半导体多相光催化应用研究进展韩兆慧

　:19982,:19984*半导体多相光催化应用研究进展韩兆慧　赵化侨*(中国科学技术大学应用化学系　合肥230026)　　本文综述了半导体多相光催化应用研究现状,对有代表性的光催化剂和新型反应装置作了介绍,阐述与评价了光催化在环境保护、卫生保健、金属催化剂制备、贵金属回收与物质合成等几个主要方面的应用研究成果,并对今后工作的重点提出了一些意见。　半导体　光催化　TiO2ProgressinAppliedResearchoftheHeterogeneousPhotocatalysisonSemiconductorsHanZhaohui　ZhaoHuaqiao(DepartmentofAppliedChemistry,UniversityofScienceandTechnologyofChina,Hefei230026,China)Abstract　Thispaperdescribestherecentappliedresearchprogressoftheheterogeneousphotocatalysisonsemiconductors.Representativephotocatalystsandnewphotoreactorsareintroduced.Theapplicationsofphotocatalysisonenvironmentalprotection,medicalandhealthcare,preparationofmetalliccatalysts,raremetalrecoveryandmaterialsynthesisaresummarizedandassessed.Moreover,theopinionsonfurtherstudiesarepresented.Keywords　semiconductors;photocatalysis;TiO2、　20。,。,。,。[1],Ollis[2]TiO2、、,。,Hoffmann[3]。,11119992化　学　进　展PROGRESSINCHEMISTRYVol.11No.1Feb.,1999,,。,,,、、。,Tennakone,[4]。,。、(e-)(h+),。TiO2,(1)e-h+,[5]。(2)—(11),TiO2hνe-+h+(1)h++H2OH++·OH(2)H++e-·H(3)e-+O2·O-2(4)·O-2+H+HO2·(5)2·O-2+H2OO2+HO-2+OH-(6)HO-2+h+HO2·(7)2HO2·O2+H2O2(8)HO2·+e-+H+H2O2(9)H2O2+e-OH-+·OH(10)H2O2+·O-2O2+OH-+·OH(11)h++e-△(12),:e-,h+H2O2·OH、HO2·。。K2S2O8、H2O2、NaIO4、KBrO3O3。,e-,(12),。,[6]。,,。。,,。,,1%[7]。[8-11]。,,。、1.,(hν)(B.G.),,。、、·2·化　学　进　展11,。,TiO2、ZnO、ZnS、CdSPbS。,。CdS,,,,。,TiO2,。1　SnO2/TiO2,[12]。1,SnO2TiO2,TiO2SnO2;,SnO2TiO2,;,。WO3/TiO2[13]、MoO3/TiO2[14]、SiO2/TiO2ZrO2/TiO2[15]。Choi[16]TiO2,Fe(Ⅲ)、Mo(Ⅴ)、Re(Ⅴ)Os(Ⅲ)。,;,。,(-),,,。,、-TiO2。-TiO2,,,。TiO2(anatase)(rutile),TiO2,h+e-。TiO22-,,:,0.5%Pt/0.5%Ag/0.5%Pt/0.5%Ag/;,0.5%Ag/0.5%Ag/0.5%Pt/0.5%Pt/[17]。TiO2[18]。,,。2.(1),,。Sherrard[19],。,·3·1　。,,。,,。(2),,[20,21]、[22,23],[24]。2[25],,。Hofstadler[20]4-,DegussaP25TiO2,,1.6,(TOC)2.8。,,。,。,,。2　、1.。,100[3],。、、、,、、,。。TiO2h+3.0V,1.36V2.07V,h+。,、,。,,。,CO2H2O,、、X-、SO2-4、PO3-4、NO-3,。Ag/TiO2,,2h,10mg/LX-3B60%。,·4·化　学　进　展11　4-[24]CO2[31][26][32][24]7[12][2][33][2][33][27][33]99.4%[28][33][29][34][30][2][35]:HP5C2OOC2H5SO○NO2+15O2hν10CO2+4H2O+H3PO4+H2SO4+HNO3(13),Obee、、[22,36],。,。,,,。CO2,HCO3-。Matthews[37],1—40mL0.1—30mg/L。,。。,。2.、、。,。,。。,Hg2+e-HgTiO2,[9]。ZnO/WO3,110min,1.0×10-4g/mLHg(Ⅱ),99.1%[38]。[39]。[40]。SO2、H2S、NONO2[41],SO2S2-SO2-3,H2SSH2。,,·5·1　。、MatsunagaOkochi,TiO2Escherichiacoli[42]。TiO24,4h,60mEinstain/m2/s,TiO20.4mg/L。,TiO21g/L,30min,。Pt/TiO260—120min,Escherichiacoli、SaccharomycescerevisiaeLactobacillusacidophilus[43]。[44]。TiO290%PhageMS2,2×10-6mol/LFeSO4·7H2O99%。·OH,·OH,·OH·OH。,,。,。Cai[45,46]。TiO2(100mg/L),10minHeLa,,。TiO2,TiO2,。:h+;·OHHO2·。