ABO3钙钛矿型复合氧化物光催化剂设计评述

20062511CHEMICALINDUSTRYANDENGINEERINGPROGRESS·1309·ABO3100022ABO3512B3A4A/B5ABO3O643A10006613200611130905ReviewofdesigningABO3perovskitephotocatalystsLIHonghuaWANGHaoYANHui(SchoolofMaterialsScienceandEngineeringBeijingUniversityofTechnologyBeijing100022China)AbstractThemainstrategiesofdesigningABO3perovskitecatalystswerereviewed.Theemphasiswasputon(1)Selectionandtuningofthebandstructure(2)SelectionofB-siteelementswhichprincipallydeterminedthephotocatalyticactivity(3)SelectionofA-siteelements(4)ValencyandvacancycontrolsbypartialsubstitutionofA-siteor/B-siteelementswhichcouldextremelyimprovethephotocatalyticactivityand(5)Enhancementofsurfaceareabyformingfineparticlesordispersingonsupportswhichcouldalsoenhancephotocatalyticactivity.KeywordsABO3;perovskite;photocatalysts;designABO3A12B6ABA1-xA′xB1-yByO31234ABA1+B5+O3A2+B4+O3A3+B3+O3ABABOAABO3512B3A451ABO32p2006052220060905H013610060112(1969)[e-mail]200625·1310·B3d∆CT∆CTd(egt2g)2p3eg2t2g∆CF∆CF∆CT[12]Sarma[3]LaBO3∆CT∆CF1LaBO3BO−96B=TiNi1dN3eg2t2g2p1t1g4t1u1t2u2eg3a1g3t1u1t2g012345678Ei/eV3eg2t2g1t2u2eg3a1g3t1u1t2g1t1g4t1uTiO96−VO96−CrO96−MnO96−FeO96−CoO96−NiO96−1BO96−B=TiNi[34]∆CT|E2t2g-E1t1g|[5][6]Yin[7]MIn0.5Nb0.5O3M=CaSrBaBaZn1/3Nb1/3O3In3+Nb5+Zn2+Nb5+B2pIn5sZn4s[78]MCo1/3Nb2/3O3M=CaSrBaCo2+3dNb5+4dCo2+O2p2.82.26eV[9]2BaCo1/3Nb2/3O3SrCo1/3Nb2/3O3CaCo1/3Nb2/3O3Nb4dNb4dNb4dCo3dx2y2Co3dz2Co3dxyCo3dyzCo3dxzegt2g2.77eV2.47eV2.27eVCoegCot2gCoegCot2gO2pO2pO2p0V1.23V+2CaCo1/3Nb2/3O3SrCo1/3Nb2/3O3BaCo1/3Nb2/3O3[9]11ABO3·1311·2BAB[10]BLaBO3BdLaBO3BABO32.1B1LaBO3B=CrMnFeCoB3+1LaBO3B3+LaCrO3LaMnO3LaFeO3LaCoO3B3+/nm0.0720.0700.0630.0610.8850.8990.9080.95014B3+CrMnFeCoLaCrO3LaMnO3LaFeO3LaCoO3LaBO3B3dBBBOVo••LaBO3CrCo2.2Bd2LaBO3Bd2LaBO3DBdLaBO3LaTiO3LaVO3LaCrO3LaMnO3LaFeO3LaCoO3D/%6.98.448.471.498.1B(3dn)d1d2d3d4d5d6dt12ge0gt22ge0gt32ge0gt32ge1gt32ge2gt512g±e11g∓LaVO3V2O52BdLaBO3B5degt2gBO6Bdd22B3ddddnABO3Bddn3eg2t2g∆CT2.3B[11]ABO3ABO3.5BCr(1.56)Mn(1.60)Fe(1.64)Co(1.70)[12]LaMnO3LaCoO3-LaBO3LaMnO3LaCrO3LaFeO3LaCoO3ABO3BBBBddBd3AAAAAYin[7]MIn0.5Nb0.5O3M=CaSrBaAH2CaIn0.5Nb0.5O3SrIn0.5Nb0.5O3BaIn0.5Nb0.5O3AARFeO3R=SmEuGd200625·1312·[13]3SmFeO3EuFeO3GdFeO334f4f54f64f7GdFeO3Gd3K2Ln2Ti3O10[14]R4fB-OR4f3SmFeO3EuFeO3andGdFeO3/%KGLKGRX-3BK3NSmFeO349.055.897.497.6EuFeO368.872.996.497.9GdFeO374.979.996.598.2AB4A/BBa1-xSrxTiO3BaTi1-xSnxO3PbTi1-xZrxO3BO312ABBLa1-xSrxCoO3SrACoCo(1)La+−31xSr+2xCo+−31xCo+4xO3La+−31xSr+2xCo++−321δxCo+−42δxO3+2δO2(1)(1)LaCoO3SrLaCoO3La1-xCexCoO3CeAACo[15]LaNiO3LaBflexibleLa1-xAxMnO3