title: Kinetics and mechanism of olefin epoxidation with aqueous H2O2 and a highly selective surface-modified TaSBA15 heterogeneous catalyst.
abstract: The reaction kinetics of cyclohexene epoxidation using aqueous H2O2 oxidant and the highly selective epoxidation catalyst Bu(cap)TaSBA15 were studied. The reaction was determined to be first-order in Ta(V) surface coverage. The reaction rate exhibited saturation with respect to increasing concentrations of cyclohexene and H2O2. An Eley-Rideal mechanism and rate equation may be used to describe the epoxidation kinetics, which are similar to those for Ti(IV)SiO2-catalyzed epoxidations. The observed kinetics may also be modeled by a double-displacement mechanism typically associated with saturation enzyme catalysts. In addition, (1)H NMR spectroscopy was employed to investigate H2O2 decomposition by Bu(cap)TaSBA15 and the unmodified TaSBA15 catalysts. Little decomposition occurred over the surface-modified material, but the unmodified material catalyzed a 30% conversion of H2O2 after 6 h. UV-visible absorbance and diffuse reflectance UV-visible (DRUV-vis) spectroscopy were used to investigate the structure of the Ta centers on the TaSBA15 catalysts. DRUV-vis spectroscopy was also used to identify a Ta(V)-based epoxidation intermediate, proposed to be a Ta(V)(eta(2)-O2) species, which forms upon reaction of the TaSBA15 and Bu(cap)TaSBA15 materials with H2O2.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Ruddy
authors.forename: T Don
authors.initials: TD
authors.lastname: Tilley
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties; D013635:Tantalum / Q000737:chemistry*; D013997:Time Factors; D014867:Water / Q000737:chemistry
chemical_list: D000475:Alkenes; D004852:Epoxy Compounds; D014867:Water; D013635:Tantalum; D012822:Silicon Dioxide; D006861:Hydrogen Peroxide