OAu(111)表面水活化氧化CO机理的密度泛函研究

2009年第54卷第8期:1150~1153www.scichina.comcsb.scichina.comSCIENCEINCHINAPRESSO/Au(111)CO,,*(),,230036;DepartmentofTheoreticalChemistry,SchoolofBiotechnology,RoyalInstituteofTechnology,S-10691Stockholm,Sweden*,E-mail:[e-mail]2008-11-15,2008-12-11(:50721091,20533030,50731160010)(:2006CB922004)-AuCO.,OHads;OHadsCOadsHOCOads;HOCOadsCO2.1/2H2Oads+H2Oads+1/2Oads+COads→H3Oads+CO2,gas,1/2CO2,H2O,CO2Oads.,,.COAu(111),CO[1~5].,CO3,ads[1,2].AgAuAuCO,,[6,7].,,.,Mullins[8,9]Au(111)CO,,77KCOCO2,CO.,,CO.,,CO2,CO.CH2O,HCOOH,H.[9],Mullins:COgas→COadsH2Ogas→H2OadsH2Oads+Oads→2OHadsCOads+OHads→HOCOadsHOCOads→CO2,gas+Hads2Hads→H2,gasOHadsOadsHOCOadsCO2,OHadsOads.,Wang[10],Au(111)2.24eV,OHadsOads.HOCOads,OHads,CO2.[9]0.93eV,.,Oads,Hads,OHads,H2Oads,COads,HOCOadsCO2,gas,..H,H.HOCOads,H.,:,,.O/Au(111)CO.,2009,54(8):1150~1153ZhangWH,LiZY,LuoY,etal.DensityfunctionalstudyonmechanismofCOoxidationwithactivatedwateronO/Au(111)surface.ChineseSciBull,2009,54(11):1973―1977,doi:10.1007/s11434-009-0057-y,HOCOadsH2OCO2,gasOH3,ads.DMol3[11,12],,GGA-PBE[13],DSPP.0.001hartree(1hartree=110.510−2J),4.0Å,,(33)k.(33)AuslabAu,,.,LST/QST[14].(Eads=(Emol+Esurf)−Emol+surf)1.Au(111)[15],fcc-hollow,2.69eV,OAu2.16Å.Au,0.11(ML)0.11eV,.Oads,,0.25eV.COAuC,atop.CO,0.25eV,0.15eV.OHO,(1(a)),0.2eV.HOCOadsCO,,trans-HOCO(1(b))cis-HOCO(1(c)).Pt(111),trans-.Au,cis-,,trans-,.OH3H3Au(1(d)).,,,OH,Ofcc,COatop,0.11ML.,:H2O+Oads→2OHadsCOads+OHads→HOCOadsHOCOads→CO2,gas+HadsHOCOads+Oads→CO2,gas+OHadsHOCOads+OHads→CO2,gas+H2OadsHOCOads+H2Oads→CO2,gas+H3Oads……COOadsCO20.39eV,77K[7].2,(TS),CO,COads2.40Å,∠OCO116°.0.25ML[6,9].,[15],COCOO,O,.Au,H.0.33eV,HOH.,Ofcc,OadsHO,OadsH1.17Å,.1a)/eV/Å/Å/Å/(°)/cm−1O(fcc)2.69O-fcc−2.16−−H2O0.11freely−−−CO(atop)0.25C-atop1.142.0202084CO(fcc)0.14C-fcc1.172.2301837CO(hcp)0.11C-hcp1.172.2501846OH(bridge)1.74O-bridge0.962.26623845OH(fcc)1.67O-fcc0.962.3003876OH(hcp)1.54O-hcp0.962.3203882cis-1.45C-atop0.972.071233689trans-1.42C-atop0.972.111233609H(fcc)2.30H-fcc−1.89−−OH33.01H-3-atop1.022.02−297426852560a),COOHHOCOOH,Au.,HOCO∠OCO..HOCOcis-trans-11512009年4月第54卷第8期0.21eV,.,1OH,OH,.OHCOHOCOadsMullins[9],2OH+CO→CO2+H2O0.11eV.,OH,[16].:COOHadsHOCOads,HOCOads.Mullins,cis-,0.32eV;trans-,,0.44eV[9],0.93eV.,trans-,,trans-.COOHtrans-HOCO0.44eV(3),trans-HOCO0.98eV(4),0.93eV[9]1.02eV[16].,.,trans-HOCOOadsOHads,trans-HOCO,cis-HOCOOH0.28eV[9],cis-HOCO,trans-HOCO..trans-HOCOadsH2O(5).,HOCOadsHH,HOCOadsOH,0.99Å.HOH3CO2,.2.0.41eV,.HCO20.3eV.OH3,,Oads,OHads.HOCOads6.,:1/2H2Oads+1/2Oads+CO+H2Oads→CO2,gas+H3Oads0.44eV.,CO21OH(a)trans-HOCO(b)cis-HOCO(c)OH3(d)Au(111)Au,C,OH2CO+O→CO2(IS)(TS)(FS)3CO+OH→HOCO(IS)(TS)(FS)4HOCO→CO2+H(IS)(TS)(FS)5HOCO+H2O→CO2+H3O(IS)(TS)(FS)6CO2,.11522trans-HOCOa)dH-Ow/ÅdH-Oc/ÅdH1-Au/ÅdH2-Au/Å∠OCOc/(°)1.660.993.163.261241.091.312.622.561440.981.802.072.14178a)d,H,H1,H2,OwOc5.