多相催化过程的分子层次研究.ppt

Cluster Geometry Reactivity ΔHr/eV Barrier/eV FeO 无 -1.248 0.24 FeO2 强 -1.838 -0.08 FeO3 弱 -2.485 0.06/Spin inversion Fe2O4 无 --------- ---------- Fe2O5 无 -2.279 0.34 ⅰ、不同表面形貌Fe2O3纳米颗粒的催化反应势垒不同 ⅱ、Fe2O3纳米颗粒625K下经过O2氧化体现低催化活性，773K下经过H2还原体现出高催化活性。 + 模型化，试图寻求实验观察现象背后的本质原因！ Density Functional Theory:Possiblity to solve a scientific problem or explain a experimental phenomenon, and how to ? Example:Experimental and theoretical Study of the reactions between neutral vanadium oxide clusters and ethylene and propene. Time-of-flight Mass Spectrometry&DFT ZC.Wang, to be submitted to Organometallics(2007) Example:O-Atom Transport Catalysis by Atomic Cations in the Gas Phase Reduction of N2O by CO.ICP/SIFT&DFT D. Kumar,J.Am.Chem.Soc.127,3545 (2005) G.K.Koyanagi, Int. J. Mass Spectrom. 2000, 194, L1. Example:Coadsorption of CO and O2 on Selected Gold Clusters: Evidence for Efficient Room-Temperature CO2 Generation. Time-of-flight Mass Spectrometry&DFT W.T. Wallace,J.Am.Chem.Soc.124,7499 (2002). Example:Reactivity of Atomic Gold Anions toward Oxygen and the Oxidation of CO: Experiment and Theory.TOFMS&DFT M.L.Kimble,J.Am.Chem.Soc.126,2526 (2004) Example:Theoretical and Experimental Consideration of the Reactions between VxOy+ and Ethylene. Guided Ion Beam Mass Spectrometer&DFT D.R.Justes,J.Am.Chem.Soc.125,6289 (2003) Energetic profile for the reaction between (a) V2O5+ and (b) V4O10+ and C2H4 Example:The Structures of Vanadium Oxide Cluster-Ethene Complexes. A Combined IR Multiple Photon Dissociation Spectroscopy and DFT Calculation Study A. Fielicke,J.Am.Chem.Soc.125,15716 (2003) Infrared multiple photon dissociation (IR-MPD) spectra of V2O5C2H4+ (I) and V2O6C2H4 + (II) together with calculated spectra for several isomers. Example:Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. STM&DFT (a) Calculated free energy diagram for HER on different materials (vs.NHE at pH = 0) shows the promising characteristics of nanoparticulate MoS2.