DFT Study of CO₂ Activation on Doped and Ultrathin MgO Films.

The bonding mode of carbon dioxide with the surface of various forms of MgO has been investigated by means of density functional theory calculations. Four supports have been considered: the bare MgO(100) surface, the surface of Al-doped MgO, and ultrathin MgO/Ag(100) and MgO/Mo(100) films. Three forms of adsorbed CO 2 have been investigated: physisorbed CO 2, chemisorbed carboxylate, CO 2 –, and carbonate, CO 3 2– . While on MgO(100) CO 2 forms either the physisorbed species or the more stable surface carbonate, on Al-doped MgO carboxylate is the preferred species. The adsorption properties of one- or two-layer MgO films differ completely as a function of the metal support. On MgO/Ag(100) the properties of adsorbed CO 2 are very similar to those of the MgO(100) surface (formation of carbonate, not of carboxylate); on MgO/Mo(100), on the contrary, both carbonate and carboxylate species can form, depending on the film thickness. On a one-layer film, both species are formed with a comparable stability, while for thicker films the carboxylate species becomes unstable. The surface of Al-doped MgO(100) exhibits similar features to that of the nondefective MgO/Mo(100) one-layer film.