过渡金属氧化物材料.ppt

Seminar I(2008.5.27)Research Progress of Ordered Mesoporous Research Progress of Ordered Mesoporous Transition-Metal Oxides MaterialsTransition-Metal Oxides Materials指导教师：申文杰指导教师：申文杰 研究员研究员研研 究究 生：郭小惠生：郭小惠 OutlineApplications SynthesisOutlookOMTMOOMTMOMainly in Catalytic Mechanism&MethodologyChallengeIntroductionPhylogeny&Property2003 The first mesoporous materials with single crystalline wall1998Mesoporous metal oxides with semicrystalline framework1995/1996The first stable mesoporous material1993/1994 Non-silica-based mesostructured materialsResearch evolution of mesoporous materialsIntroduction-phylogeny WO31992 Periodic mesoporoussilicates M41SNature,1992,359,710 Nature,1994,368:317 Angew.Chem.,1995,34,2014 Nature,1998,396,152 Nature,1992,359,710 Nature,1994,368:317 Angew.Chem.,1995,34,2014 Nature,1998,396,152 Chem.Commun.,2003,98 Cr2O3ZrOZrO2 2TiO2MCM-41Introduction-properties JLarge surface areas JUniform pore size JRedox activity JElectric and optical propertiesPhotoelectricity Energy sources CatalysisElectromagnetism Sensor Electrochemistry Challenges for transition metal oxides synthesis:Challenges for transition metal oxides synthesis:L Lack of knowleack of knowled dge about other elements except for silicon and aluminumge about other elements except for silicon and aluminumUncontrolled condensation yields macroscopic phase segregationUncontrolled condensation yields macroscopic phase segregationDifficult to remove the templates and create porous materialsDifficult to remove the templates and create porous materialsOMTMOOMTMOOutlineApplications OutlookOMTMOOMTMOIntroductionPhylogeny&PropertyMainly in Catalytic ChallengeSynthesisMechanism&Methodology Synthetic mechanismFerdi Schuth,Chem.Mater.2001,13,3184-3195Hard templating:Specific topological stabilityVeracityPredictabilityControllabilitySoft templating:Amorphous material Structure collapses ThermodynamicsBasic PrinciplesKineticsSoft templatingJie Fan et al.,Chem.Mater.2008,20,909921The thermal stability of mesostructured metal-oxide phases depends on:1.The degree of charge-matching at the organicinorganic interface-isoelectric points2.The strength of interactions between inorganic species and surfactant head-groups3.The flexibility of the MOM bond angles in the constituent metal oxides 4.The Tammann temperature of the metal oxide5.The occurrence of redox reactions in the metal-oxide wallM.A.Carreon et al.,Eur.J.Inorg.Chem.2005,27-43Nonionic amphiphile-zirconium isopropoxide interactionAnionic amphiphile-zirconium n-propoxide interactionSoft templating(Cont.)The interactions between organic and inorganic species:velectrostatic interactions(ionic bonding)vvan der Waals interactions(hydrogen bonding)vcovalent bondingoligomersmicellizationself-assembleHydrolysis condensationCovalent bondingSoft templating(Cont.)Proposed scheme for the method of Zr-TMS formation with anionic amphiphiles and zirconium n-propoxideMichael S.Wong et al.,Chem.Mater.1998,10,2067-2077Soft templating(Cont.)Strategies to control the hydrolysis/condensation rates:JSpecific pH rangesJStabilizing ligandsJNonaqueous mediaJPreformed nanoclustersJLimited addition of waterMethods for strengthing the pore walls:Jusing silica as a co-support in a niobium-tungsten oxide frameworkJattaching anionic species,such as phosphates and sulfates,to the zirconia pore wall surfaceJHydrothermally treating a surfactant-containing titania-zirconia mesostructure to crystallize the titania component before calcinationJsynthesizing mesostructures with walls thick enough to allow partial crystallization without pore collapseJuse of nanoparticulate precursors in supramolecular templatingCrystallization of mesoporous metal oxidesJunko N.Kondo et al.,Chem.Mater.2008,20(3):835847vCrystallization by calcination in airCrystallization of mesoporous metal