Vacancy formation and CO adsorption on gold-doped ceria surfaces

We study the effect of gold doping on oxygen vacancy formation and CO adsorption on the (1 1 0) and (1 0 0) surfaces of ceria by using density functional theory, corrected for on-site Coulomb interactions (DFT + U). The Au dopant substitutes a Ce atom in the surface layer, leading to strong structural distortions. The formation of one oxygen vacancy near a dopant atom is energetically “downhill” while the formation of a second vacancy around the same dopant requires energy. When the surface is in equilibrium with gaseous oxygen at 1 atm and room temperature there is a 0.4 probability that no oxygen atom left the neighborhood of a dopant. This means that the sites where the dopant has not lost oxygen are very active in oxidation reactions. Above 400 K almost all dopants have an oxygen vacancy next to them and an oxidation reaction in such a system takes place by creating a second vacancy. The energy required to form a second vacancy is smaller on (1 1 0) than on (1 0 0). On the (1 1 0) surface, it is much easier to form a second vacancy on the doped surface than the first vacancy on the undoped surface. The energy required to form a second oxygen vacancy on (1 0 0) is comparable to that of forming the first vacancy on the undoped surface. Thus doping makes the (1 1 0) surface a better oxidant but it has a small effect on the oxidative power of the (1 0 0) surface. On the (1 1 0) surface CO adsorption results in formation of a carbonate-like structure, similar to the undoped surface, while on the (1 0 0) surface direct formation of CO₂ is observed, in contrast to the undoped surface. The Au dopant weakens the bond of the surrounding oxygen atoms to the oxide making it a better oxidant, facilitating CO oxidation.