过渡金属氧化物材料

Click to edit Master text styles,Second level,Third level,Fourth level,Fifth level,*,Click to edit Master title style,Seminar I (2008.5.27),Research Progress of Ordered,Mesoporous,Transition-Metal Oxides Materials,指导教师：申文杰 研究员,研 究 生：郭小惠,Outline,Applications,Synthesis,Outlook,OMTMO,Mainly in Catalytic,Mechanism & Methodology,Challenge,Introduction,Phylogeny & Property,Introduction,Synthesis,Outlook,Applications,2003,The first,mesoporous,materials with single crystalline wall,1998,Mesoporous,metal oxides with,semicrystalline,framework,1995/1996,The first stable,mesoporous,material,1993/1994,Non-silica-based,mesostructured,materials,R,esearch evolution of,mesoporous,materials,Introduction-,phylogeny,WO,3,1992 Periodic,mesoporous,silicates M41S,Nature, 1992, 359, 710 Nature, 1994,368:317,Angew,. Chem.,1995,34, 2014 Nature, 1998, 396, 152,Chem.,Commun,., 2003, 98,Cr,2,O,3,ZrO,2,TiO,2,MCM-41,Introduction,-properties,Large surface areas,Uniform pore size,Redox,activity,Electric and optical properties,P,hotoelectricity,Energy sources,Catalysis,E,lectromagnetism,Sensor,Electrochemistry,Challenges for transition metal oxides synthesis:,L,ack of knowle,d,ge about other elements except for silicon and aluminum,Uncontrolled condensation yields macroscopic phase segregation,Difficult to remove the templates and create porous materials,OMTMO,Outline,Applications,Outlook,OMTMO,Introduction,Phylogeny & Property,Mainly in Catalytic,Challenge,Introduction,Synthesis,Mechanism & Methodology,Synthesis,Outlook,Applications,Synthetic mechanism,Ferdi Schuth,Chem. Mater.,2001,13,3184 -3195,Hard,templating,:,Specific topological stability,Veracity,Predictability,Controllability,Soft,templating,:,Amorphous material Structure collapses,Thermodynamics,Basic Principles,Kinetics,Soft,templating,Jie,Fan et,al.,Chem,. Mater.,2008,20,909921,The thermal stability of,mesostructured,metal-oxide phases depends on:,The degree of charge-matching at the organicinorganic interface-,isoelectric,points,The strength of interactions between inorganic species and surfactant head-groups,The flexibility of the MOM bond angles in the constituent metal oxides,The,Tammann,temperature of the metal oxide,The occurrence of,redox,reactions in the metal-oxide wall,M. A.,Carreon,et al.,Eur,. J.,Inorg,. Chem.,2005, 27-43,Nonionic,amphiphile,-zirconium,isopropoxide,interaction,Anionic,amphiphile,-zirconium,n,-propoxide,interaction,S,oft,templating,(Cont.),The interactions between organic and inorganic species:,electrostatic interactions (ionic bonding),van,der,Waals interactions (hydrogen bonding),covalent bonding,oligomers,micellization,self-assemble,H,ydrolysis,condensation,Covalent bonding,Soft,templating,(Cont.),Proposed scheme for the method of,Zr,-TMS formation with anionic,amphiphiles,and zirconium,n,-propoxide,Michael S. Wong et al.,Chem. Mater.,1998,10,2067-2077,S,oft,templating,(Cont.),Strategies to control the hydrolysis/condensation rates:,Specific pH ranges,Stabilizing,ligands,Nonaqueous,media,Preformed,nanoclusters,Limited addition of water,Methods for,strengthing,the pore walls:,using silica as a co-support in a niobium-tungsten oxide framework,attaching anionic species, such as phosphates and sulfates, to the,zirconia,pore wall surface,Hydrothermally treating a surfactant-containing,titania-zirconia,mesostructure,to crystallize the,titania,component before,calcination,synthesizing,mesostructures,with walls thick enough to allow partial crystallization without pore collapse,use of,nanoparticulate,precursors in,supramolecular,templating,Crystallization of,mesoporous,metal oxides,Junko N. Kondo et al.,Chem. Mater.,2008,20(3):,835847,Crystallization by,calcination,in air,Crystallization of,mesoporous,metal oxides (Cont.),Reinforcement