Partial oxidation of methanol on well-ordered V(2)O(5)(001)/Au(111) thin films

The partial oxidation of methanol to formaldehyde on well-ordered thin V(2)O(5)(001) films supported on Au(111) was studied. Temperature-programmed desorption shows that bulk-terminated surfaces are not reactive, whereas reduced surfaces produce formaldehyde. Formaldehyde desorption occurs between 400 K and 550 K, without evidence for reaction products other than formaldehyde and water. Scanning tunnelling microscopy shows that methanol forms methoxy groups on vanadyl oxygen vacancies. If methanol is adsorbed at low temperature, the available adsorption sites are only partly covered with methoxy groups after warming up to room temperature, whereas prolonged methanol dosing at room temperature leads to full coverage. In order to explain these findings we present a model that essentially comprises recombination of methoxy and hydrogen to methanol in competition with the reaction of two surface hydroxyl groups to form water.