Dissociative adsorption of methane on the Cu and Zn doped (111) surface of CeO₂

The development of economical heterogeneous catalysts for the activation of methane is a major challenge for the chemical industry. Screening potential candidates becomes more feasible using rational catalyst design to understand the activity of potential catalysts for CH₄ activation. The focus of the present paper is the use of density functional theory to examine and elucidate the properties of doped CeO₂. We dope with Cu and Zn transition metals having variable oxidation state (Cu), and a single oxidation state (Zn), and study the activation of methane. Zn is a divalent dopant and Cu can have a +1 or +2 oxidation state. Both Cu and Zn dopants have an oxidation state of +2 after incorporation into the CeO₂ (111) surface; however a Hubbard +U correction (+U = 7) on the Cu 3d states is required to maintain this oxidation state when the surface interacts with adsorbed species. Dissociation of methane is found to occur locally at the dopant cations, and is thermodynamically and kinetically more favorable on Zn-doped CeO₂ than Cu-doped CeO₂. The origins of this lie with the Zn(II) dopant moving towards a square pyramidal geometry in the sub surface layer which facilitates the formation of two-coordinated surface oxygen atoms, that are more beneficial for methane activation on a reducible oxide surface. These findings can aid in rational experimental catalyst design for further exploration in methane activation processes.