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Abstract

Well ordered V₂O₃(0001) layers may be grown on Au(111) surfaces. These films are terminated by a layer of vanadyl groups which may be removed by irradiation with electrons, leading to a surface terminated by vanadium atoms. We present a study of methanol adsorption on vanadyl terminated and vanadium terminated surfaces as well as on weakly reduced surfaces with a limited density of vanadyl oxygen vacancies produced by electron irradiation. Different experimental methods and density functional theory are employed. For vanadyl terminated V₂O₃(0001) only molecular methanol adsorption was found to occur whereas methanol reacts to form formaldehyde, methane, and water on vanadium terminated and on weakly reduced V₂O₃(0001). In both cases a methoxy intermediate was detected on the surface. For weakly reduced surfaces it could be shown that the density of methoxy groups formed after methanol adsorption at low temperature is twice as high as the density of electron induced vanadyl oxygen vacancies on the surface which we attribute to the formation of additional vacancies via the reaction of hydroxy groups to form water which desorbs below room temperature. Density functional theory confirms this picture and identifies a methanol mediated hydrogen transfer path as being responsible for the formation of surface hydroxy groups and water. At higher temperature the methoxy groups react to form methane, formaldehyde, and some more water. The methane formation reaction consumes hydrogen atoms split off from methoxy groups in the course of the formaldehyde production process as well as hydrogen atoms still being on the surface after being produced at low temperature in the course of the methanol → methoxy + H reaction.