工业钛液制备介孔TiO2及其催化性能研究

412四川大学学报(工程科学版)Vol.41No.220093JOURNALOFSICHUANUNIVERSITY(ENGINEERINGSCIENCEEDITION)Mar.2009　　:1009-3087(2009)02-0103-05TiO2田从学1,2,张　昭1＊,张明俊1,罗　妮1(1.,610065;2.,617000)　:,CTAB/P123、TiO2,、、TiO2。XRD、、N2FT-IR。、TiO2。,,,TiO2,3.23nm,SBET281.5m2/g。,TiO2,。:;;;;:O614.41;TQ424.25:APreparationofMesoporousTitaniafromIndustrialTitanylSulfateanditsCatalyticPerformancesTIANCong-xue1,2,ZHANGZhao1＊,ZHANGMing-jun1,LUONi1(1.SchoolofChem.Eng.,SichuanUniv.,Chengdu610065,China;2.SchoolofBiologicalandChemicalEng,PanzhihuaUniv.,Panzhihua617000,China)Abstract:UsingindustrialtitanylsulfatesolutionasTisource,theprecursorofmesoporousTiO2wassynthesizedviasupramolecularself-assemblyrouteundercompositetemplates(CTAB/P123),whichinducedthehydrolysisandcondensationoftitanium.MesoporousTiO2wasobtainedaftertemplateremovalbyozoneoxidation,multipleextrac-tionandmulti-stepcalcinations.ThesampleswerecharacterizedbyXRD,particlesizedistribution,N2absorptionanddesorptionmethodandFT-IR.Theprecursor,intermediateandproductwereallanataseTiO2withmesoporousstructureofhexagonalarrangement.Thetotaltitaniacontentandcrystallinitywereincreasedwithtemplateremoval,andmesoporousTiO2hadanarrowporesizedistribution,withSBETof281.5m2/g,averageporediameterof3.23nm.ThecatalyticperformanceofmesoporousTiO2wasstrengthenedbytheincteaseofspecificsurfacearea,ana-tasecrystalimprovementandsmallamountofSO42-absorptionandbonding.AndresultsshowedthatTiO2sampleshavehighactivityonphotocatalyticoxidationofmethyleneblueandesterificationforethylacetate.Keywords:mesoporoustitania;industrialtitanylsulfate;compositetemplates;photocatalysis;esterification:2008-06-29:(50474071):(1973-),,,.:.　＊E-mail:[e-mail]:10.15961/j.jsuese.2009.02.002　　1972Fujishima,、、、,、、、,、[1-3〗。MCM-41,[4〗。TiO2,,,,、、、、。TiO2,、[5〗。SO42-/MxOy,,SO42-/TiO2[6〗,TiO2。TiO2,Sol-Gel,。,、TiO2[7-9〗,,。,,,、TiO2,、TiO2,,。1　1.1　(CTAB)EO20PO70EO20(P123)/(1∶3,),,。(TiOSO4,TiO2260.25g/L,512g/L,1.97,0.19)1∶1()。100℃,70℃,70℃,1∶1pH,。:Ti/CTAB/P123=1∶0.2∶0.02,H2O/Ti=30∶1,70℃4h,120℃2h。、,110℃TiO2,A。A36h、/4,B。B,10℃/min,125℃1h,300℃1h,450℃2h,TiO2,C。D。XRDPHILIPS'X(XPertproMPD),CuKα1(λ=0.154056nm),:2θ=1～10°,2θ=20～70°;N2-(Quantachrome,NOVA1000e),BET,BJH;(Nicolet560),KBr,400～4000cm-1,0.05cm-1,20cm-1/min;(JL-1166);、;,。1.2　,4W,365nm。60mg/L,1.0g/L;,40L/h。,10min,。,10min,,721678nm。。=(A0-A)/A0×100%。,A010min,A。1.3　0.2mol、0.4mol,0.9493g(3%),80℃,30min104()41　,,()。2　2.1　XRD1、2。1　TiO2XRDFig.1　LowangleX-raydiffractionpatternsoftitania2　TiO2XRDFig.2　WideangleX-raydiffractionpatternsoftitaniaA、B、C2.2～2.5°,,(100)、(110)(200),2θ=2.2～2.5°d1003.5～3.9nm,,,[10〗。