title: Mechanisms of initial propane activation on molybdenum oxides: a density functional theory study.
abstract: We report the first detailed density functional theory study on the mechanisms of initial propane activation on molybdenum oxides. We consider 6 possible mechanisms of the C-H bond activation on metal oxides, leading to 17 transition states. We predict that hydrogen abstraction by terminal Mo=O is the most feasible reaction pathway. The calculated activation enthalpy and entropy are 32.3 kcal/mol and -28.6 cal/(mol/K), respectively, in reasonably good agreement with the corresponding experimental values (28.0 kcal/mol and -29.1 cal/(mol/K)). We find that activating the methylene C-H bond is 4.7 kcal/mol more favorable than activating the methyl C-H bond. This regioselectivity is correlated with the difference in strength between a methylene C-H bond and a methyl C-H bond. Our calculations suggest that a combined effect from both the methylene and the methyl C-H bond cleavages leads to the experimentally observed overall kinetic isotopic effects from propane to propylene on the MoO(x)/ZrO(2) catalysts.
authors.affiliation: Department of Chemistry and Institute of Physical Chemistry, State Key Laboratory for Physical Chemistry of Solid Surfaces and Center for Theoretical Chemistry, Xiamen University, Xiamen 361005, China.
authors.forename: Gang
authors.initials: G
authors.lastname: Fu
authors.forename: Xin
authors.initials: X
authors.lastname: Xu
authors.forename: Xin
authors.initials: X
authors.lastname: Lu
authors.forename: Huilin
authors.initials: H
authors.lastname: Wan