过渡金属氧化物材料PPT课件

1、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,2,Outline,Applications,Synthesis,Outlook,OMTMO,Mainly in Catalytic,Mechanism & Methodology,Challenge,Introduction,Synthesis,Outlook,Applications,3,2003 The first mesoporous materials

2、 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,Research evolution of mesoporous materials,Introduction-phylogeny,WO3,1992 Periodic mesoporous silicates M41S,N

3、ature, 1992, 359, 710 Nature, 1994,368:317 Angew. Chem.,1995,34, 2014 Nature, 1998, 396, 152 Chem. Commun., 2003, 98,Cr2O3,ZrO2,TiO2,MCM-41,4,Introduction-properties,Large surface areas Uniform pore size Redox activity Electric and optical properties,Photoelectricity,Energy sources,Catalysis,Electro

4、magnetism,Sensor,Electrochemistry,Challenges for transition metal oxides synthesis: Lack of knowledge about other elements except for silicon and aluminum Uncontrolled condensation yields macroscopic phase segregation Difficult to remove the templates and create porous materials,OMTMO,5,Outline,Appl

5、ications,Outlook,OMTMO,Mainly in Catalytic,Challenge,Introduction,Outlook,Applications,6,Synthetic mechanism,Ferdi Schuth, Chem. Mater. 2001, 13, 3184 -3195,Hard templating : Specific topological stability Veracity Predictability Controllability,Soft templating : Amorphous material Structure collaps

6、es,7,Thermodynamics,Basic Principles,Kinetics,Soft templating,Jie Fan et al.,Chem. Mater. 2008, 20, 909921,8,Soft templating (Cont.,The interactions between organic and inorganic species: electrostatic interactions (ionic bonding) van der Waals interactions (hydrogen bonding) covalent bonding,9,olig

7、omers,micellization,self-assemble,Hydrolysis 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, 2067-2077,10,Soft templating (Cont.,Strategies to con

8、trol 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 an

9、d 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 nanop

10、articulate precursors in supramolecular templating,11,Crystallization of mesoporous metal oxides,Junko N. Kondo et al., Chem. Mater. 2008, 20(3): 835847,Crystallization by calcination in air,12,Crystallization of mesoporous metal oxides (Cont.,Reinforcement of pore wall,Junko N. Kondo et al., Chem.

11、Mater. 2008, 20(3): 835847,13,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

12、 pattern (C)SEM image for crystallized mesoporous Ta2O5 with TMOS-CVD support after removal of SiO2,14,Synthetic strategy,Ferdi Schuth, Chem. Mater. 2001, 13, 3184 -3195,Hard templating : Specific topological stability Veracity Predictability Controllability,Soft templating,15,Preparation method: su

13、rface modification method evaporation method solid-liquid method,Nanocasting,Template,16,Nanocasting (Cont.,T. Valdes-Sols et al., Materials Research Bulletin, 41 (2006) 21872197,Nanocasting mechanism,17,Nanocasting-Ordered mesoporous silica mold,In2O3, WO3, Fe2O3, Cr2O3, CeO2, Co3O4, MnxOy, SnO2, N

14、iO,SBA-15,KIT-6,Michael Tiemann, Chem. Eur. J. 2007, 13, 8376- 8388,18,Nanocasting-Carbon cast,TiO2, ZrO2, Al2O3, ZnO, CeO2, CuO, MgO,19,Combined 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,Ti

15、O2 (A) CCM-TiO2C (B) CCM-TiO2CASH,TEM HRTEM and SAED patterns of TiO2,Powder XRD pattern,Nitrogen adsorptiondesorption isotherms & pore size distributions,20,Outline,Outlook,OMTMO,Challenge,Introduction,Synthesis,Outlook,Applications,21,Applications,Stucky et al., Acc. Chem. Res., 2007, 40(9): 784-7

16、92 Pedro Tartaj et al., J. Phys. D: Appl. Phys. 36 (2003) R182R197,In vivo: Hyperthermia drug delivery NMR imaging In vitro: diagnosis,22,Zheng-Rong Tian et al., SCIENCE, 1997, 276: 926-930,Application - oxidation of alkanes,23,Photocatalytic activity for water decomposition,Application,Junko N. Kon

17、do 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 SiO2,24,Outline,OMTMO,Introduction,Synthesis,Outlook,Applications,25,Chiral materials,challenges facing the molecular assembly of

18、 mesostructured materials,Crystallization framwork,External field,Application,Mechanism,Confined space,Outlook,Synthesis,Magnetic, Electric, Flow-field,1D, 2D, 3D confinement,Soft templating,Ordered mesoporous transition- metal oxide materials,Morphology,Hard templating,Maybe,Jie Fan et al., Chem Ma

19、ter., 2008, 20, 909-921,26,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