负载型磷钨酸催化剂的制备及其光催化性能陶国忠

、。2DO[1-2]。。。。、。。、[3]。、。、、、。2080、。、、、[4-11]。、、[12-25]。。、、。DegussaP25、PVAKegginHPW/TiO2HPW/PVAMn2+Mn2++1121.2002372.200237TiO2HPWPVAHPW/TiO2HPW/PVAMn2+HPW、Mn2+、pHMn2+。HPW/TiO2TiO2HPW/PVA。HPW20%、Mn2+40mg·L-1、pH6.7HPW/TiO2Mn2+83.1%6。TQ032.41A1000-3770(2011)[e-mail][e-mail]3710201110TECHNOLOGYOFWATERTREATMENTVol.37No.10Oct.,201132DOI:10.16796/j.cnki.1000-3770.2011.10.0102H2O+2h+→MnO2+4H+。HPW、Mn2+、pHMn2+。11.1ARQ/CYDZCP≥99.0%PVAAR≥99.0%AR65.0%～68.0%DegussaP25。UV-2102PCThermoNicoletNexus670-300TEM。1.2。1.00gDegussaP2550mL0.1mol·L-128h175℃30min30min400℃2h100℃120℃HPW/TiO2。HPW/TiO2360℃5h。PVA。1.50gPVA50mL70℃2h60℃36hHPW/PVA。HPW/PVA360℃5h。1.30.50gHPW/TiO2HPW/PVA500mL40min6.5cm、10cm800r·min-120℃365nm300W25cm30min。2hMn2+。Mn2+=(ρ0-ρ2h)/ρ0ρ0Mn2+ρ2h2hMn2+。22.1Mn2+1Mn2+20℃pH=6.7Mn2+75mg·L-10.5gHPW/TiO2、HPW/PVAHPW40%。1TiO2、HPW/TiO2HPW/PVAMn2+20min。Mn2+。2.22Mn2+20℃pH=6.70.5gMn2+40mg·L-1。1Mn2+Fig.1ThedarkadsorptioncurveofcatalystforMn2+insolution010203040506050556065707580t/minHPW/PVAHPW/TiOTiO
(Mn)/mgL2Mn2+Fig.2EffectofHPWloadingonremovalefficiencyofMn2+010203040020406080100w(HPW)/%HPW/TiOHPW/PVAMn
/%335Mn2+Fig.5ThereuseofsupportedcatalystinthephotoxidationofMn2+012345678910020406080100
HPW/TiOHPW/PVAMn/%2HPW/PVAHPW30%Mn2+HPWHPW30%Mn2+。HPWMn2+14.2%HPW。HPW/PVAHPWPVA、Mn2+。HPW/TiO2TiO2HPWHPW20%Mn2+83.1%。TiO2HPWKegginTiO2HPWTiO2TiO2。HPWTiO2HPW。2.3Mn2+3Mn2+20℃pH=6.70.5g20%HPW/TiO230%HPW/PVA。3Mn2+15～55mg·L-1HPW/TiO2Mn2+1xA=1-e-ktxAt2h。HPW/PVAMn2+1Mn2+40mg·L-1Mn2+Mn2+Mn2+。2.4pH4pHMn2+20℃Mn2+40mg·L-10.5g20%HPW/TiO230%HPW/PVA。4pHHPW/PVAMn2+pHpHHPW/TiO2Mn2+H+Mn2+。pHpH。2.5520℃pH=6.7Mn2+40mg·L-10.5g20%HPW/TiO230%HPW/PVA。3Mn2+Fig.3EffectofinitialconcentrationofMn2+onremovalefficiencyofMn2+102030405060020406080100
(Mn)/mgLHPW/TiOHPW/PVAMn
/%4pHFig.4EffectofpHofsolutiononremovalefficiencyofMn2+234567020406080100pHHPW/TiOHPW/PVAMn
/%3710345HPW/TiO2HPW/PVA64Mn2+MnO2。HPW/TiO284.5%、HPW/PVA90.7%。2.6TiO2HPW/TiO2TEMTiO230～40nmHPW/TiO240～60nmTiO2HPW。P25TiO2HPWTiO2。6HPW、PVAHPW/PVAIR。6Keggin41300～400cm-1793cm-1W－2Oc－2W、892cm-1W－Oe－W、985cm-1W=Od、1080cm-1P－O。HPW/PVA[PW12O40]3-Keggin。PVAHPWHPW。3PVAHPW/TiO2HPW/PVADegussaP25。Mn2+Mn2+Mn2+Mn2+PVA。、、。HPW/TiO2HPW/PVA2。[1],,,.[J].,2004,21(2):10-13.[2],,,.[J].,2004,21(4):39-40.[3],,,.[J].,2003,19(6):1-5.[4],,,.TiO2[J].,2004,32(3):21-25.[5],,,.[J].,2007,24(3):334-337.[6],,,.POM-APS-TiO2[J].,2003,19(4):24-26.[7],,,.H6P2W18O62/SiO2[J].:,2005,21(4):6-9.[8],,,.PW11M[J].,2007,24(7):786-789.[9],,,.