TiO2介孔材料光催化降解造纸废水影响因素的研究

　2010200810ChemicalResearchandApplicationVol.20,No.10Oct.,2008　:2008-01-23;:2008-06-13:(Z2006B07);(2005383):(1965-),,,。Email:[e-mail]:1004-1656(2008)10-1385-06Ni2+/TiO2徐会颖,周国伟＊,魏英勤(,　　250353):-NiNi2+/TiO2。X(XRD)、(TEM)、(FT-IR)N2。Ni、、pH、。:Ni2+/TiO2:Ni2%、1.5g/L、pH=4、;4h,100%;12h,CODCr83.4%。:Ni2+/TiO2;;:O614.411　　:A,TiO2。、TiO2。,80%,、。。,[1]。,TiO2。,[2]。,TiO2、[3]。TiO2。-Ni2+/TiO2,,Ni、pH、、。1　1.1　NiTiO2NiTiO2[4]:(PluronicP123),30,(TBT),1。,。P123:HCl:::TBT=0.025:1:6.5:6.5:1。,TBT0%、1%、2%、3%、4%。50℃7,130℃,350℃6,。0%Ni2+/TiO2(TiO2)、1%Ni2+/TiO2、2%Ni2+/TiO2、3%Ni2+/TiO24%Ni2+/TiO2。1.2　X(D/MAX2200PC),0.06°/s。TEM(JEM-100CXⅡ)。BET(Brunauer-Emmett-Teller)BJH化学研究与应用第20卷(Barrett-Joyner-Halenda)ASAP2020(Micromertics),200℃3。(FT-IR)Tensor27,KBr;:32,:4cm-1。1.3　,375W,。,pH、、,(KQ2200,80W)30min,,,。8000r/min15min,TiO2,。,pH。GB11914-89CODCr,CPPA[5],:(%)=[(A0-A)/A0]×100%:A0-465nm;A-465nm。2　2.1　NiTiO22.1.1　XRD1NiTiO2350℃XRD,XRD2θ=25.3°(101),37.9°(004),47.8°(200),54.3°(211),63.7°(204),TiO2。TiO2(101),,,。TiO2,,TiO2。,TiO2。XRDNiO,Ni2+。图1　不同配比的Ni掺杂TiO2在350℃下焙烧的XRD图a:pureTiO2;b:1%Ni2+/TiO2;c:2%Ni2+/TiO2;d:3%Ni2+/TiO2;e:4%Ni2+/TiO2Fig.1　TheXRDpatternsofdifferentNidopedTiO2calcinedat350℃2.1.2　TEM2350℃2%Ni2+/TiO2TEM(ED)。TEM,10nm。,,。(101)、(004)、(200)、(103)(211),[6]。XRD。图2　掺杂2%Ni2+/TiO2的TEM照片及电子衍射图谱Fig.2　TheTEMandelectronicdiffractionphotographof2%dopedNi2+/TiO21386第10期徐会颖等:Ni2+/TiO2介孔材料光催化降解造纸废水影响因素的研究2.1.3　N2-图3　不同Ni掺杂量Ni2+/TiO2的N2吸附脱附等温线和孔径分布曲线Fig.3　TheN2adsorption-desorptionisothermandporesizedistributionofdifferentNidopedratioNi2+/TiO2图4　纯介孔TiO2(a)和2%Ni2+/TiO2(b)的FT-IR谱图Fig.4　TheFT-IRspectraofpureTiO2(a)and2%Ni2+/TiO2(b)3NiNi2+/TiO2N2。3:TiO22%Ni2+/TiO2N2-IUPACIV,H1,[7]。BJH,2%Ni2+,TiO2,8.8nm10.6nm。BET159m2/g136m2/g。,。Ni4%,,B,,BET422m2/g。:4%Ni2+/TiO2。XRD,Ni,Ni2+/TiO2,Ni4%,NiTiO2,TiO2,4%Ni2+/TiO2。2.1.4　FT-IR4TiO22%Ni2+/TiO2350℃6FT-IR,400-1000cm-1TiO2Ti-O,1620cm-1H-O-H,3200cm-1,1625cm-13356cm-1TiO2H2O。Ni,Ni-O,4Ni-O。NiTi-O。FT-IRP123(C-CC-O-C),350℃,。2.2　,。CODCr500.0,。1387化学研究与应用第20卷2.2.1　Ni图5　不同Ni掺杂量的介孔TiO2对造纸废水色度和CODCr去除率的影响催化剂用量1.5g/L;初始pH=4;通氧Fig.5　TheinfluenceofdiferentNidopedratioporousTiO2onchromaandCODCrremovalofpapermakingwastewaterCatalyzerdosage1.5g/L;OriginalpH=4;aeratingwithoxygen5:NiTiO2CODCr,CODCrNi。4,Ni2%TiO2100%,,Ni1%3%TiO26100%,TiO290%。TiO2,NiTiO2。,,-,,;,,-,TiO2,TiO2·OH,。1%Ni2+/TiO2CODCrTiO2,2%Ni2+/TiO2CODCrTiO2。CODCr,TiO2Ni2+2%。2.2.2　pH图6　pH值对2%Ni2+/TiO2降解造纸废水的影响催化剂用量1.0g/L;取样时间3h;通氧Fig.6　TheinfluenceofpHon2%Ni2+/TiO2degradationofpapermakingwastewaterCatalyzerdosage1.5g/L;samplingtime3h;aeratingwithoxygenpH、,。