FeMn掺杂干凝胶的制备表征及催化臭氧氧化邻二氯苯性能英文

(WuliHuaxueXuebao)ActaPhys.-Chim.Sin.,2010,26(9)：2443-2448Received:February25,2010;Revised:May5,2010;PublishedonWeb:July2,2010.*Correspondingauthor.Email:[e-mail],[e-mail];Tel/Fax:[phone].TheprojectwassupportedbytheNationalNaturalScienceFoundationofChina(20836008,U0633003),ScienceandTechnologyDepartmentofZhejiangProvince,China(2007C13061),andNationalHighTechnologyResearchandDevelopmentProgramofChina(2007AA06Z339,2008BAC32B06,2007AA06A409).(20836008,U0633003),(2007C13061)(2007AA06Z339,2008BAC32B06,2007AA06A409)鬁EditorialofficeofActaPhysico-ChimicaSinica[Article]、Mn、*(,,310027)：-Fe、Mn(XFeXMn),(o-DCB).X(XPS)、X(XRD)、(TEM)、(SEM)、Fe、Mn.:XFeXMn,,;44%o-DCB,XFeXMno-DCB58%72%,XFeXMn;XFeXMn,5h2%8%.：-;;;;：O643Preparation,CharacterizationandCatalyticActivityforortho-DichlorobenzeneOzonationofFe-,Mn-DopedXerogelsHUANGYanZHANGXing-WangLEILe-Cheng*(InstituteofIndustrialEcologyandEnvironment,DepartmentofChemicalandBiologicalEngineering,ZhejiangUniversity,Hangzhou310027,P.R.China)Abstract：Metal-dopedxerogelsweresynthesizedbythesol-gelmethodandtheircatalyticperformancewasevaluatedforthecatalyticozonationofsimulatedmicro-pollutedwatercontainingortho-dichlorobenzene(o-DCB).TheobtainedsampleswerecharacterizedbyX-rayphotoelectronspectroscopy(XPS),transmissionelectronmicroscopy(TEM),X-raydiffraction(XRD),scanningelectronmicroscopy(SEM),mercuryporosimetryandnitrogenadsorption.ResultsshowthatFe3+oxidesandMn3+oxidesarepresentintheFe-dopedxerogel(XFe)andtheMn-dopedxerogel(XMn),respectively.NoobviousdiffractionpeakscorrespondingtoametallicphasewerepresentintheXRDpatternsofthexerogels.Also,themetallicparticleswerefoundtobesmall;therefore,themetallicparticleswerewelldistributedoverthexerogelsupports.Catalyticozonationexperimentsindicatedthattheremovalrateofo-DCBwas44%withsingleozonation,andthisincreasedto58%and72%withcatalyticozonationusingXFeandXMn,respectively,whichsuggeststhatmetal-dopedxerogelsarepromisingcatalystsfortheozonationprocess.Wealsoinvestigatedmetalleachingfromthemetal-dopedxerogeltothewatersolutiontotestthestabilityofthecatalysts,andabout2%and8%metalleachingforXFeandXMnwasobtainedwithin5h.KeyWords：Sol-gelmethod;Xerogel;Characterization;Catalyticozonation;ortho-Dichlorobenzene2443ActaPhys.-Chim.Sin.,2010Vol.26Heterogeneouscatalyticozonationisaneffectiveapproachtodecomposerecalcitrantcontaminants,suchaschlorinatedaro-maticcompounds,withoutextraadditionofchemicalsandener-gy.Themaincatalystsusedinthisprocessareactivatedcarbon(AC)[1-2],metaloxides(e.g.,TiO2,CeO2-MnOx,CeO2-Co3O4,FeOOH,Co3O4[3-6]),andsupportedcatalysts(e.g.,CoOx/Al2O3,Cu-Al2O3,Cu-TiO2,Cu/AC,Fe/AC,Mn/AC,Pt/AC,Ru/AC,Fe2O3/Al2O3,CeO2/AC[6-11]).Supportedcatalystsaremoreattractivetore-searchers,duetothesynergisticeffectoftheirsupportsandac-tivecomponentsinthereaction.Thus,researchersarealwaysin-terestedinthedevelopmentofefficientandstablesupportedcat-alysts.Xerogels/aerogels(classifiedbydryingmethods)[12-15],whichwerefirstdevelopedinthelate1980s,havebeenusedasadsor-bentsandcatalystsbecauseoftheirlargesurfaceareaandporetextureflexibility[16].Recently,transition-metaldopedaerogelswithtunableporositywerepreparedbyadditionofthecorre-spondingmetalsaltstotheinitialmixture[17].Themetalprecursorcancatalyzethepolymerizationorgelationprocess,whichcaninturnaffectthemorphologyandtheporetextureofthexerogel/aerogel[16].Furthermore,itispossibletocombinetheporetextureofthexerogel/aerogelwiththeacidcharacterofthemetallicox-idesincatalyticreactions[18].Cr-,Mo-,W-,Ni-,andPd-dopedaerogels/xerogelshavebeenpreparedandusedascatalystsintheisomerizationreactionof1-buteneandthehydrogenationre-actionofethylene[17,19].Theapplicationofmetal-dopedxerogelsforozonationhasbeenseldomreported[20-21].Inaddition,ironandmanganeseareusuallyusedascatalystsinozonationprocesses,becauseofnotonlytheiroriginalexistenceinnaturalwatersbutalsotheircatalyticabilities.Therefore,inthiswork,wepreparedFe-andMn-dopedxerogelsandtestedtheircatalyticactivityfortheozo-nationofo-DCB,acommonmicro-pollutantinwater.Therela-tionshipbetweenthecatalyticactivityandthepropertiesofxero-gelsampleswasexplored.Meanwhile,theamountofmetalleachingfromthexerogelcatalystswasalsodetermined.1Experimental1.1MaterialsAllchemicalsusedwereofanalyticalgradeunlessstatedoth-erwise.Acetone,formaldehyde(massfractionof37%)andortho-dichlorobenzene(o-DCB,CP)wereobtainedfromSinopharmChemicalReagentCo.,Ltd.(China).ResorcinolwaspurchasedfromTianjinDamaoChemicalReagentFactory(China).Man-ganeseacetatetetrahydratewaspurchasedfromFisherScientificWorldwideCo.,Ltd.(China).Ferrousacetate(massfractionof95%)waspurchasedfromAcrosOrganics(Geel,Belgium).Ac-tivatedcarbon(AC)(YixinIndustrialCo.,Ltd.,China)utilizedintheexperimentswaspreparedfromolivestonesbydirectsteamactivation.Allthecatalystsinthecontextwerecrushedandsievedtoparticleswithasizeof37-74μmpriortoreaction.1.2XerogelpreparationMetal-dopedxerogelswerepreparedbythemethodreportedbyMoreno-Castillaandhiscoworkers[22].Inbrief,resorcinol(R)andformaldehyde(F)were