Kinetics and thermodynamics of H2O dissociation and CO oxidation on the Pt/WC (0001) surface: A density functional theory study

Abstract

Adsorptions of H2O and CO on the Pt/WC(0001) [pseudomorphic platinum monolayer on WC(0001)] surface have been studied with periodical slab model by PW91 approach of GGA within the framework of density functional theory (DFT). The reaction pathways and mechanisms of H2O dissociation and CO oxidation are also investigated. For a comparison, similar calculation scheme are performed on the Pt (111) surface as well. The adsorption energies of H2O and CO on both concerned surfaces suggest that H2O binds preferentially on the Pt/WC (0001) surface, while CO prefers the metal surface Pt (111), agreeing well with the experimental observation that the tungsten carbides based material is less susceptible to CO poisoning than platinum. The activation energies for the stepwise H2O dehydrogenation reaction show that the progress of H2O dissociation is similar on the two surfaces; and coincidentally the oxidation of CO by surface hydroxyl is much more likely to occur than that by surface oxygen which comes up with the H2O dissociation. Although the activation barrier of H2O dissociation on the Pt/WC (0001) is similar to that on Pt (111), the key oxidant OH specials which play a key role in turning over surface carbon monoxide to carbon dioxide prefer the Pt/WC(0001) surface, and the improved CO oxidation reaction progress confirms that the Pt/WC surface is more CO-tolerant than the pure Pt. According to the electronic structure analysis we find that the increased CO tolerance is ascribed to the downshift of Pt d-band center because of the charge transfer from WC support to the coating surface.