6:pH,,pH,pH12,。pH,-0.059V/pH,+2.6eV,pH,,pH,[8]。,,pH,。pH,。1388第10期徐会颖等:Ni2+/TiO2介孔材料光催化降解造纸废水影响因素的研究7。pH,,,pH,,;,。:TiOH+H+TiOH2+(1)TiOH+OHTiO-+H2O(2),pH,,,。pH,TiO2,。[9]。6,pH3,,,CODCr。,pH4。2.2.3　图7　催化剂用量对2%Ni2+/TiO2降解造纸废水的影响初始pH=4;取样时间3h;通氧Fig.7　Theinfluenceofcatalyzerdosageon2%Ni2+/TiO2degradationofpapermakingwastewaterOriginalpH=4;Sampletime3h;aeratingwithoxygen,,,·OH。—,。,·OH,。,,,。,[10]。7:2%Ni2+/TiO21.5g/L,。2.2.4　图8　外加氧化剂对2%Ni2+/TiO2降解造纸废水的影响催化剂用量1.5g/L;初始pH=4Fig.8　Theinfluenceofaddionaloxidanton2%Ni2+/TiO2degradationofpapermakingwastewaterCatalyzerdosage:1.5g/L;OriginalpH=4,-。。,,。8:。,TiO2-,,。,[11]。,,:ecb-+Ti4+※Ti3+(3)Ti3++O2※Ti4+-O2-·(4)Ti4+-O2-·+H3O+→※Ti4+OH2+HO2·(5)2HO2·※H2O2+O2(6)、。,。2.2.5　1　CODCrTable1　Theinfluenceofirridiationtimeon2%Ni2+/TiO2degradationofpapermakingwastewaterh24681012CODCr%32.644.347.561.475.683.4%40.8100.0100.0100.0100.0100.02%Ni2+/TiO2;1.5g/L;pH=4;。1389化学研究与应用第20卷1CODCr。1,CODCr。2%Ni2+/TiO2,4,100%;12h,CODCr83.4%。3　(TBT),(PluronicP123),-Ni2+TiO2。Ni2+TiO2,。2%Ni2+,8.8nm10.6nm,BET159m2/g136m2/g。Ni2+TiO2CODCr;2%Ni2+/TiO2;pH=4;1.5g/L;4,100%;12h,CODCr83.4%。:[1]SahooDK.,GuptaR.Evaluationofligninolyticmicroorganismsforefficientdecolorizationofasmallpulpandpapermilleffluent[J].RimpyGuptaProc.Biochem,2005,40:1573.[2]YeberMC,RodrlguezJ,FreerJ.Advancedoxidationofapulpmillbleachingwastewater[J].Chemosphere,1999,39(10):1679.[3]PérezM,TorradesF,PeralJ,etal.Multivariateapproachtophotocatalyticdegradationofacellulosebleachingeffluent[J].Appl.Catal.B,2001,33:89.[4]YuanS,ShengQ,ZhangJ,etal.SynthesisofLa3+dopedmesoporoustitaniawithhighlycrystallizedwalls[J].MicroporousMesoporousMater,2005,79:93.[5].[M].:,2001:380.[6]ShibataH,OguraT,MukaiT,etal.Directsynthesisofmesoporoustitaniaparticleshavingacrystallinewall[J].J.Am.Chem.Soc,2005,127:16396.[7]BoscF,AyralA,AlbouyPA,etal.Asimplerouteforlow-temperaturesynthesisofmesoporousandnanocrystallineanatasethinfilms[J].Chem.Mater,2003,15:2463.[8]DavitP,MartraG,ColucciaS.PhotocatalyticdegradationoforganiccompoundsonTiO2powders———FT-IRinvestigationofsurfacereactivityandmechanisticaspects[J].J.Jpn.Petro.Inst,2004,47(6):359.[9]MachadoAEH,deMirandaJA,deFreitasRF.Destructionoftheorganicmatterpresentineffluentfromacelluloseandpaperindustryusingphotocatalysis[J].J.Photochem.Photobiol.A,2003,155:231.[10]PérezM,TorradesF,PeralJ,etal.Multivariateapproachtophotocatalyticdegradationofacellulosebleachingeffluent[J].Appl.Catal.B,2001,33:89.[11]LinH,ZhouG,LiuY,etal.PreparationofmesoporousTiO2-SiO2