of pore wall,Junko N. Kondo et al.,Chem. Mater.,2008,20(3):,835847,Carbon filling consolidation,Crystallization of,mesoporous,metal oxides (Cont.),Reinforcement of pore wall,Junko N. Kondo et al.,Chem. Mater.,2008,20(3):,835847,Silica-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 SiO2,Synthetic strategy,Ferdi Schuth,Chem. Mater.,2001,13,3184 -3195,Hard,templating,:,Specific topological stability,Veracity,Predictability,Controllability,S,oft,templating,:,Preparation method:,surface modification method,evaporation method,solid-liquid method,Nanocasting,Template,Ordered,mesoporous,silica,SBA-15,KIT-6,FDU-12,SBA-16,Ordered,mesoporous,carbon,CMK-3,Nanocasting,(Cont.),T. Valdes-,Sols,et al., Materials Research Bulletin, 41 (2006) 21872197,Nanocasting,mechanism,Nanocasting,-,Ordered,mesoporous,silica mold, In,2,O,3, WO,3, Fe,2,O,3, Cr,2,O,3, CeO,2, Co,3,O,4,Mn,x,O,y,SnO,2,NiO,Co,3,O,4,NiO,CeO,2,Cr,2,O,3,SBA-15,KIT-6,Michael,Tiemann, Chem.,Eur,. J. 2007, 13, 8376- 8388,Co,3,O,4,NiO,CeO,2,Cr,2,O,3,Wenbo,Yue,et al.,Chem. Mater.,2007,19,2359-2363,Nanocasting,-,Carbon cast, TiO,2, ZrO,2, Al,2,O,3,ZnO, CeO,2,CuO,MgO,Waitz,et al.,Appl,. Phys.,Lett,. 2007, 90: 1231081-3,ZnO,50 nm,Jan,Roggenbuck,et al., J. AM. CHEM. SOC., 2005, 127(4): 1096-1097,MgO,60 nm,C,ombined assembly by soft and hard (CASH),JINWOO LEE et al.,nature materials,2008, 7, 222-228,Schematic representation of CASH method,block copolymer (PI-,b,-PEO),TiO2,(A) CCM-TiO,2,C (B) CCM-TiO,2,CASH,TEM HRTEM and SAED patterns of TiO,2,Powder XRD pattern,Nitrogen adsorption,desorption,isotherms,& pore size distributions,Outline,Outlook,OMTMO,Introduction,Phylogeny & Property,Applications,Mainly in Catalytic,Synthesis,Mechanism & Methodology,Challenge,Introduction,Synthesis,Outlook,Applications,Applications,Stucky,et al.,Acc. Chem. Res.,2007, 40(9):,784-792,Pedro,Tartaj,et al., J. Phys. D:,Appl,. Phys. 36 (2003) R182R197,I,n vivo:,H,yperthermia,drug delivery,NMR imaging,In vitro:,diagnosis,Zheng-Rong,Tian,et al., SCIENCE, 1997, 276: 926-930,A,pplication -,oxidation of,alkanes,-,P,hotocatalytic,a,ctivity,for water decomposition,Application,Junko 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 SiO2,Introduction,Phylogeny & Property,Outline,OMTMO,Applications,Mainly in Catalytic,Synthesis,Mechanism & Methodology,Outlook,Challenge,Introduction,Synthesis,Outlook,Applications,Chiral,materials,-challenges facing the molecular assembly of,mesostructured,materials,C,rystallization,framwork,External field,A,pplication,M,echanism,Confined space,Outlook,S,ynthesis,Magnetic, E,lectric, Flow-field,1D, 2D, 3D,confinement,Soft,templating,O,rdered,mesoporous,transition- metal oxide materials,Morphology,Hard,templating,M,aybe,Jie,Fan et al.,Chem,Mater., 2008, 20, 909-921,Antonelli,D.M.et,al.,Angew,. Chem. Int. Ed., 1995, 34, 2014,C T,Kresge,et al.,Nature, 1992, 359, 710-712,Ferdi,Schuth,Chem. Mater.,2001,13,3184 -3195,JINWOO LEE et al.,nature materials, 2008, 7, 222-228,Jie,Fan et al.,Chem,Mater., 2008, 20, 909-921,Junko N. Kondo et al,Chem. Mater.,2008, 20,835-847,Jan,Roggenbuck,et al., J. AM. CHEM. SOC., 2005, 127(4): 1096-1097,Kake,Zhu et al.,Chem.,Commun,., 2003, 1, 98-99,M. A.,Carreon,et al.,Eur,. J.,Inorg,. Chem.,2005, 27-43,Michael,Tiemann,Chem.,Eur,. J.,2007, 13, 8376-8388,Michael S. Wong et al.,Chem. Mater.,1998,10,2067-2077,Pedro,Tartaj,et al., J. Phys. D:,Appl,. Phys. 36 (2003) R182R197,Qisheng,Huo,et al.,Nature, 1994, 368, 317-321,Stucky,et al.,Acc. Chem. Res.,2007, 40(9):,784-792,Wenbo,Yue,et al.,Chem. Mater.,2007,19,2359-2363,Waitz,et al.,Appl,. Phys.,Lett,. 2007, 90: 1231081-3,Xiaoyong,Lai et al,Angew,. Chem. Int. Ed.,2007, 46, 738-741,Yang,P.D.et,al., Nature, 1998, 396: 152,Yoshiko,Takahara,et al.,Chem. Mater.,2001,13,1194-1199,Reference,Thank You !,