Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules

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)(center dot+) 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.