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SeminarI(2008.5.27),ResearchProgressofOrderedMesoporousTransition-MetalOxidesMaterials,指导教师:申文杰研究员研究生:郭小惠,Outline,Applications,Synthesis,Outlook,OMTMO,MainlyinCatalytic,Mechanism&Methodology,Challenge,Introduction,Synthesis,Outlook,Applications,2003Thefirstmesoporousmaterialswithsinglecrystallinewall,1998Mesoporousmetaloxideswithsemicrystallineframework,1995/1996Thefirststablemesoporousmaterial,1993/1994Non-silica-basedmesostructuredmaterials,Researchevolutionofmesoporousmaterials,Introduction-phylogeny,WO3,1992PeriodicmesoporoussilicatesM41S,Nature,1992,359,710Nature,1994,368:317Angew.Chem.,1995,34,2014Nature,1998,396,152Chem.Commun.,2003,98,Cr2O3,ZrO2,TiO2,MCM-41,Introduction-properties,LargesurfaceareasUniformporesizeRedoxactivityElectricandopticalproperties,Photoelectricity,Energysources,Catalysis,Electromagnetism,Sensor,Electrochemistry,Challengesfortransitionmetaloxidessynthesis:LackofknowledgeaboutotherelementsexceptforsiliconandaluminumUncontrolledcondensationyieldsmacroscopicphasesegregationDifficulttoremovethetemplatesandcreateporousmaterials,OMTMO,Outline,Applications,Outlook,OMTMO,MainlyinCatalytic,Challenge,Introduction,Outlook,Applications,Syntheticmechanism,FerdiSchuth,Chem.Mater.2001,13,3184-3195,Hardtemplating:SpecifictopologicalstabilityVeracityPredictabilityControllability,Softtemplating:AmorphousmaterialStructurecollapses,Thermodynamics,BasicPrinciples,Kinetics,Softtemplating,JieFanetal.,Chem.Mater.2008,20,909921,Softtemplating(Cont.),Theinteractionsbetweenorganicandinorganicspecies:electrostaticinteractions(ionicbonding)vanderWaalsinteractions(hydrogenbonding)covalentbonding,oligomers,micellization,self-assemble,Hydrolysiscondensation,Covalentbonding,Softtemplating(Cont.),ProposedschemeforthemethodofZr-TMSformationwithanionicamphiphilesandzirconiumn-propoxide,MichaelS.Wongetal.,Chem.Mater.1998,10,2067-2077,Softtemplating(Cont.),Strategiestocontrolthehydrolysis/condensationrates:SpecificpHrangesStabilizingligandsNonaqueousmediaPreformednanoclustersLimitedadditionofwaterMethodsforstrengthingtheporewalls:usingsilicaasaco-supportinaniobium-tungstenoxideframeworkattachinganionicspecies,suchasphosphatesandsulfates,tothezirconiaporewallsurfaceHydrothermallytreatingasurfactant-containingtitania-zirconiamesostructuretocrystallizethetitaniacomponentbeforecalcinationsynthesizingmesostructureswithwallsthickenoughtoallowpartialcrystallizationwithoutporecollapseuseofnanoparticulateprecursorsinsupramoleculartemplating,Crystallizationofmesoporousmetaloxides,JunkoN.Kondoetal.,Chem.Mater.2008,20(3):835847,Crystallizationbycalcinationinair,Crystallizationofmesoporousmetaloxides(Cont.),Reinforcementofporewall,JunkoN.Kondoetal.,Chem.Mater.2008,20(3):835847,Crystallizationofmesoporousmetaloxides(Cont.),Reinforcementofporewall,JunkoN.Kondoetal.,Chem.Mater.2008,20(3):835847,Silica-coatingBTMSaccumulation,High-resolutionTEMimagesofcrystallizedmesoporousNb2O5.,TMOS-CVD,(A)High-resolutionTEMimage(B)EDpattern(C)SEMimageforcrystallizedmesoporousTa2O5withTMOS-CVDsupportafterremovalofSiO2,Syntheticstrategy,FerdiSchuth,Chem.Mater.2001,13,3184-3195,Hardtemplating:SpecifictopologicalstabilityVeracityPredictabilityControllability,Softtemplating:,Preparationmethod:surfacemodificationmethodevaporationmethodsolid-liquidmethod,Nanocasting,Template,Nanocasting(Cont.),T.Valdes-Solsetal.,MaterialsResearchBulletin,41(2006)21872197,Nanocastingmechanism,Nanocasting-Orderedmesoporoussilicamold,In2O3,WO3,Fe2O3,Cr2O3,CeO2,Co3O4,MnxOy,SnO2,NiO,SBA-15,KIT-6,MichaelTiemann,Chem.Eur.J.2007,13,8376-8388,Nanocasting-Carboncast,TiO2,ZrO2,Al2O3,ZnO,CeO2,CuO,MgO,Combinedassemblybysoftandhard(CASH),JINWOOLEEetal.,naturematerials,2008,7,222-228,SchematicrepresentationofCASHmethod,blockcopolymer(PI-b-PEO),TiO2(A)CCM-TiO2C(B)CCM-TiO2CASH,TEMHRTEMandSAEDpatternsofTiO2,PowderXRDpattern,Nitrogenadsorptiondesorptionisotherms&poresizedistributions,Outline,Outlook,OMTMO,Challenge,Introduction,Synthesis,Outlook,Applications,Applications,Stuckyetal.,Acc.Chem.Res.,2007,40(9):784-792PedroTartajetal.,J.Phys.D:Appl.Phys.36(2003)R182R197,Invivo:HyperthermiadrugdeliveryNMRimagingInvitro:diagnosis,Zheng-RongTianetal.,SCIENCE,1997,276:926-930,Application-oxidationofalkanes,-Photocatalyticactivityforwaterdecomposition,Application,JunkoN.Kondoetal.,Chem.Mater.2008,20,835847,(A)High-resolutionTEMimage(B)EDpattern(C)SEMimageforcrystallizedmesoporousTa2O5withTMOS-CVDsupportafterremovalofSiO2,Outline,OMTMO,Introduction,Synthesis,Outlook,Applications,Chiralmaterials,-challengesfacingthemolecularassemblyofmesostructuredmaterials,Crystallizationframwork,Externalfield,Application,Mechanism,Confinedspace,Outlook,Synthesis,Magnetic,Electric,Flow-field,1D,2D,3Dconfinement,Softtemplating,Orderedmesoporoustransition-metaloxidematerials,Morphology,Hardtemplating,Maybe,JieFanetal.,ChemMater.,2008,20,909-921,Antonelli,D.M.etal.,Angew.Chem.Int.Ed.,1995,34,2014CTKresgeetal.,Nature,1992,359,710-712FerdiSchuth,Chem.Mater.2001,13,3184-3195JINWOOLEEetal.,naturematerials,2008,7,222-228J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