TiO2光催化处理废水中贵重金属的研究进展李川

TiO2李　川　古国榜　柳　松(,510640)　　TiO2、。TiO2、、TiO2、、、、pH、O2、、、。(Cr(Ⅵ)、Hg(Ⅱ)、Cd(Ⅱ))、。,。　　　ProgressintreatmentofheavymetalsandpreciousmetalsinwastewaterbyTiO2photocatalysisLiChuan　GuGuobang　LiuSong(DepartmentofAppliedChemistry,SouthChinaUnivesityofTechnology,Guangzhou510640)Abstract　Areviewwasgivenforprinciples,parametersandapplicationoftreatmentofheavyandnoblemetalsinwastewaterbytitaniumdioxidephotocatalysis.Parametersincludecrystalconfiguration,sizeandspecialarea,dosageoftitaniumdioxide,modifier,lightanditsintensity,metalions,pH,O2,holescavenger,othercationsandanions,immobilizationandreactor.Themethodoftreatmentofindividualmetalions(Cr(Ⅵ),Hg(Ⅱ),Cd(Ⅱ)),selectivelyrecoveryofnoblemetalsandsynergisticinteractionbetweenremovalofmetalsanddegradationoforganicwastesbyphotocatalysiswereshown.Atlast,existingproblemsandfurtherinvestigationswerepointedout.Keywords　photocatalysis;wastewater;heavyandnoblemetals:2003-01-17;:2003-05-28:(1970～),,,,。　　,:、、、、、、、、、[1,2]。,。,,,。,。,。。1　TiO21.1　TiO2,,,,。n×10-12s,;//。,、、。,,[3]。1.2　TiO2　　,。3[2,4]:①;②,(),;③,Pb(Ⅱ)、Mn(Ⅱ)Ti(Ⅰ)。411Vol.4,No.11200311TechniquesandEquipmentforEnvironmentalPollutionControlNov.20032　TiO2　　,,,。,,TiO2。2.1　TiO2,TiO2;Ti,O2;,,,[5,6]。TiO2Hg(Ⅱ)[5]。TiO2Cd(Ⅱ),,TiO2,Cd(Ⅱ)[6]。2.2　TiO2,e-,(Ag(I)O2),(Pb(Ⅱ))TiO2(h+),e-、h+,,,e-、h+。HgCl2,HgPt/TiO2TiO2[2]。Pt/TiO2Pb(Ⅱ)PbO2,TiO2[7,8]。TiO2AgPt,PtAg[9]。3　TiO23.1　TiO23.1.1　TiO2晶型　　3[10]:、。,,。,,、、、。,TiO2,-。,,,。Ag(Ⅰ)[2],TiO2,TiO2,TEM,TiO2。3.1.2　粒径和比表面积[11]。,TiO2,TiO2,,。,,,TiO2,,。110nm,。,。-,。TiO2,TiO2,Cd(Ⅱ)[6]。15nm,。Ni2+/Ni0,Ni(Ⅱ)。,,TiO2Ni(Ⅱ),,0.6V,Ni(Ⅱ)[12]。TiO2。。3.1.3　TiO2的用量　　,TiO2,,,[13,14]。TiO20.2—2g/L。3.2　TiO23.2eV,387nm。,,,711　:TiO2[15]。PtCl2-6[16],。3.3　,,pH。,TiO2(+),;TiO2(-),[17]。,,,,TiO2,,。Mn2+/Mn0-1.18V,,。,,Mn(Ⅱ),,Mn(Ⅱ)[13]。pH。,,,,。,,,。3.4　,,、。,Hg2+/Hg0HgCl2/Hg0。AuCl-4Au(CN)-4[18,19]。H2PtCl6、Na2PtCl6H2Pt(OH)6,;Pt(NO2)2(NH3)2[20]。TiO2Hg(NO3)2Hg,HgCl2Hg[2]。,L-H。pH,,,[2,21]。TiO2HgCl2[2],Hg0。3.5　pHTiO2pH,TiO2pH=6.25,pH6.25,TiO2,pH6.25,TiO2,,。TiO2E-pH[17]。pH[21]。,pH;,pH。Mn(Ⅱ)TiO2()pH,[13]。Cr(Ⅵ)pH,;,pHCr(Ⅵ),Cr(Ⅲ)OH-[2]。3.6　　,O2·-,·OH。O2,[21]。,,O2,[6,21]。,Pt/TiO2Pb(Ⅱ),、PbO2Pb(Ⅱ),,Pb(Ⅱ)。O2。pH=3.1,TiO2AuCl-4Au,,O2Au[17]。O2Fe(Ⅲ)Cr(Ⅵ),Fe(Ⅲ),Cr(Ⅵ),。3.7　(),。,。[22]。,“”,。,84,,。:、、()、()、、。。3.8　Fe(Ⅲ)P-25[5,21],Fe(Ⅲ),Hg(Ⅱ)。AgCu(Ⅱ),Cu(Ⅱ)[24]。Zn(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)、Ca(Ⅱ)Cr(Ⅵ)[24]。,。,,,。Ni(Ⅱ)SO2-4Cl-[25]。Cr(Ⅵ)[24]。Cl-PtCl2-6,Pt[26]。3.9　TiO2、。,TiO2TiO2。4　,。,()。Pt[26]Cr[27]。,。4.1　4.1.1　铬、,0.05mg/L。Na2S2O3、FeSO4、Na2S、SO2Cr(Ⅵ)Cr(Ⅲ),Cr(OH)3。Cr(Ⅵ)。,,Cr2O2-7。,Cr(Ⅵ)。