First principles studies of CO and O chemisorption on LaO surfaces.

Periodic density functional theory calculations were performed to study the surface structures and stabilities of the LaO catalyst in CO and O environments, relevant to the conditions of the oxidative coupling of methane (OCM) reaction. Thermodynamic stabilities of the clean surfaces were predicted to follow the order of (001) ≥ (011) ≫ (110) > (111) > (101) > (100), with their direct band gaps at the Γ point following the similar order of (001) > (011) > (110) > (111) > (100) > (101). Hubbard U corrections to the La 4f and 5d orbitals do not qualitatively change the predictions of surface energies and band gaps. For the most stable (001) surface, CO chemisorption to form carbonate species is exothermic by -0.60 eV with a negligible energy barrier of 0.07 eV, whereas O chemisorption to form peroxide species is endothermic by 0.64 eV with a considerable energy barrier of 1.29 eV. For the slightly less stable (011) surface, both CO and O chemisorption can occur at different surface sites, and the same applies to the other studied surfaces. Dissociation temperatures of surface carbonate species range from 300 to 1000 K at p of 1 bar, which follow the order of (101) ≈ (110) > (111) ≈ (100) ≈ (011) ≫ (001), showing their strong sensitivity to the surface structure. Dissociation temperatures of surface peroxide species are mostly lower than the room temperature except for those of the (011) and (111) surfaces, although the significant kinetic barriers predicted should prevent their facile dissociation. Insights into the temperature-programmed desorption experiments and the methane reactivity of LaO in the OCM reaction were also given based on the results of our calculations.