不同活性物种对光催化降解水中邻苯二甲酸二甲酯动力学的贡献研究安继斌

2010,19(6):[e-mail](KZCX2-YW-QN103)(40973068)(SKLOG2009A02)(1984)*E-mail:[e-mail];[e-mail]2010-05-04**1.7300502.5106403.100049DMPpHLangmuir-HinshelwoodDMPDMPDMPTiO2DMP•OHDMP94%ecb-hvb+O2•-H2O2X132A1674-5906201006-1369-05(PhthalicacidestersPAEs)8020%30%[1][2-3][4-5][6]PAEs[7-8]PAEs[9-10]EPAPAEs(•OH)[11-13]TiO2[14][15]DMPDMPpHROSs•OHO2•-H2O2DMP(LC-20A)GGZ-125Emax=365nmPHS-3B()(AR)ARTiO2DegussaP25100µmol·L-1150mLTiO230minTiO2-DOI:10.16258/j.cnki.1674-5906.2010.06.0131370196201063mL0.2µmLC-20A229nmDiamonsilC18250×4.6mm5µm30℃25%75%0.6mL·min-1pHPHS-3BDMP1.00g·L-1pH6.5DMPTiO212DMP90%Langmuir-HinshelwoodDMPy=0.0251+0.0193xDMPTiO20.0193min-135.9min0.250.501.002.003.00g·L-1DMP21.00g·L-1DMP0.0179min-12.00g·L-1DMP0.0193min-1DMPTiO2TiO2[16]pHDMPpH3.05.07.09.02.00g·L-1pH3DMPpHTiO26.3TiO2DMPH+DMPDMPTiO2DMPpH0204060801001200.20.40.60.81.0ct/c0t/minTiO20.25g/LTiO20.50g/LTiO21.00g/LTiO22.00g/LTiO23.00g/L0.51.01.52.02.53.00.0160.0170.0180.019k1/min-1ρ(Catalyst)/(g/L)Fig.2EffectofTiO2dosageonthephotocatalyticdegradationrateconstantofDMP010203040500.00.20.40.60.81.0y=0.0251+0.0193xR2=0.995-ln(ct/c0)t/min0204060801001200.20.40.60.81.0ct/c0t/minFig.1PhotocatalyticdegradationkineticofDMP0204060801001200.10.20.30.40.50.60.70.80.91.0ct/c0t/minpH=3pH=5pH=7pH=934567890.0100.0120.0140.0160.0180.020k1/min-1pH3pHDMPFig.3EffectofpHvaluesonthephotocatalyticdegradationrateconstantofDMP1371pH6.3TiO2DMPpHOH-•OH[17]DMPDMP50100150200µmol·L-14DMP50µmo·L-1200µmol·L-10.0286min-10.0103min-1DMPTiO2DMPTiO2[18]DMPLangmuir-Hinshelwood[19-21]101kKkKc=+10111ckkkK=+2k1min-1kµmol·min-1KDMPTiO2Langmuir-Hinshelwoodµmol-11/k1551/k1C0k2.5050µmol·min-1K0.0274µmol-1DMPTiO2TiO2hvb+•OHDMPROSsDMPTiO23.2eV387.5nmTiO2TiO2hvb+ecb-hvb+ecb-•OHO2•-H2O21~5[12,22]TiO2+hvecb-+hvb+1hvb++H2O/-OH•OH+H+2ecb-+O2O2•-3O2•-+O2•-+H+H2O2+O24HO2•+H++ecb-H2O25TiO2ecb-hvb+•OHO2•-H2O25KI2-N26ecb-O2•-O2[23]N2O26▲O2•-TiO2•OHN26▼O2O26080100120140160180200405060708090y=14.5443+0.3992xR2=0.9881/k1c/(µmol/L)5DMP1/k1Fig.5TherelationshipbetweenintialconcentrationofDMPand1/k10204060801001200.00.20.40.60.81.0ct/c0t/minc0=50µmol/Lc0=100µmol/Lc0=150µmol/Lc0=200µmol/L501001502000.0100.0150.0200.0250.030k1/min-1c/(µmol/L)Fig.4EffectofinitialconcentrationofDMPonthephotocatalyticdegradationrateconstantofDMP137219620106DMPO2O2•-TiO2ecb-O2•-DMPhvb+•OHhvb+•OHhvb+TiO2H2OTiO2-OH-•OH[24]I-hvb+•OH[25]2-KIhvb+•OH5▼5DMP0.0193min-1I-hvb+•OH0.0004min-1•OH0.0010min-11DMPhvb+•OH98%•OH95%hvb+3%TiO2DMP•OH1TiO2DMPLangmuir-Hinshelwoody=0.0251+0.0193x0.0193min-135.9min2DMPTiO2DMP•OHDMP3TiO2ecb-hvb+•OHO2•-H2O25TiO2DMP•OHDMP95%ecb-hvb+O2•-H2O2[1],,,.