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©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(400044;#639798),40,,,E2mail:zdwei@cqu.edu.cn2003202217,2003205215;CO,,MechanismofMethanolOxidationonElectrocatalystsWeiZidong,LiLanlan,LiLi,ChanSiewhwa#(SchoolofChemicalEngineering,ChongqingUniversity,Chongqing400044,China;#FuelCellResearchStrategic,NanyangTechnologicalUniversity,50NanyangAvenue639798,Singapore)AbstractItissignificanttoclarifythemechanismofmethanolelectroxidationfordeveloppingthecatalystswithahighefficiency.Thispaperprovidesabriefdescriptionofmechanismofmethanolelec2tro2oxidationonPt,catalystpoisoningandthedevelopmentofCO2resistantcatalysts.Emphasisislaidontheinfluenceofsurfacestructure,compositionofcatalystandelectrodepotentialoncatalysisactivity.Thereisalargeroomleftinthedevelopmentofbettercatalysts.Fundamentalresearchisindispensabletoavoidapurelyempiricalapproach,whichisawayoftime2consumingandenergy2consuming,insearchingforthebettercatalyst.KeywordsMethanoloxidation,Catalyst,DMFCH22O2,(DMFC),,,,,,DMFC,,,CO,CO2:CH3OHCOads+4H++4e-+H2OCO2+6H++6e9http:öö©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(100K),:()180K;140K[25][2,5],,,200300K,COH[2],öBagotzky:,,,(HCO),GasteigerRu,Gasteiger[6]ö,,CO,,10(at)%,,COCO,,,C3V[7],HCOPt(110)2(12)OH(CH3O)[8,9]Pt(110)2(12),COH(HCO)[10],Bagotzky,ö;,,,,,,[11],,,,[12],,;,,PtH,,,,,,[13],Pt(610)Pt(310)Pt(210)[14]Pt(331)Pt(332)[15](110),Pt(110),,,,,0120041http:öö©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(),()[16]2COads(,COPt0.851.0COöPt)[17],,COPtR2P[18]PtdPCO2P3,CORPtdPCO2P3,CORPt,Pt,PtHOMOCO2P3(Pt),,CO,CO,,:(110)(100)(111)[19]Pt(100)Pt(111),CO1;Pt(110),0.96:,,,CO;,CO,3DMFC,CO:;COO2H2O2CO,,COCOCO,:;:Pt,,LawrenceBerkelyPt2Ru[20],PtPt2RuCOLangmuir2Hinshelwood:PtCOads+RuOHadsCO2+H++e-Ru+H2OOHads+H++e-COads+OHadsCO2+H++e-0.20.25V,0.5V,,0.20.3V,0.25V[5,21,22],Anderson[23]42(:ScSe;:YTe;:LaPo)Pt42PtOHads:OHads,Sn,Anderson[23],Pt2Ru,,11http:öö©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.öLHClO4()011molöLHClO410-6molöLSn2+()Fig.1CyclicvoltammogramsofapurePtin0.1molöLHClO4(solidline)andin0.1molöLHClO4with10-6molöLSn2+(dashedline)at50mVösPt2SnSnOHads[12],,Pt2SnPt2RuPt2Sn[24]:SnPt;,Ptupd2Sn,,1,,Sn(SnO,SnOH)(PtO,PtOH);(),upd2Sn,0.35V,CO;0.35V,SnOH,COCO22,Pt2Ru,Ru,RuOH,RuOH0.05V,0.25V,SnOH,0.10V,Pt2RuPt2Sn,RuSn,SnPtLee[25]Pt2SnPt2RuCO:CO,CO,COMorimoto[26]COPtPt2RuPt2SnPt2Sn2Ru,COPt(0.5V);(0.60.8V)Pt2Ru,CO012V;Pt2Sn,,,CO,Pt2SnCOGotz[27]Pt2MoGrgur[28]MoOOH(MoMoO(OH)2),PtCOPtMoRuAnderson,Pt2MoPt2CrPt2AuPt2IrPt2ZnPtCO,CO,Pt,,CO,Pt,Pt2Ru2Sn2W[29]Pt2Ru2Sn2WöC[30]Pt2Ru2Os[31]Pt2Cr2Cu[32],,Pt2WO3,W2120041http:öö©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(),Pt10%Ru()Pt40%Ru()N2015molöLH2SO4Fig.2CyclicvoltammetriccurvesofelectrodesinN2-saturated015molöLH2SO4atasweeprateof100mVös.ThecurvescorrespondtoelectrodesmadefromNafion-bondedcarboncatalyzedbyelectro-chemicaldepositionofPt(boldsolidline),Pt10%Ru(thinsolidline)andPt40%Ru(dottedline),re-spectively.Theloadingofmetalcatalystsis80Lgöcm2caforall.VoltagevaluereferstosaturatedpotassiumchlorideAgClöAg100mVös;:AgClöAgWO3WOH,WO3WO3,PtWOx,,WO3Hx2WO3,COads,OHads,COads4,,(IR,Raman,UVöVis)(AES,LEED,XPS,SPM),,,,,,,[1]WVielstich,XHXia.J.Phys.Chem.,1995,99:10421.[2]NKizhakevariam,EMStuve,Surf.Sci.,1993,286:246.[3]GAAttard,KChibane,HDEbertetal.Surf.Sci.,1989,224:311.[4]DHEhlers,ASpitzer,HDEbertetal.Surf.Sci.,1985,160:57.[5]BASexton.Surf.Sci.,1981,102:271.[6]HGasteiger,NMarkovic,PRossetal.J.Phys.Chem.,1993,97:12020.[7]SWasmus,AKver.J.Electroanal.Chem.,1999,461:1431.[8]JWang,RIMasel,Surf.Sci.1991,235:199.[9]JWang,RIMasel.J.Vac.Sci.Tech.,1991,A9:1987.[10]KFranaszczuk,EHerrero,PZelenayetal.J.Phys.Chem.,1992,96:8509.[11]ZDWei,HTGuo,ZYTang.J.PowerSource,1996,58:239.[12].,:2003.[13].,1998,(4):88.[14],JClevilier.,1990,(11):998.[15]SGSun,ACChen,TSHuangetal.J.Electroanal.Chem.,1992,340:213.[16],.:,2000.[17]LJacek,NRPhilip.Electrocatalysis.NewYork:Wiley2VCH,Inc,1998.[18],,.,1993,38:2252.[19]EHerrero,KFranasczuk,AWeichowski.J.Phys.Chem.,1994,98:5074.[20]HGasteiger,NMarkovic,PRoss.Phys.Chem.,1995,99:8290.31http:öö©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[21]ABAnderson,EGrantscharora,PShiller.J.Electrochem.Soc.,1995,142:1880[22]JSobkowski,KFranaszczuk,APiasecki.J.Electroanal.Chem.,1985,196:145156.[23]ABAnderson,EGrantscharora,SSeong.J.Electrochem.Soc.,1996,143:2075.[24],,.,2002,18(12):1120.[25]SJLee,SMukerjee,EATicianellietal.ElectrochimicaActa,1999,44:3283.[26]YMorimoto,BErnest.Yeager.J.Electroanal.Chem.,1998,441:77.[27]PKShen,ACCTseung.J.Electrochem.Soc.,1994;141:3082.[28]BNGrgur,NMMarkovic,PNRoss.J.Phys.Chem.,1998,102,2494.[29]ASAric,ZPoltarzewski,HKimetal.J.PowerSource,1995,55:159.[30]ASAric,PCreti,NGiordanoetal.J.Appl.Electroc