Density functional theory study of CO adsorption on molybdenum sulfide.

CO adsorption on four MoSx (stoichiometric and nonstoichiometric) clusters has been investigated by using density functional method. It is found that CO prefers adsorption on the coordinatively unsaturated (1010) surface. The adsorption energy of high coverage shows the additivity as compared with that of one CO adsorption, and there is no significant repulsive interaction between the end-on adsorbed CO probes. The computed CO stretching frequencies (2000-2080 cm(-1)) agree perfectly with the experimental data (a broad band centered at 2070 cm(-1) with a tail extent to 2000 cm(-1)). No bridged CO adsorption is favored energetically under high CO concentration, and this might explain the catalytic ability of MoSx for C1 products instead of higher hydrocarbons and alcohols.