Catalysis in electrochemistry : from fundamentals to strategies for fuel cell development

519 Pages·81.466 MB·English

by  Elizabeth Santos

CATALYSIS IN
ELECTROCHEMISTRY
WileySeriesonElectrocatalysisandElectrochemistry
AndrzejWieckowski,SeriesEditor
FuelCellCatalysis:ASurfaceScienceApproach,MarcT.M.Koper
ElectrochemistryofFunctionalSupramolecularSystems,MargheritaVenturi,Paola
Ceroni,andAlbertoCredi
Fuel Cell Science: Theory, Fundamentals, and Biocatalysis, Andrzej Wieckowski
andJensNørskov
CatalysisinElectrochemistry:FromFundamentalstoStrategiesforFuelCell
Development,ElizabethSantosandWolfgangSchmickler
CATALYSIS IN
ELECTROCHEMISTRY
FROM FUNDAMENTALS TO
STRATEGIES FOR FUEL CELL
DEVELOPMENT
Editedby
Elizabeth Santos
Wolfgang Schmickler
Copyright©2011JohnWiley&Sons,Inc.Allrightsreserved.
PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey
PublishedsimultaneouslyinCanada
Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformor
byanymeans,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptas
permittedunderSection107or108ofthe1976UnitedStatesCopyrightAct,withouteithertheprior
writtenpermissionofthePublisher,orauthorizationthroughpaymentoftheappropriateper-copyfeeto
theCopyrightClearanceCenter,Inc.,222RosewoodDrive,Danvers,MA01923,[phone],fax
[phone],oronthewebatwww.copyright.com.RequeststothePublisherforpermissionshould
beaddressedtothePermissionsDepartment,JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ
07030,[phone],fax[phone],oronlineathttp://www.wiley.com/go/permission.
LimitofLiability/DisclaimerofWarranty:Whilethepublisherandauthorhaveusedtheirbesteffortsin
preparingthisbook,theymakenorepresentationsorwarrantieswithrespecttotheaccuracyor
completenessofthecontentsofthisbookandspecificallydisclaimanyimpliedwarrantiesof
merchantabilityorfitnessforaparticularpurpose.Nowarrantymaybecreatedorextendedbysales
representativesorwrittensalesmaterials.Theadviceandstrategiescontainedhereinmaynotbesuitable
foryoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthepublishernor
authorshallbeliableforanylossofprofitoranyothercommercialdamages,includingbutnotlimitedto
special,incidental,consequential,orotherdamages.
Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactour
CustomerCareDepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)
572-3993orfax(317)572-4002.
Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmay
notbeavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteat
www.wiley.com.
LibraryofCongressCataloging-in-PublicationData:
Santos,Elizabeth
Catalysisinelectrochemistry:fromfundamentalstostrategiesforfuelcelldevelopment/editedby
ElizabethSantosandWolfgangSchmickler
p. cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-40690-8(cloth)
PrintedinSingapore
eBookISBN: 978-0-470-92941-4
oBookISBN:978-0-470-92942-1
ePubISBN: 978-0-470-93473-9
10 9 8 7 6 5 4 3 2 1
ToCristinaGiordanoandWolfVielstich,
OurMentorsandParentsinScience
E.S.andW.S.
