DFT study on the reaction of O2 dissociation catalyzed by gold surfaces doped with transition metal atoms Original Research Article

Periodic density functional theory (DFT) calculations have been used to study the effect of doping a gold model surface with atoms of other transition metals on the catalysis of the reaction of oxygen dissociation. It was found that the doping of gold surfaces with atoms of Rh, Ir or Ni stabilizes the adsorbate–surface interactions with a concomitant decrease of the activation energy barriers for the oxygen dissociation to values that are smaller than the adsorption energies of molecular oxygen (O2*) on those surfaces. These findings suggest that O2 dissociation is possible at normal conditions on these bimetallic surfaces, which is very relevant not only for the oxidation of CO to CO2 but for other oxidation reactions. In the case of the most active bimetallic surface obtained by doping with Ni atoms, it is shown that the reaction of CO oxidation is more favorable than the reaction of CO dissociation, i.e., suggesting that CO methanation will be less likely. Finally, useful relationships relating the activation energy barrier for the reaction of O2 dissociation with the Bader charge in the doping element, with the reaction energy, with the adsorption energy of the reaction products and with the adsorption energy of an oxygen atom were obtained.