Abstract: Density functional theory calculations were carried out to investigate the influence of doping transition metal (TM) ions into the ceria surface on the activation of surface lattice oxygen atoms. For this purpose, the structure and stability of the most stable (111) surface termination of CeO₂ modified by TM ions was determined. Except for Zr and Pt dopants that preserve octahedral oxygen coordination, the TM dopants prefer a square-planar coordination when substituting the surface Ce ions. The surface construction from octahedral to square-planar is facile for all TM dopants, except for Pt (1.14 eV) and Zr (square-planar coordination unstable). Typically, the ionic radius of tetravalent TM cations is much smaller than that of Ce⁴⁺, resulting a significant tensile-strained lattice and explaining the lowered oxygen vacancy formation energy. Except for Zr, the square-planar structure is the preferred one when one oxygen vacancy is created. Thermodynamic analysis shows that TM-doped CeO₂ surfaces contain oxygen defects under typical conditions of environmental catalysis. A case of practical importance is the facile lattice oxygen activation in Zr-doped CeO₂(111), which benefits CO oxidation. The findings emphasize the origin of lattice oxygen activation and the preferred location of TM dopants in TM-ceria solid solution catalysts.

Key words: Lattice oxygen activation, TM-doped CeO₂(111), Density functional theory calculations, Oxygen vacancy, Square-planar coordination, Coordination transformation, CO oxidation