title: Mechanisms of methane activation and transformation on molybdenum oxide based catalysts.
abstract: We present a comprehensive survey of different C-H activation pathways over various kinds of active sites of terminal oxygens [=O] and bridge oxygens [-O-] by using Mo3O9 model systems. This allows us to provide some insights into fundamental issues concerning C-H activation by metal oxo species involved in many heterogeneous, homogeneous, and enzymatic processes. We show that H abstraction is the most feasible reaction pathway for the activation of a C-H bond on molybdenum oxides; and that [=O] is more active than [-O-]. Our calculations also suggest that (2+2) can be an alternative if M=O bond possesses a high polarity, while (5+2) can provide another effective pathway if two M=O bonds are in close proximity. Implications for the related heterogeneous, homogeneous, and enzymatic processes are discussed.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, Department of Chemistry and Institute of Physical 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