、,,-。D,。(100)d1001。XRD(2),TiO2(JCPDS21-1272)(2),,TiO2。A,B,,,,,C,TiO2。2DC,。TiO2TiO2[5〗。1,(d),(SBET)(ST)。1　TiO2Tab.1　PhysicochemicalpropertiesandstructureofTiO2d100/nmw(TiO2)/%d/μmSBET/(m2·g-1)ST/%A3.8969.251.62264.91.36B3.7886.001.43235.40.89C3.5692.100.96281.50.93D-95.861.25121.21.00　　1,TiO2,,C。,TiO2,,,,C。DA、BC。TiO2230m2/g,CSBET281.5m2/g,D,。3CN2。3(a),N2,ⅣLangmiur-,H1,0.40～0.80,TiO2,,[11〗,XRD。(3(b)),,3.56nm,BJHVP=0.187cm3/g,DBJH=3.23nm。TiO2,,SO42-,105　2,:TiO2(a)(b)3　TiO2N2(a)(b)Fig.3　Nitrogenisotherms(a)andporesizedistribu-tion(b)ofmesoporoustitania1%(1)。TiO2,,B,,450℃,,CB。4。4　FT-IRFig.4　FT-IRpatternsofthesamples,,,C—H(2800～2900cm-1)(1500cm-1),,1。FT-IR1047cm-11129cm-1SO42-。,,。2.2　TiO25。5　TiO2Fig.5　PhotocatalyticoxidationactivityofTiO2onMethyleneBlueC,D,AB。,C,,,,,120min98.4%,。A、B,,,A、B,D。,,TiO2,[12〗。,TiO2。2.3　TiO2B、C、D、6。6,TiO2D,C,90min106()41　91%。6　TiO2Fig.6　CatalyticactivityofTiO2onesterificationofeth-ylacetateSO42-TiO21210～1213cm-1,1125～1137cm-1,1047～1051cm-1,[13〗。SOTi—O,L,H2O,。30.89%～1.00%,,,,,,。CB,,,B。3　　,CTAB、P123TiO2,、、,SO42-TiO2。:,TiO2,,SO42-,。,,TiO2。:[1]FujishimaA,HondaK.Electrochemicalphotolysisofwateratasemiconductorelectrode[J〗.Nature,1972,238(5358):37-38.[2〗OllisDF,AlEH.Photocatalysticpurificationandtreat-mentofwaterandair[M〗.Elseevier,Amsterdam,1993.[3〗FoxMA,DulayMT.Heterogeneousphotocatalysis[J〗.ChemRev,1993,93:341-357.[4〗KresgeCT,LeonowiezME,RothWJ,etal.Orderedmesoporousmolecularsievessynthesizedbyliquid-crystaltemplatemechanism[J〗.Nature,1992,359(6397):710-712.[5〗WangY,JiangZH,YangFJ.Preparationandphotocata-lyticactivityofmesoporousTiO2derivedfromhydrolysiscondensationwithTX-100astemplate[J〗.MaterialsSci-enceandEngineeringB,2006,128(1):229-233.[6〗ArataK,HinoM,YamagataN.Acidityandcatalyticactiv-ityofzirconinmandtianiumsulfatesheat-treatedathightemperature.SolidSuperacidCatalysts[J〗.BullChemSocJpn,1990,63:244-266.[7〗TianCongxue,ZhangZhao,HeJingping,etal.SynthesisoforderedmesoporousTiO2fromindustrialTiOSO4bycom-positesurfactantstemplatemethod[J〗.JournalofSichuanUniversity:EngineeringScienceEdition,2006,38(1):63-67[,,,.TiOSO4TiO2[J〗.:,2006,38(1):63-67.〗[8〗TianCongxue,ZhangZhao,HeJingping,etal.Thermaltreatmentstudyfortheprecursorofmesoporoustitania[J〗.RareMetalMaterEng,2006,35(Z2):185-189[,,,.TiO2[J〗.,2006,35(Z2):185-189.〗[9〗LiuQiang,TianCongxue,ZhangZhao.Compositetemplatesynthesisofmesoporoustitaniaanditstemplateremoval[J〗.TheChineseJournalofNonferrousMetals,2007,17(5):807-812.[,,.[J〗.,2007,17(5):8