[J].,2003,13(1):9-14.HUXiaoyu,ZHANGKerong,SUNJunhong,etal.EnviromentalcontaminationbyphthalatesinChina[J].ChinsesJournalofHealthLabortoryTechnology,2003,13(1):9-14.[2]LIUH,LIANGHC,LIANGY,etal.Distributionofphthalateestersinalluvialsediment:AcasestudyatJiangHanPlain,CentralChina[J].Chemosphere,2010,78(4):382-388.[3]ZENGF,CUIKY,XIEZY,etal.Phthalateesters(PAEs):Emergingorganiccontaminantsinagriculturalsoilsinperi-urbanareasaroundGuangzhou,China[J].EnvironmentalPollution,2008,156(2):425-434.[4],,.[J].,2006,26(1):120-124.SHAYujuan,XIAXinghui,XIAOXiangqun.DistributioncharactersofphthalicacidesterinthewatersmiddleandlowerreachesoftheYellowRiver[J].ChinaEnvironmentalScience,2006,26(1):1220-124.[5]LERTSIRISOPONR,SODAS,SEIK,etal.Abioticdegradationoffourphthalicacidestersinaqueousphaseundernaturalsunlightirradiation[J].JournalofEnvironmentalSciences-China,2009,21(3):285-290.[6]WANGP,WANGSL,FANCQ.Atmosphericdistributionofparticulate-andgas-phasephthalicesters(PAEs)inaMetropolitanCity,Nanjing,EastChina[J].Chemosphere,2008,72(10):1567-1572.[7],,.[J].,2003,25(5):286-288.LINXingtao,WANGXiaoyi,RENRen.Environmentalendocrinedisruptorastudyofphthalateesters[J].EnvironmentalPollutionandControl,2003,25(5):286-288.0204060801001200.10.20.30.40.50.60.70.80.91.0ct/c0t/minKIIsopropanolN2Noscavengers6Fig.6ThecontributionofdifferentROSsduringphotocatalyticdegradationprocessTable1Scavengersused,reactivespeciesquenched,andkforDMPafterquenchedROSs/(k·min-1)R2N2O2•-0.00670.991KIhvb+and•OH0.00040.965Isopropanl•OH0.00100.952DMP－－0.01930.9951373[8]BABICHMA,CHENSB,GREENEMA,etal.Riskassessmentoforalexposuretodiisononylphthalatefromchildren'sproducts[J].RegulatoryToxicologyandPharmacology,2004,40(2):151-167.[9]JAROSOVAA.Phthalicacidesters(PAEs)inthefoodchain[J].CzechJournalofFoodSciences,2006,24(5):223-231.[10]MATSUMOTOM,HIRATAIKM,EMAM.Potentialadverseeffectsofphthalicacidestersonhumanhealth:Areviewofrecentstudiesonreproduction[J].RegulatoryToxicologyandPharmacology,2008,50(1):37-49.[11]TUERKJ,SAYDERB,BOERGERSA,etal.Efficiency,costsandbenefitsofAOPsforremovalofpharmaceuticalsfromthewatercycle[J].WaterScienceandTechnology,2010,61(4):985-993.[12]ANTC,YANGH,SONGWH,etal.MechanisticConsiderationsfortheAdvancedOxidationTreatmentofFluoroquinolonePharmaceuticalCompoundsusingTiO2HeterogeneousCatalysis[J].JournalofPhysicalChemistryA,2010