Theoretical study of the influence of Na on CO adsorption and dissociation on Pd(1 1 1): Long-range or short-range interactions between co-adsorbates?

Abstract

The co-adsorption of CO and C, O on Na pre-covered Pd(111) surface are studied by density functional theory (DFT). CO adsorption is affected by the short-range Na–CO electrostatic interactions, especially the Na–O attraction, and the Na-induced long-range surface polarizability as well as the indirect interactions through substrates. Na stabilizes C and O adsorptions, particularly O adsorption, though both C–Pd and O–Pd bonds are elongated. Na reduces CO dissociation barrier by ∼25%. The promotional effects are primarily ascribed to the short-range Na–O electrostatic interaction which stabilizes the transitional state. The Na-induced long-range effects are not significant and hardly promote CO dissociation.