Testa[28]EPREDTA,Cr(Ⅵ)Cr(Ⅲ):Cr(Ⅵ)e-Cr(V)e-Cr(Ⅳ)e-Cr(Ⅲ),。Chen-thamarakshan[29],pH、NH+4,Cr(Ⅵ)。Colón[30],Cr(Ⅵ),。4.1.2　汞Hg(Ⅱ),0.005mg/L,。0.001mg/L。。,、、、。,。TiO2。Khalil[31],Hg(Ⅱ)、pH、Hg(Ⅱ)TiO2,,O2,Hg(NO3)2HgCl2。Skubal[5]TiO2,Hg(Ⅱ),99.9%,30mg/LFe(Ⅲ)Hg(Ⅱ)TiO2。4.1.3　镉,,0.005mg/L。Cd(Ⅱ)Zn(Ⅱ),,TiO2。Chenthamarakshan[32](),Cd(Ⅱ),;()。(),Cd(Ⅱ)。Skubal[6]TiO2,Cd(Ⅱ),90%Cd(Ⅱ)。4.2　。,pH、O2()。((3∶1,v/v))。Litter[2],TiO2Ag+、Cu2+S2O2-3,,S2O2-3SO2-4,Cu2+911　:TiO2。Litter[2],,pH=3.1,Rh(Ⅲ)Pd(Ⅱ),Pd(Ⅱ),Rh(Ⅲ);pH=11.8,Pt(Ⅳ),Rh(Ⅲ)Pd(Ⅱ)TiO2。Borgarello[33],pH=7.39,Pt(Ⅳ)、Rh(Ⅲ)Au(Ⅲ),,TiO2Au。Pt(Ⅳ),Au(Ⅲ),Rh(Ⅲ),pH;,pH=0,Au(Ⅲ)TiO2,Pt(Ⅳ)Rh(Ⅲ),pH=0,Pt(Ⅳ)Rh(Ⅲ)。4.3　,、。Schrank[34]Cr(Ⅵ)(),,Cr(Ⅵ),;,Cr(Ⅵ),;Cr(Ⅵ),Cr(Ⅵ),Cr(Ⅵ)。,,。5　,,;,。,、、。。,,,,;;。[1]..:,1986.60—90[2]LitterM.I.Heterogeneousphotocatalysis:Tansitionmetalionsinphotocatalyticsystems.AppliedCatalysisB:Environmental,1999,23:89—114[3]LinsebiglerA.L.,LuG.,YatesJ.T.PhotocatalysisonTiO2surfaces:Principles,mechanismsandselectedresults.Chem.Rev.,1995,95:735—758[4]BabaR.,KondaR.,FujishimaA.,etal.Photoelec-trochemicaldepositionofmetalsonTiO2powdersinthepres-enceofalcohol.Chem.Lett.,1986,176(8):1307—1310[5]SkubalL.R.,MeshkovN.K.Reductionandremovalofmer-curyfromwaterusingarginine-modifiedTiO2.J.Photochem.Photobiol.A:Chem.,2002,148:211—214[6]SkubalL.R.,MeshkovN.K.,RajhT.,etal.Cadmiumre-movalfromwaterusingthiolacticacid-modifiedtitaniumdioxidenanoparticles.J.Photochem.Photobiol.A:Chem.,2002,148:393—397[7]TanakaK.,HaradaK.,MurataS.PhotocatalyticdepositionofmetalionsontoTiO2powder.SolarEnergy,1986,36:159—161[8]TorresJ.,Cervera-MarchS.KineticsofthephotoassistedcatalyticoxidationofPb(Ⅱ)inTiO2suspensions.Chem.Eng.Sci.,1992,47:3857—3862[9]SclafaniA.,HerrmannJ.M.Influenceofmetallicsilverandofplatinum-silverbimetallicdepositsonthephotocatalyticactivityoftitania(anataseandrutile)inorganicandaqueousmedia.J.Photochem.Photobiol.A:Chem.,1998,113:181—188[10]..:,2000.4[11],,,.TiO2———.,2000,28(4):11—13,34[12]MorishitaS.,SuzukiK.Photoelectrochemicaldepositionofnickelontoparticlesformationofnickelpatternswithoutre-sists.Bull.Chem.Soc.Jpn.,1994,67:843—846[13]MingY.,ChenthamarakshanC.R.,RajeshwarK.Radical-mediatedphotoreductionofmanganese(II)speciesinUV-irra-diatedtitaniasuspensions.J.Photochem.Photobiol.A:Chem.,2002,147:199—204[14]GoswamiD.Y.Areviewofengineeringdevelopmentsofaque-ousphasesolarphotocatalyticdetoxificationanddisinfectionprocess.J.SolarEnergyEng.,1997,119:101—107[15]AbdullahM.,LewG.K.C.,MatthewsR.W.Effectsofcommoninorganicanionsonratesofphotocatalyticoxidationoforganiccarbonoverilluminatedtitaniumdioxide.J.Ph