CONTENTS
Preface ix
PrefacetotheWileySeriesonElectrocatalysisandElectrochemistry xi
Contributors xiii
1. VolcanoCurvesinElectrochemistry 1
RogerParsons
2. Electrocatalysis:ASurveyofFundamentalConcepts 17
AlejandroJorgeArvia,Agust´ınEduardoBolzán,andMiguelA´ngelPasquale
3. DynamicsandStabilityofSurfaceStructures 67
MargretGiesenandGuillermoBeltramo
4. ElectrocatalyticPropertiesofSteppedSurfaces 127
JuanM.Feliu´,EnriqueHerrero,andV´ıctorCliment
5. ComputationalChemistryAppliedtoReactionsin
Electrocatalysis 165
AxelGrossandSebastianSchnur
6. CatalysisofElectronTransferatMetalElectrodes 197
ElizabethSantosandWolfgangSchmickler
7. CombiningVibrationalSpectroscopyandDensityFunctional
TheoryforProbingElectrosorptionandElectrocatalyticReactions 223
MarcT.M.Koper
8. ElectrochemicalCatalysts:FromElectrocatalysisto
Bioelectrocatalysis 249
AlejandroJorgeArvia,Agust´ınEduardoBolza´n,andMiguelA´ngelPasquale
9. ElectrocatalysisatBimetallicSurfacesObtained
bySurfaceDecoration 297
HelmutBaltruschat,SiegfriedErnst,andNickyBogolowski
vii
viii CONTENTS
10. COAdsorptiononPlatinumElectrodes 339
ÁngelCuestaandClaudioGutiérrez
11. ExploringMetalOxides:ATheoreticalApproach 375
Mo´nicaCalatayudandFrederikTielens
12. ElectrocatalysisatLiquid–LiquidInterfaces 427
BinSu,HubertH.Girault,andZdeneˇkSamec
13. Platinum-BasedSupportedNanocatalystsforOxidationof
MethanolandEthanol 453
ErnestoR.Gonza´lez,EdsonA.Ticianelli,andErmeteAntolini
14. ImpactofElectrochemicalScienceonEnergyProblems 487
ElizabethSantosandWolfgangSchmickler
Index 499
PREFACE
By many, Professor Wolf Vielstich is con-
sideredtobethefatherofmodernfuelcell
research. His originally German textbook
Brennstoffelemente, which appeared in
1965,wasquicklytranslatedintoRussian,
English (Fuel Cells, Wiley, 1970), and
Spanish and is a classic. Even today, it
is an excellent source for the scientific
backgroundbehindelectrochemicalenergy
conversion.Intotal,ProfessorVielstichhas
been active in fuel cell research for more
than50years,andonlyafewyearsagohe
begantoedit,togetherwithA.Lamm,H.Yokokawa,andH.Gasteiger,theHandbook
ofFuelCells—Fundamentals,Technology,Applications,whoselastvolumeshavejust
beenpublished.WeinterviewedhimelectronicallyathishomeinSalta,Argentina.
INTERVIEWWITHWOLFVIELSTICH
Whatmadeyoubecomeinterestedinfuelcellsasearlyasthe1950s?
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,experimentsonhigh-temperatureFCswereinprogress,while
IworkedonalkalineH /O cellsatlowtemperatures.Then,inthe1960s,itwasa
2 2
goodideatochooseH /O cells,withliquidreactants,forelectricpowerandwater
2 2
supply (from the cell reaction) for the NASA Apollo programm. The Wernher von
Braunorganizationaskedmyadviceaboutintroducinga1-to2-kWFCunit,andI
suggestedDr.JoseGinerfromourElectrochemistryDepartmentatBonnUniversity
todothejob.Itwasasuccess,andNASAisstillusingthisalkalineFCtoday.
Sincethattimetherehasbeenanebbandflowinfuelcellactivities.Whatare
theperspectivesatpresent?
During the last 10 years, the automobile industry, including General Motors and
Daimler,hasbeenoptimisticaboutdevelopinganacid-typeH –airunitforapplication
2
inelectriccars.Butuptonow,costsofproductionarestilltoohigh,andinaddition
thesupplyofhydrogenintheformofgasorliquidisanunsolvedproblem.
ix
x PREFACE
Whatisthemostpromisingfuelforfuelcells:hydrogen,methanol,something
else?
WhilepowerdensityandenergycapacityaresatisfactoryinthecaseofH /O cells,
2 2
as has been demonstrated by their recent use in motorgliders (DLR-Motorsegler
Antares),thisisnotatallthecaseformethanolorethanol.
Atpresent,thereismuchactivityinfuelcellresearch.Whatarethechallenges
forfundamentalscienceinthisareatoday?
