Angew 2012 EtOH-Pt 氧化机理的理论计算.doc

Angew 2012 EtOH-Pt 氧化机理的理论计算 HeterogeneousCatalysis DOI:10.1002/anie.201104990 OriginofLowCO2SelectivityonPlatinumintheDirectEthanolFuelCell** RichardKavanagh,Xiao-MingCao,Wen-FengLin,*ChristopherHardacre,andP.Hu* Thedirectethanolfuelcell(DEFC)representsoneofthemostexcitingfuturecleanenergysolutionsinmodernresearch,becauseethanolcanbesustainablyproducedfrombiomass,isrelativelynontoxicand,mostimportantly,hasahighenergydensity.[1–8]Theexceptionalenergydensityisduetothetransferof12electronsfromethanolduringcompleteelectrochemicaloxidation(asopposedtosixelectronsfrommethanolortwofromhydrogen).ThepracticalityofsuchadeviceiscontingentonitsabilitytoselectivelycatalyzethetotaloxidationofethanoltoCO2.[9,10]However,theCO2selectivityinthecurrentethanolfuelcellsisverylow,andthemainproductsareaceticacid(resultinginthetransferofonlyfourelectrons)andacetaldehyde(onlytwoelectrons)inmostsystemsreported.[11–13]Herein,weaddresstheoriginoflowCO2selectivityintheDEFC,arguablythemostimportantquestiontobeansweredinthefield,usingfirst-principlescalculations. ThepioneeringworkonDEFCscanbetracedbacktothe1950s,[14]butitwasnotuntillaterthattheselectivitywascomprehensivelyinvestigatedwithIRspectroscopyshowingCO2tobeaminorproduct.[15]Behmandco-workers[1]performedathoroughinvestigationontheselectivityunderawiderangeofconditionsandemployingawiderangeofmorphologies,andtheyconvincinglyshowedthatplatinumcatalystsexhibitselectivitytowardsCO2intheregionof0.5–7.5%,whichisfarshortoftheselectivityneededforeconomicimplementationofthetechnology.Thisproblemhasprovendifficulttosurmountempirically.Recentworkhasmadesignificantprogressintermsofactivityandselectivity,[2]butfurtherimprovementsarerequired.Theoreticalstudieshavemadeconsiderableadvances[2,16–18]andidentifiedtheplatinummonoatomicstepasthemostlikelysitefortotalethanoloxidationandconcludedthattheclose-packedsurfacesareunsuitable.[17] Despitetheextensiveexperimentalandtheoreticalworkthathasbeencarriedout,theinhibitingfactorsinCO2formationremainun