[J].,2006,20(4):554-558.[10]MarcìG,Garcìa-LópezE,PalmisanoL,etal.Preparation,charac-terizationandphotocatalyticactivityofTiO2impregnatedwiththeheteropolyacidH3PW12O40:Photo-assisteddegradationof2-propanolingas-solidregime[J].AppliedCatalysisB:Environmental,2009,90(3/4):497-506.[11]YanagidaS,NakajimaA,SasakiT,etal.PreparationandphotocatalyticactivityofKeggin-iontungstateandTiO2hybridlayer-by-layerfilmcomposites[J].AppliedCatalysisA:General,2009,366(1):148-153.[12]DillertR,BahnemannD,HidakaH.Light-induceddegradationofperfluorocarboxylicacidsinthepresenceoftitaniumdioxide[J].Chemosphere,2007,67(4):785-792.[13]HoriH,HayakawaE,EinagaH,etal.Decompositionofenvironmentallypersistentperfluorooctanoicacidinwaterbyphotochemicalapproaches[J].EnvironmentalScience&Technology,2004,38(22):6118-6124.[14]HoriH,TakanoY,KoikeK,etal.Decompositionofenvironmentally6PVA、HPW/PVAFig.6IRspectrogramofpolyvinylalcohol,phosphotungsticacidandHPW/PVAcatalyst020406080100PVAHPW/PVAHPW40003500300025002000150010005000τ(λ)/%σ/cm-135PREPARATIONANDPHOTOCATALYTICACTIVITYOFSUPPORTEDPHOSPHOTUNGSTICACIDCATALYSTTaoGuozhong1,QinJuan1,ChenAiping2(1.EngineeringResearchCenterofLargeScaleReactorEngineeringandTechnologyMinistryofEducationEastChinaUniversityofScienceandTechnology,Shanghai200237,China;2.KeyLaboratoryforUltrafineMaterialsMinistryofEducationEastChinaUniversityofScienceandTechnology,Shanghai200237,China)Abstract:Twosupportedphosphotungsticacid(HPW)photocatalystsentitledasHPW/TiO2andHPW/PVAwerepreparedviaimmersionandcodissplution,respectively.EffectsofHPWloading,initialconcentrationofMn2+andpHofreactionsystemontheremovalefficiencyofMn2+fromwaterwerestudiedunderultravioletlightirradiation.Theseparationandrecoveryofsupportedcatalystanditsreusewerealsoinvestigated.ExperimentalresultsshowthatthephotocatalyticactivityofHPW/TiO2ishigherthanpureTiO2andHPW/PVA.TheremovalefficiencyofMn2+is83.1%underphotocatalyticreactionconditionsasfollows:20%HPWloading,initialρ(Mn2+)=40mg·L-1,pH=6.7.Noevidentdecreaseinphotocatalyticactivitywasfoundafter6threuseofHPW/TiO2.Keywords:phosphotungsticacid;photocatalyticoxidation;titaniumdioxide;polyvinylalcohol;manganeseionpersistenttrifluoroaceticacidtofluorideionsbyahomogeneousphotocatalystinwater[J].EnvironmentalScience&Technology,2003,37(2):418-422.[15]HoriH,HayakawaE,KoikeK,etal.Decompositionofnonafluoro-pentanoicacidbyheteropolyacidphotocatalystH3PW12O40inaqueoussolution[J].JournalofMolecularCatalysisA:Chemical,2004,211(1/2