CuLa共掺杂TiO2光催化氧化水中的氨氮刘佳

72Vol．7No．220132ChineseJournalofEnvironmentalEngineeringFeb．2013Cu/LaTiO211*211．4000452．550003-Cu/LaTiO2XRD、XPSBETTiO2。4～8nmCu/LaTiO2LaLa3+CuCu2+、Cu+TiO2。。TiO2X703A1673-9108201302-0457-06PhotocatalyticcatalyticoxidationofammoniainaqueoussolutionsbyCu/La-codopedTiO2LiuJia1LongTianyu1ChenQianlin2DuKun11．KeyLaboratoryofEco-EnvironmentofThreeGorgesRegionofMinistryofEducationChongqingUniversityChongqing400045China2．CollegeofChemicalandChemicalEngineeringGuizhouUniversityGuiyang550003ChinaAbstractTheCu/La-codopedTiO2nanoparticleswerepreparedbyhydrolysis-precipitationmethod．Thenano-TiO2wascharacterizedbyX-raydiffractometerXRDX-rayphotoelectronspectraXPSandtheBETsurfaceareas．ThephotocatalyticdegradationofammoniainaqueoussolutionsbydopedTiO2powdersunderUVirradiationwasstudied．Resultsofstructuralcharacterizationindicatethatthecatalysthasthebetteranatasephasetheporesizerangis4～8nmandtheincorporationofLaasLa3+andCuasCu2+Cu+existinCu/La-codopedTiO2nanoparticles．Experimentalresultsshowthatthetreatmentofammoniaandcokingwastewaterex-hibithighphotocatalyticactivitybymodifiedTiO2catalyst．Keywordscodoped-TiO2copperlanthanumphotocatalyticoxidationammonia2009ZX07104-002CSTC2011BB70852011－12－072012－03－271985～。[e-mail]*[e-mail]2、、、、TiO2400nm-。12。TiO2TiO2Ni/B、La/N、La/S、La/C、Fe/B、Fe/NS/BTiO2。TiO23。、、COD。。、。、45。-TiO2TiO2、7TiO2。11．1、、、、、、、、、、、。。X-X-PertXXESCALABMkIINova1000JJ-1YHW-102A721。1．2X-PertXXRD。CuKa0．1540nm。40kV40mA0．033°。XPSESCALABMkIIVacuumGeneratorsX。AlKa1486．6eVX10－8PaC1s284．80eV。NOVA1000N277K。COD。1．3-TiO2。27．2mL190mL1∶40A。80mL0．1mol/LCuNO32LaNO33500mLBAB1h6h105℃700℃3hCu/LaTiO2Cu/La-TiO2。CuNO32CuTiO2Cu/TiO2LaNO33LaTiO2La/TiO2TiO2。1．4125W365nm。20min30min20min。22．12．1．1XRD1-XRD。1。XRD101Scherrer6-8D101=Kλ/B1/2cosθ1KScherrerK=0．89λXλ=0．1542nmB1/2radθ°。Cu/La-TiO225．7nm。1XRDFig．1X-raydiffractionXRDpatternsofdifferentphotocatalysts2．1．2XPS2Cu/La-TiO2XPS。La、Cu、Ti、CO。3aCu/La-TiO2Cu2pXPS。3bLa3dXPS。Lorentzi-an-Gaussian3。3aCu2p3/2932．71eV934．65eVCu2p1/2953．89eV。Cu2p3/2932．2～933．18542Cu/LaTiO22Cu/La-TiO2XPSFig．2X-rayphotoelectronspectraofCu/La-TiO2eVCu+。941．29eVCu2+910。CuCu2+、Cu+TiO2。CuTiO2Cu2+、Cu+Ti4+Komandur11。3Cu2pLa3dXPSXPSFig．3High-resolutionXPSspectraofthe2pregionofCuinCu/La-TiO2andthe3dregionofLainCu/La-TiO23bLa3d5/2835eV839．45eVLa3d3/2852．1eV854．56eV。La3d3/2La3d5/2La2pLa4fLa3dLa3d3/2La3d5/2。La—O。Cu/LaTiO2La9。2．1．3BETBETN2-DFT4。4-Fig．4Nitrogenadsorption-desorptionisothermsofdifferentcatalystsinsertthecurveofporesizedistribution-。IUPAC6Ⅳ。。TiO212。