+δδSrBaKCs[16]MiyauchiWang[1718]SrTiO3ON2-NOKato[19]LaNiO-NaTaO39270nm56%[10]LaFeO3ASr2+BCu2+LaFeO3Cu2+(Sr2+)LaFeO3Fe3+(La3+)Cu2+Fe3+(Sr2+La3+)LaFeO3EgLaFeO3EgLaFeO3LaFeO3ASr2+BLaFeO3Sr2+Fe4+LaFeO3LaFeO351073K(10m2/g)--[20]50m2/g[21]11ABO3·1313·Yin[22]sol-gel750BaCo1/3Nb2/3O330nm19.7m2/g2.2m2/gPtsol-gelCH3OH/H2OH218.1µmol/(h·g)3.5µmol/(h·g)[2325]LaCoO3CoAl3O3La-Co/ZrO21123KLaCoO3ZrO21123KLa-CoZrO2La2Zr2O7Co3O46ABO3ABO3[1]PariGMathiJayaSSubramoniamGetal.Density-functionaldescriptionoftheelectronicstructureofLaM03(M=ScTiVCrMnFeCoNi)[J].Phys.Rev.B1995511657516581.[2]ArimaTTokuraYTottanceJB.Variationofopticalgapsinperovskite-type3dtransition-metaloxides[J].Phys.Rev.B199348(23)1700617009.[3]SarmaDDSantraAKRaoCNR.ElectronicstructuresofpervoskiteoxidesoftransitionmetalsofthetypeLaMO3(M=Ti-Ni)asrevealedbyMSXAinvestigations[J].J.SolidStateChem.1994110393396.[4]SarmaDDChainaniA.Electronic-structureofperovskiteoxidesLaMO3(M=Ti-Ni)fromhigh-energyelectronspectroscopicinvestigations[J].J.SolidStateChem.1994111(1)208–216.[5]GerischerHHellerA.Theroleofoxygeninphotooxidationoforganic-moleculesonsemiconductorparticles[J].J.Phys.Chem.199295(13)52615267.[6].--[M].1987408.[7]YinJZouZYeJ.PhotophysicalandphotocatalyticpropertiesofMIn0.5Nb0.5O3(M=CaSrandBa)[J].J.Phys.Chem.B2003107(1)6165.[8]YinJZouZYeJ.PhotophysicalandphotocatalyticactivitiesofanovelphotocatalystBaZn1/3Nb2/3O3[J].J.Phys.Chem.B2004108(34)1279012794.[9]YinJZouZYeJ.Anovelseriesofthenewvisible–light–drivenphotocatalystsMCo1/3Nb2/3O3(M=CaSrandBa)withspecialelectronicstructures[J].J.Phys.Chem.B2003107(21)49364941.[10].ABO3[D].2002.[11]HuheeyJHKeiterEAKeiterRL.Inorganicchemistryprinciplesofstructureandreactivity[M].NewYorkHarperCollins1993171.[12]PaulingLPaulingP.Chemistry[M].1975175.[13]NiuXSLiHHLiuGG.PreparationcharacterizationandphotocatalyticpropertiesREFeO3(RE=SmEuGd)[J].J.Mol.Catal.AChem.2005232(12)8993.[14]ZhangLZhangWGZhuJWetal.RapidsynthesisofultratineK2Ln2Ti3O10(Ln=LaNdSmGdDy)seriesanditsphotoactivity[J].J.SolidStateChem.2005178(3)761768.[15]NitadoriTMisonoM.CatalyticpropertiesofLa1−xA′xFeO3(A′=SrCe)andLa1−xCexCoO3[J].J.Catal.198593459–466.[16]BuciumanFCPatcasFZsakJ.TPR–studyofsubstitutioneffectsonreducibilityandoxidativenon–stoichiometryofLa0.8A'0.2MnO3+δperovskites[J].J.ThermalAnal.Calorimetry200061(3)819825.[17]MiyauchiMTakashioMTobimatsuH.PhotocatalyticactivityofSrTiO3codopedwithnitrogenandlanthanumundervisiblelightillumination[J].Langmuir200420(1)232236.[18]WangJYinSKomatsuMZhangQSaitoFSatoT.Photo–oxida