Nowadays, much fundamental fuel cell research is focused on the catalysis of
◦
methanolandethanoloxidationattemperaturesbelow80 C.Theoretically,withoxi-
−
dation to CO , methanol can deliver six e per molecule; at present, commercial
2
cellsdeliver250mAcm−2andacellvoltageof400mVat60◦C,andthesixe−per
moleculeisalmostattained.Butforapplicationinelectriccarsafactorofatleast4to
5inpowerdensitywouldbenecessary.Usingethanol,present-daycatalystsshowan
evenlowerenergydensitythanwithmethanolandoffernomorethan2–3electrons
permolecule,whilethecompleteoxidationtoCO involves12electrons.Acatalyst
2
breakingtheC–Cbondhasstilltobefound.
Thisyear,thefirstcommercialall-electriccars,heavilysubsidized,havebeen
marketedinJapan.Aretheyjustamarketinghypeoraretheyalreadyaviable
alternativetoconventionalcars?
All-electriccars,usingLiionbatteries,stillhaveaproblem.Duetothehighcosts,only
smallcarswithlimitedpowerandenergycapacityarebeingbuilt.Hybridsystems,
as produced by Toyota today, use only small battery sets; this makes sense in this
particularapplication.
Whatrolewillelectriccarsplayin20yearstime?Whichtechnologieswillthey
use:fuelcells,batteries,oracombinationofboth?
Withoutamarkedchangeintheavailabilityofgasand/oroil,evenin20yearstime
all-electric cars, using fuel cells or batteries, will make only a small contribution,
mainlyduetothehighproductioncosts.
E.Santos
W.Schmickler
PREFACE TO THE WILEY SERIES ON
ELECTROCATALYSIS AND ELECTROCHEMISTRY
TheWileySeriesonElectrocatalysisandElectrochemistrycoversrecentadvancesin
electrocatalysisandelectrochemistryanddepictsprospectsfortheircontributionto
theindustrialworld.Theseriesillustratesthetransitionofelectrochemicalsciences
from its beginnings in physical electrochemistry (covering mainly electron trans-
ferreactions,conceptsofelectrodepotentials,andstructureoftheelectricaldouble
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
interfacialspectroscopy.
The scope of this series ranges from electrocatalysis (practice, theory, relevance
to fuel cell science and technology) to electrochemical charge transfer reactions,
biocatalysisandphotoelectrochemistry.Whileindividualvolumesmayappearquite
diverse,theseriespromisesup-to-dateandsynergisticreportsoninsightstofurther
the understanding of properties of electrified solid/liquid systems. Readers of the
series will also find strong refernce to theoretical approaches for predicting elec-
trocatalytic reactivity by high-level theories such as DFT. Beyond the theoretical
perspective, further vehicles for growth are provided by the sound experimental
backgroundanddemonstrationofthesignificanceofsuchtopicsasenergystorage,
syntheses of catalytic materials via rational design, nanometer-scale technologies,
prospectsinelectrosynthesis,newresearchinstrumentation,surfacemodificationsin
basic research on charge transfer and related interfacial reactivity. In this context,
onemightnoticethatnewmethodsthatarebeingdevelopedforonespecificfieldare
readilyadaptedforapplicationinanother.
Electrochemistry has benefited from numerous monographs and review articles
duetoitsapplicabilityinthepracticalworld.Electrocatalysishasalsobeenthesub-
jectofindividualreviewsandcompilations.TheWileySeriesonElectrocatalysisand
Electrochemistryhopestoaddressthecurrentactivityinbothofthesecomplementary
fieldsbycontainingvolumesthatindividuallyfocusontopicsofcurrentandpoten-
tial 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 sci-
ence,biochemistry,andbiology,andtherebybringtogetheravastrangeofliterature
thatcoverseachtopic.Whilethetitleofeachvolumeinformsofthespecificconcen-
trationchosenbythevolumeeditorsandchapterauthors,theintegraloutcomeofthe
series aims is to offer a broad-based analysis of the total development of the field.
xi