49547DFT。4～8nmIUPACⅣ。Cu/La。TiO2123．88m2/gCu/La-TiO2124．67m2/gDegussaP-25TiO250m2/g。Cu/La-TiO21314。2．2100mg/L5。5Cu/La-TiO2。5Fig．5PhotocatalyticoxidationactivityofdifferentcatalystsforammoniaLa3+TiO2La—OTiO2。TiO2。f15。XPSCuCu2+、Cu+TiO2。Cu2+3d94s2Cu2+/Cu+0．154VCu+。Cu+TiO2Cu2Oh+16。Li17Cu2OTiO2。TiO2。。2．32．3．1Cu/La-TiO26。1g/L。TiO2。6Fig．6Effectofcatalystdosingonammoniaremovalrate2．3．2pHNaOHHClpHCu/La-TiO21g/LpH7。7pHFig．7EffectofpHonammoniaremovalratepH20642Cu/LaTiO2pHpH9．5。18NH+4+H2O→NH3+H3O+pKaNH+4=9．2462pH9．246NH3NH+4。pH7NH+499．5%pHNH3。NH3pHOH－·OH。pH10．5OH－。2．3．3H2O2H2O22h8。8H2O2Fig．8EffectofconcentrationofH2O2onammoniaremovalrate8H2O2H2O2H2O20．5mol/L91．3%。H2O219H2O2→2·OH3NH3+·OH→·NH2+H2O4·NH2+H2O2→·NHOH+H2O5·NH2+·OH→NH2OH6H2O20．5mol/LH2O2H2O2+·OH→H2O+·HO27·HO2+·OH→H2O+O28H2O2·OH。2．4COD2798．36mg/L258mg/LpH12．9COD144．03mg/L70．1mg/LpH8．7。SS、COD2716．06mg/L252．81mg/LpH11．74。1g/LpH9．52hCu/La-TiO23。1。1TiO2Table1DegradationofcokingwastewaterbyTiO2%CODTiO239．243．538．456．3Cu/TiO241．244．739．556．9La/TiO243．749．139．657．4Cu/La-TiO249．355．941．963．81TiO2、COD、COD。2H2O2Cu/La-TiO2、COD89．4%90．3%7．43mg/LCOD13．97mg/L。《》GB8978-96NH3-N≤15mg/LCODcr≤100mg/L。H2O2。16472H2O2Table2EffectofH2O2ondegradationofcokingwastewater%CODTiO252．470．145．670．2Cu/TiO258．．973．851．381．6La/TiO264．580．453．587．8Cu/La-TiO272．389．468．990．331TiO2XRD、XPS、BET。Cu/La-TiO2LaLa3+CuCu2+、Cu+TiO2。2。1g/LpH9．5H2O20．5mol/L90%。3COD、。、COD《》。1FoxM．A．DulayM．T．Heterogeneousphotocatalysis．Chem．Rev．1993931341-3572HoffmannM．R．MartinS．T．ChoiW．etal．Environ-mentalapplicationsofsemiconductorphotocatalysis．Chem．Rev．199595169-963．．20083691272-1276WeiFengyuZengHualingShiBinetal．Effectofsulphurandironco-dopingonphotocatalyticactivityoftitaniumdi-oxide．JournaloftheChineseCeramicSociety20083691272-1276inChinese4．．20082992537-2541TangLinaLiuLifenDongXiaoyan．Photocatalyticreduc-tionofnitrateusingmetal-dopedtitania．EnvironmentalSci-ence20082992537-2541inChinese5．．20042439-11GongLeiXuXiaojun．Technologiesofcokeplantwastewatertreatment．IndustrialWaterTreatment20042439-11inChinese6AkhlA．JawadA．S．ScottB．Structuraleffectsofcodop-ingofNbandScintitaniumdioxidenanoparticles．Eur．J．Inorg．Chem．2008496948-9537LeeP．L．ZhangX．SunD．D．etal．SynthesisofbimodalporousstructuredTiO2microspherewithhighphotocatalyticactivityforwatertreatment．ColloidsandSurfacesAPhys-icochem．Eng．Aspects20083241-3202-2078HuY．TsaiH．L．HuangC．L．Phasetransformat-ionofprecipitatedTiO2nanoparticles．Mater．Sci．Eng．A20033441209-2149BriggsD．SeahM．P．PracticalSurfaceAnalysisbyAugerandXrayPhot