Unravelling CO Activation on Flat and Stepped Co Surfaces: A Molecular Orbital Analysis

Structure sensitivity in heterogeneous catalysis dictates the overall activity and selectivity of a catalyst whose origins lie in the atomic configurations of the active sites. We explored the influence of the active site geometry on the dissociation activity of CO by investigating the electronic structure of CO adsorbed on 12 different Co sites and correlating its electronic structure features to the corresponding C-O dissociation barrier. By including the electronic structure analyses of CO adsorbed on step-edge sites, we expand upon the current models that primarily pertain to flat sites. The most important descriptors for activation of the C-O bond are the decrease in electron density in CO’s 1π orbital , the occupation of 2π anti-bonding orbitals and the redistribution of electrons in the 3σ orbital. The enhanced weakening of the C-O bond that occurs when CO adsorbs on sites with a step-edge motif as compared to flat sites is caused by a distancing of the 1π orbital with respect to Co. This distancing reduces the electron-electron repulsion with the Co d-band. These results deepen our understanding of the electronic phenomena that enable the breaking of a molecular bond on a metal surface.