TiO2光催化反应及其在废水处理中的应用

:199712,:199823,33TiO2333(430072)TiO2,CO2H2OTiO2,,,,TiO2TiO2TiO2-BasedPhotocatalysisandItsApplicationsforWasteWaterTreatmentShenWeirenZhaoWenkuanHeFeiFangYouling(DepartmentofChemistry,WuhanUniversity,Wuhan430072,China)AbstractTiO22basedheterogeneousphotocatalysishasthepotentialtodegradeenvironmentalpollutantsbysolarenergy.ThecontaminantscanbemineralizedtoCO2,H2Oandothersmallmolecules.ThepaperdealswiththeprincipleandmechanismofphotocatalysisonTiO2,thewaysforenhancingphotocatalyticefficiency,andthemethodsandproblemsofTiO2photocatalysisfordegradationsofseveraltypicalcontaminants.TherecentdevelopmentsinTiO2photocatalysisanditsapplicationprospectsforthetreatmentofwastewaterareintroduced.KeywordsTiO2;heterogeneousphotocatalysis;degradation;wastewatertreatment1972FujishimaHonda[1]TiO2,,,,[27],,TiO2TiO2(3.2eV),104199812PROGRESSINCHEMISTRYVol.10No.4Dec.,1998©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.3%,,,,,,,[48],,,,,,TiO2TiO211,(valenceband,VB)(conductionband,CB),(,Eg),(e-),(h+),,,,,:TiO2+H2Oe-+h+h++H2OOH+H+h++OH-OHO2+e-O2-,O2-+H+HO22HO2O2+H2O2H2O2+O2-OH+OH-+O2,,OH-H2O[9],;;,[10,11][12][2],21KgEg,[13]:Kg(nm)=1240Eg(eV),TiO2pH13.2eV,387nm,();(),05310©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.31,,,(),,,TiO2:,TiO211(1)TiO2,[3]TiO6,1,Ti4+6O2-,;,TiTi(3.79~,3.04~)(3.57~,3.96~),Ti-O(1.934~,1.980~)(1.949~,1.980~)10(,),8(,)(3.894gcm-3)(4.250gcm-3),(3.3eV)(3.1eV)TiO2O2,,,(2),,,,,a=4.593~c=2.959~Eg=3.1eVQ=4.250gcm-3$G0f=-212.6kcalmole-11TiO2a=3.784~c=9.515~Eg=3.3eVQ=3.894gcm-3$G0f=-211.4kcalmole-11534TiO2©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.Salvador[14]TiO2(001),Ti3+2Vo-Ti3+H2OH2O2,Ti3+-Ti3+(2.59~)Ti4+-Ti4+(4.59~),,52(3)TiO2(H2O,O2)TiO2,TiO2H2O(OH)O2,,[15]TiO2,TiO2(110),Yamashita[17]TiO2(110)TiO2(100),CO2H2O,TiO2(100)TiO2(110),TiO2(100),TiO2(110),TiO2(100),TiO2(100)TiO(TiO)TiO2(110),,,CO2H2O,;,TiO2(110),TiO2(110)Sanjines[16],TiO2(101)21TiO2,,TiO2,TiO2(1),,,,,,,,,,,TiO2,,(2),,,,(3)DegussaP225TiO2,TiO2()Bickley[18],,(),,,,,25310©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,TiO2(4.0m2g-1),2(5.8m2g-1),,,31TiO2,TiO2(),TiO2:Ti(OR)4TiX4Ti(OH)4TiO(OH)2TiO2,(TiCl4)TiO2DegussaP225TiO2,70%30%,50m2g-1,,20nm,,,,,[19],(300)TiO212nm,100m2g-1,700,(37m2g-1),,,DegussaP225TiO2,,DegussaP225TiO22TiO2(),,,2,,,,2,,,,Kisler,[20],,2030,,,,,,,CO2,CO2,,Dagan[21]TiO285%,600m2g-1,0.5gcm-3X50~,DegussaP225TiO2TiO2,,[4],,TiO2,,,TiO23534TiO2©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.400