Surface reactions on inverse model catalysts: CO adsorption and CO hydrogenation on vanadia- and ceria-modified surfaces of rhodium and palladium

Reducible transition metal oxides are well-known promoters of the hydrogenation of CO on noble metal surfaces. In this study the promotional effect of vanadia and ceria adlayers on Rh and Pd surfaces was investigated with emphasis on the effect of the oxidation state on CO adsorption and catalytic activity. Inverse supported catalysts were prepared by UHV deposition of V and Ce on the noble metal surface (Rh(111), Pd(111) or Rh foil). After oxidation and specified reduction, the reaction kinetics on polycrystalline Rh was measured at atmospheric pressure, and the molecular and dissociative chemisorption of CO on Rh(111) and Pd(111) and the methanation kinetics on Rh(111) were investigated by molecular beam techniques. On Rh(111), the probability of CO dissociation and the reaction rate are enhanced by submonolayer VO_x deposits. Local pressures between 10^-2 and 1 mbar are sufficient to drive the methanation at 573 K with measurable amounts of products, accompanied by significant restructuring of the catalyst surface. Although the reaction on Rh is generally promoted by small quantities of vanadia and ceria, the reaction rates depend strongly on the extent and temperature of hydrogen reduction. The observed increase of the reaction rate by reduction up to 673 K can be correlated to concomitant changes of the structure and composition of the VO_x deposits. If the reduction temperature is raised above 673 K, metallic V is partially dissolved in the bulk, and the resulting V/Rh subsurface alloy exhibits a particularly high activity. Contrary to vanadia, ceria islands on Rh promote the initial reaction only after a low-temperature reduction, but the activity decreases after reduction above 573 K.