oxides(Cont.)vReinforcement of pore wall Junko N.Kondo et al.,Chem.Mater.200820(3):835847Carbon filling consolidationCrystallization of mesoporous metal oxides(Cont.)vReinforcement of pore wall Junko N.Kondo et al.,Chem.Mater.2008,20(3):835847Silica-coating BTMS accumulation High-resolution TEM images of crystallized mesoporous Nb2O5.TMOS-CVD(A)High-resolution TEM image(B)ED pattern(C)SEM image for crystallized mesoporous Ta2O5 with TMOS-CVD support after removal of SiO2Synthetic strategyFerdi Schuth,Chem.Mater.2001,13,3184-3195Hard templating:Specific topological stabilityVeracityPredictabilityControllabilitySoft templating:Preparation method:vsurface modification methodvevaporation methodvsolid-liquid methodNanocasting TemplateOrdered mesoporous silicaSBA-15KIT-6FDU-12SBA-16Ordered mesoporous carbon CMK-3Nanocasting(Cont.)T.Valdes-Sols et al.,Materials Research Bulletin,41(2006)21872197Nanocasting mechanismNanocasting-Ordered mesoporous silica mold In2O3,WO3,Fe2O3,Cr2O3,CeO2,Co3O4,MnxOy,SnO2,NiOCo3O4NiOCeO2Cr2O3SBA-15KIT-6KIT-6Michael Tiemann,Chem.Eur.J.2007,13,8376-8388Co3O4NiOCeO2Cr2O3Wenbo Yue et al.,Chem.Mater.2007,19,2359-2363Nanocasting-Carbon cast TiO2,ZrO2,Al2O3,ZnO,CeO2,CuO,MgOWaitz et al.,Appl.Phys.Lett.2007,90:1231081-3ZnO50 nm50 nmJan Roggenbuck et al.,J.AM.CHEM.SOC.,2005,127(4):1096-1097MgO60 nm60 nmCombined assembly by soft and hard(CASH)JINWOO LEE et al.,nature materials,2008,7,222-228Schematic representation of CASH methodblock copolymer(PI-b-PEO)TiO2 TiO2(A)CCM-TiO2C(B)CCM-TiO2CASHTEM HRTEM and SAED patterns of TiO2Powder XRD patternNitrogen adsorptiondesorption isotherms&pore size distributionsOutlineOutlookOMTMOOMTMOIntroductionPhylogeny&PropertyApplications Mainly in Catalytic SynthesisMechanism&MethodologyChallengeApplications Stucky et al.,Acc.Chem.Res.,2007,40(9):784-792Pedro Tartaj et al.,J.Phys.D:Appl.Phys.36(2003)R182R197In vivo:Hyperthermiadrug deliveryNMR imaging In vitro:diagnosisZheng-Rong Tian et al.,SCIENCE,1997,276:926-930 Application-oxidation of alkanes-Photocatalytic activity for water decompositionApplicationJunko N.Kondo et al.,Chem.Mater.2008,20,835847(A)High-resolution TEM image(B)ED pattern(C)SEM image for crystallized mesoporous Ta2O5 with TMOS-CVD support after removal of SiO2IntroductionPhylogeny&PropertyOutlineOMTMOOMTMOApplications Mainly in Catalytic SynthesisMechanism&MethodologyOutlookChallengeChiral materials-challenges facing the molecular assembly of mesostructured materialsCrystallizationCrystallizationframworkframworkExternal fieldApplication Application Mechanism Mechanism Confined spaceOutlookOutlookSynthesis Synthesis Magnetic,Electric,Flow-field1D,2D,3D confinementSoft templatingOrdered mesoporous Ordered mesoporous transition-metal oxide materialstransition-metal oxide materialsMorphology Hard templatingMaybe Maybe Jie Fan et al.,Chem Mater.,2008,20,909-921Jie Fan et al.,Chem Mater.,2008,20,909-9211.Antonelli,D.M.et al.,Angew.Chem.Int.Ed.,1995,34,2014 2.C T Kresge et al.,Nature,1992,359,710-7123.Ferdi Schuth,Chem.Mater.2001,13,3184-31954.JINWOO LEE et al.,nature materials,2008,7,222-2285.Jie Fan et al.,Chem Mater.,2008,20,909-9216.Junko N.Kondo et al,Chem.Mater.,2008,20,835-8477.Jan Roggenbuck et al.,J.AM.CHEM.SOC.,2005,127(4):1096-10978.Kake Zhu et al.,Chem.Commun.,2003,1,98-999.M.A.Carreon et al.,Eur.J.Inorg.Chem.2005,27-4310.Michael Tiemann,Chem.Eur.J.2007,13,8376-838811.Michael S.Wong et al.,Chem.Mater.,1998,10,2067-207712.Pedro Tartaj et al.,J.Phys.D:Appl.Phys.36(2003)R182R19713.Qisheng Huo et al.,Nature,1994,368,317-321 14.Stucky et al.,Acc.Chem.Res.,2007,40(9):784-792 15.Wenbo Yue et al.,Chem.Mater.2007,19,2359-236316.Waitz et al.,Appl.Phys.Lett.2007,90:1231081-317.Xiaoyong Lai et al,Angew.Chem.Int.Ed.,2007,46,738-74118.Yang,P.D.et al.,Nature,1998,396:152 19.Yoshiko Takahara et al.,Chem.Mater.2001,13,1194-1199Reference