(SOD)O-2·H2O2·OH,。,。TiO2,,。,。,。、,。1.。TiO2,H2PtCl6(14)TiO2Pt[17]:Pt4++2H2OPt0+4H++O2(14)Pt0+Pt4+Pt4+24ePt2Pt4+Pt4+34ePt3Pt4+…Ptm(15),Pt4+(15),·6·化　学　进　展11Pt/TiO2。Pt、Pd、Rh、Au、AgIrZnO、WO3TiO2,Pt-Rh、Ag-RhPt-Pd[47],。2.。(15)。Herrmann[48],300KTiO2,。TiO2,。,,400nm。Hung[49]Na2S2O3h+,。TiO2,3∶1,,。[50]。,,。,h+,e-。,[2],,。、1.,。Tada[51]TiO21,3,5,7-(1,3,5,7-tetramethylcyclotetrasiloxane),(PMS),FT-IR,,。,,,,。TiO2,,[52]。ZnO(1—10nm)[53],,。ZnOZnO,,。4mol/L,。HoffmanCdS[54],,TiO2ZnOCdS,CdS。,,。2.。Yue[55]。TiO2,100W,,84±2℃。,·7·1　480℃,3×107Pa。,,。TiO20.4%Feγ-Al2O3,,17.5×10-6mol/gTiO2/h。,,,。CO2、、。Pd、Rh、PtAuTiO2,Pd/TiO2TiO235[56]。O2ZnO,H2O2[57]。h+e-,()()()(),2mmol/L。H2O2,。,。H2O2(8)(9),。H2O2,。1972FujishimaHondaTiO2,。,。。CdS、K4Nb6O17、SrTiO3TiO2,SrTiO3TiO2[58]。TiO2,H27,Ti4+W6+、Ta5+、Nb5+,H2;In3+、Zn2+Li+[59]。,e-h+。Pt-RuO2/TiO2,250—400nme-Pt,h+RuO2,e-h+,H2。,Pt-RuO2/TiO2[60]。H2:2H2O+2e-H2+2OH-(16)H2TiO2Pt,,pH,。,,,。,,。,,,。,。,,,。·8·化　学　进　展11、,,、、、,。,,。,,。,,。,,,(、、、)。,,。[1](CaiNC),(DongQH),化学通报(Chem.Bull.),1991,(7),9.[2]OllisDF,PelizzettiE,SerponeN,Environ.Sci.Technol.,1991,25(9),1523.[3]HoffmannMR,MartinST,ChoiWetal.,Chem.Rev.,1995,95,69.[4]TennakoneK,J.Photochem.PhotoBiol.A:Chem.,1993,71,199.[5](ZhengH),(TangHX),(WangYZ),环境科学进展(Adv.Environ.Sci.),1996,4,1.[6]MarternST,LeeAT,HoffmannMR,Environ.Sci.Technol.,1995,29(10),2567.[7]OllisDF,Environ.Sci.Technol.,1985,19(6),480.[8](WuHB),(DongXL),中国环境科学(ChinaEnviron.Chem.),1997,17(1),93.[9]TennakoneK,KetipearachchiUS,Appl.Catal.B:Environ.,1995,5(4),343.[10]ZhangY,CrittendenJC,HandDWetal.,Environ.Sci.Technol.,1994,28(3),435.[11]VinodgopalK,WynkoopDE,Environ.Sci.Technol.,1996,30(7),1660.[12]VinodgopalK,KamatPV,Environ.Sci.Technol.,1995,29(3),841.[13]DoYR,YeeW,DwightKetal.,J.SolidStateChem.,1994,108,198.[14]PappJ,SoledS,DwightKetal.,Chem.Mater.,1994,6,496.[15]FuX,ClarkLA,YangQetal.,Environ.Sci.Technol.,1996,30(2),647.[16]ChoiW,TremirA,HoffmannMR,J.Phys.Chem.,1994,98,13669.[17]SclafaniA,MozzanegaMN,HerrmannJM,J.Catal.,1997,168(1),117.[18](BaoDH),(GuHS),(KuangAX),无机材料学报(J.Inorg.Mater.),1996,11(3),453.[19]SherrardKB,MarriottPJ,AmietRG,Environ.Sci.Technol.,1995,29(9),2235.[20]HofstadlerK,BauerR,NovalicSetal.,Environ.Sci.Technol.,1994,28(4),670.[21]MartinCA,BaltanásMA,CassanoAE,Environ.Sci.Technol.,1996,30(7),2355.[22]ObeeTN,BrownRT,Environ.Sci.Technol.,1995,29(5),1223.[23]HaarstrickA,KutOM,HeinzleE,Environ.Sci.Technol.,1996,30(3),817.[24]PeillNJ,HoffmannMR,Environ.Sci.Technol.,1995,30(9),2806.·9·1　[25]RichardsonSD,ThrustonAD,ColletteTWetal.,Environ.Sci.Technol.,1996,30(11),3