearchersinthetwodisciplines,aswellastodocumentthatelec-
trocatalysisandelectrochemistryaredynamicfieldsthatexpandrapidlyandlikewise
rapidlychangeintheirscientificprofiles.
Creationofeachvolumerequiredtheeditor’sinvolvement,vision,enthusiasm,and
time.TheSeriesEditorthanksallVolumeEditorswhograciouslyacceptedhisinvita-
tions.SpecialthanksareforMs.AnitaLekhwani,theSeriesAcquisitionEditor,who
extendedtheinvitationtotheSeriesEditorandisawonderfulhelpintheSeriesassem-
blingprocess.
ANDRZEJWIECKOWSKI
SeriesEditor
&PREFACE
The collection of chapters in this first volume of the “Electrocatalysis and
Electrochemistry” series originates from a workshop organized by Andrzej
Wieckowski, Jens Nørskov, and myself at the Lorentz Centerof Leiden University,
Leiden, The Netherlands, from October 16–20, 2006. The “Lorentz Workshop” on
“Fuel Cell Catalysis: A Surface Science Approach” (http://www.lorentzcenter.nl/
lc/web/2006/220/info.php3?wsid¼220)broughttogethersome70electrochemists
andfuelcellscientistsfromEurope,NorthAmericaandAsiatodiscussandidentify
majorresearchthemes inthe“surfacescience approach”tocatalytic reactionsatthe
solid–liquid interface relevant to fuel cells. Emphasis was on a molecular-level
description of catalysis for low-temperature polymer-electrolyte membrane fuel
cells, both hydrogen–oxygen fuel cells and direct alcohol fuel cells, based on well-
defined systems probed with state-of-the-art experimental and theoretical tools. The
Workshop in Leiden served as a continuation of two earlier workshops. The first
one, organized in Denmark in July 2003 by Wieckowski and Nørskov, was entitled
“Theory and Surface Measurements of Fuel Cell Catalysis.” That workshop was
oneofthefirstscientificmeetingsthatbroughttogetherexperimentalistsandtheore-
ticians to discuss molecular-level understanding of fuel cell reactions, and clearly
stimulated and identified some important research questions that are still reflected
in the current scientific literature. A second one-day workshop was organized by
Wieckowski in May 2005, as a satellite meeting to the Electrochemical Society
Meeting in Quebec City, Canada, and also provided a discussion forum dedicated
the interplay between theory and experiment in fuel cell catalysis. The idea for the
Leiden Fuel Cell Catalysis workshop was born in Quebec City, and finally materia-
lizedattheuniqueandspecialfacilitiesoftheLorentzCenteratLeidenUniversity.
The18chaptersinthisbookwerewrittenbyleadingexpertsinthefield,andaretoa
largeextentbasedonthepresentationsgivenbytheauthorsattheLorentzWorkshop.
The first chapter by Shimshon Gottesfeld, who was actually the last speaker at the
Workshop, gives an historical account of fuel cell catalysis, but also includes
the author’s reflections on some of issues discussed at the meeting, in particular in
relation to the oxygen reduction reaction. The rest of the book is divided into five
parts.Chapters2–5constitutethe“TheoryPart”ofthebook,discussingtheclassical,
quantum-mechanical, and statistical-mechanical aspects of the modeling of electro-
catalytic reactions, from Marcus theory and its various extensions to large-scale
first-principles quantum-chemical simulations based on Density Functional Theory.
Chapters 6–11give anexperimentalaccount of the suggested mechanismsof some
ix