(IR)(HREELS).,1.Trans-cis-HOCOOH36093689cm−1,.,OH3,3HH2O,,CO.Au(111)CO,,.:(1),CO0.39eV.(2),H,H0.25eV.OH2OOH0.33eV.(3)CO+OH→trans-HOCO0.44eV.trans-cis-0.05eV.trans-HOCOads0.98eV,.OHtrans-HOCOads,CO2.H2Otrans-HOCOads0.41eV,H3O.,H3O,CO2,CO2.,,.1DateM,OkumuraM,TsubotaS,etal.Vitalroleofmoistureincatalyticactivityofsupportedgoldnanoparticles.AngewChem-IntEdit,2004,43:2129—2132[doi]2BoccuzziF,ChiorinoA.FTIRstudyofCOoxidationonAu/TiO2at90Kandroomtemperature.Aninsightintothenatureofthereactioncenters.JPhysChemB,2000,104:5414—5416[doi]3HaydenBE,RendallME,SouthO.Electro-oxidationofcarbonmonoxideonwell-orderedPt(111)/Snsurfacealloys.JAmChemSoc,2003125:7738—7742[doi]4LeiT,ZeiMS,ErtlG.ElectrocatalyticoxidationofCOonPt-modifiedRu(0001)electrodes.SurfSci,2005,581:142—154[doi]5BergeldJ,KasemoB,ChakarovDV.COoxidationonPt(111)promotedbycoadsorbedH2O.SurfSci,2001,495:L815—L820[doi]6SuHY,YangMM,BaoXH,etal.TheeffectofwaterontheCOoxidationonAg(111)andAu(111)surfaces:AFirst-Principlestudy.JPhysChemC,2008,112:17303—17310[doi]7BongiornoA,LandmanU.Water-enhancedcatalysisofCOoxidationonfreeandsupportedgoldnanoclusters.PhysRevLett,2005,95:106102—106105[doi]8KimTS,GongJL,OjifinniRA,etal.WateractivatedbyatomicoxygenonAu(111)tooxidizeCOatlowtemperature.JAmChemSoc,2006,128:6282—6283[doi]9OjifininiRA,FroemmingNS,GongJL,etal.Water-enhancedlow-temperatureCOoxidationandisotopeeffectsonatomicoxy-gen-coveredAu(111).JAmChemSoc,2008,130:6801—6812[doi]10WangGC,TaoSX,BuXH.Asystematictheoreticalstudyofwaterdissociationoncleanandoxygen-preadsorbedtransitionmetals.JCatal,2006,244:10—16[doi]11DelleyB.Anall-electronnumericalmethodforsolvingthelocaldensityfunctionalforpolyatomicmolecules.JChemPhys1990,92:508[doi]12DelleyB.FrommoleculestosolidswiththeDMol3approach.JChemPhys,2000,113:7756—7764[doi]13PerdewJP,BurkeK,ErnzerhofM.Generalizedgradientapproximationmadesimple.PhysRevLett,1996,77:3865—3868[doi]14GovindN,PetersenM,GitzgeraldG,etal.Ageneralizedsynchronoustransitmethodfortransitionstatelocation.CompMaterSci,2003,28:250—258[doi]15ZhangWH,LiZY,LuoY,etal.Afirst-principlesstudyofNOadsorptionandoxidationonAu(111)surface.JChemPhys,2008,129:134708—134712[doi]16GongXQ,HuP.ThecatalyticroleofwaterinCOoxidation.JChemPhys,