title: Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules.
abstract: The oxidation of methanol to formaldehyde on silica supported vanadium oxide is studied by density functional theory. For isolated vanadium oxide species silsesquioxane-type models are adopted. The first step is dissociative adsorption of methanol yielding CH3O(O=)V(O-)2 surface complexes. This makes the O=V(OCH3)3 molecule a suited model system. The rate-limiting oxidation step involves hydrogen transfer from the methoxy group to the vanadyl oxygen atom. The transition state is biradicaloid and needs to be treated by the broken-symmetry approach. The activation energies for O=V(OCH3)3 and the silsesquioxane surface model are 147 and 154 kJ/mol. In addition, the (O=V(OCH3)3)(2) dimer (a model for polymeric vanadium oxide species) and the O=V(OCH3)3(*+) radical cation are studied. For the latter the barrier is only 80 kJ/mol, indicating a strong effect of the charge on the energy profile of the reaction and questioning the significance of gas-phase cluster studies for understanding the activity of supported oxide catalysts.
authors.affiliation: Institut für Chemie der Humboldt Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany.
authors.forename: Jens
authors.initials: J
authors.lastname: Döbler
authors.forename: Marc
authors.initials: M
authors.lastname: Pritzsche
authors.forename: Joachim
authors.initials: J
authors.lastname: Sauer