nm,,2,,,11(1)TiO2:(),Pt[22,23],Ag[24]Ir[25]Au[26]Ru[27]Pd[28](2),,Fe3+,Litter[29]Fe3+TiO2Choi[30]21TiO2,,0.1%0.5%Fe3+Mo5+Ru3+Os3+Re5+V4+Rh3+,Co3+Al3+,,,,(),,,[31],TiO2,(600nm)(3)22Al2O3[32]SiO2[33]ZrO2[34]TiO2,,,,,,,,TiO2CdS,CdSTiO2,CdSTiO2,CdS,2,TiO2,CdS,,CdSTiO2[34]TiO2CdSe[35]ZnOTiO2[36]TiO2SnO2[37]TiO2PbS[38]TiO2WO3[38],(4),,,B[39][40]Ru(byp)32+[41][42],,,,,2(5)Uchihana[43],OH-EDTA,22,TiO2PtTiO22.3[44]45310©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.2,Fox[2]Linsebigler[3][45]21TiO2(Q-TiO2),,,,,1-10nm,,,,22,Q2TiO2,,[46](Nafion)[47],Uchida[48](PVPD)Q2TiO2,TiO2,,,11TiO2,,,,,,,TiO2(0.5mgcm-3),(batchreactor)Mills[49]NDC21,,,,:(1)2TiO2[50,51];(2)(),400600[52,53];(3)TiO2,TiO2[5456];(4)TiO2,[57];(5)TiO2[58]sol2gel,,5534TiO2©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.[59][60],,,,,,,,31TiO2TiO2,TiO2,Sopyan[61],TiO2,,120,,,,Kim[50]TiO2,,,TiO2,,,Vinodgopal[62]TiO242TiO2,,H2OCO2PO43-SO42-NO3-,,,TiO211(1),,[6368][67],,95%(2)Klopffer[69],,s2,110-7,,,[70],[71]TiO2,PO3-4,CODCr70%-90%,(3),,[75][76](NPE2n),Hidaka[7780],,,Pelizzetti[81],,,65310©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.TiO2TiO22226GTiO2SiO251,B,TiO256TiO2,WO363,GTiO264,1TiO265(7),TiO266HTiO268atrazineTiO2,ZnO70(DDT)TiO2,TiO2Pt72,2,4,52TiO273(DDVP),(DTHP)TiO274TiO271()TiO2,TiO277,78()TiO279()TiO276,80TiO281TiO2SiO259,60TiO2Ni215,TiO28242TiO26222,2,72TiO2,TiO2Pt83,84,85,3,32,TiO286CFC113(CCl2FCClF2)TiO287,88,TiO2,SiO2,TiO2Al2O391TiO289,90TiO292TiO293TiO294,95CN-TiO299,101Au(CN)4-H2O2TiO2100I-,SCN-TiO2SnO237Cr2O2-7TiO2,ZnOTiO299-101Hg,CH3HgClTiO2()1027534TiO2©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,CO2,,,,,(4),,,,,[82][82]42[49,62][8385](5)(CFCs),,,,,[87,88]Takita[87]TiO2CCl2FCClF2(CFC113)Kanno[88]TiO2CFC113TiO2WO3,,,TiO2WO3CFC113,100h99.6%,,[89][90]CO2HF(6),,,TiO2,,,TiO2TiO2Berry[92]TiO2[93]TiO2,TiO2,,,,2TiO2[94],TiO2,Heller[95]100LmTiO2,TiO2,,,21,TiO2,Cr2O2-7,1977Miyaka[96]TiO2,Cr2O2-7Cr3+Yoneyama[97]Cr2O2-7[98]ZnOTiO2,Frank[99]TiO2CN-OCN-,CO2N2NO-3Serpone[100]TiO2Au(CN)-4Au,CN-NH3CO2,,,,Hidaka[101]OCN-CO2N285310©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,,TiO2,,,,,,,,[103],,,,[103,104],,,TiO2,[1]FujishimaA,HondaK,Nature,1972,238(5358),3738.[2]FoxMA,DulayMY,Chem.Rev.,1993,93(1),341357.[3]LinsebiglerAL,LuG,YatesJT,Chem.Rev.,1995,95(3),735758.[4]HoffmannMR,MartinST,ChoiWetal.,Chem.Rev.,1995,95(1),6996.[5],,1993,11(2),7681.[6],,,,1994,2(3),5057.[7],,,,1996,4(3),118.[8]OllisDF,PelizzettiE,SerponsN,Environ.Sci.T