Coverage dependence of oxygen decomposition and surface diffusion on rhodium 111: a DFT study.

A systematic study of oxygen adsorption, decomposition and diffusion on Rh111 and its dependence on coadsorbed oxygen molecules has been performed using density functional theory calculations. First, the bonding strength between metal surface and adsorbed oxygen molecules has been studied as a function of initial oxygen coverage. The bonding strength decreases with increasing oxygen coverage, which points towards a self-inhibition of the adsorption process. The potential energy hypersurface (PES) for the dissociation of oxygen molecules adsorbed on a threefold fcc position perpendicular to the surface was calculated using a combined linear/quadratic synchronous transit method with conjugate gradient refinements. The results indicate that a minor amount of oxygen on the surface enhances the decomposition of further oxygen molecules, while this process is inhibited at higher coverage. Moreover, PES calculations of a single site jump of atomic oxygen on rhodium 111 indicate that the activation energy increases as well with increasing oxygen coverage. All results are discussed with respect to a rhodium based catalytic NOx reduction/decomposition system proposed by Nakatsuji, which decomposes nitrogen oxides in oxygen excess.