Effect of transition metal Fe adsorption on CeO2 (110) surface in the methane activation and oxygen vacancy formation: A density functional theory study

Abstract

Methane activation and oxygen vacancy formation over transition metal Fe adsorption on CeO2 (110) are studied by using the method of density functional theory (DFT)+U method. A set of model configurations are generated by placing Fe at five surface sites, viz., O-top site, O-bridge site, Ce-bridge site, Ce-top and double oxygen-bridge sites. The study shows that the energetically most favorable configuration is Fe adsorption at the double oxygen-bridge site. Based on the calculated surface, subsurface and the second oxygen vacancies formation energy with (or without) Fe adsorption, it shows that the Fe adsorption is in favor of the surface, subsurface and second oxygen vacancies formation. For the surface and subsurface oxygen vacancy on the Fe/CeO2 (110) surface, the main factor responsible for lowering of Evac is that the adsorption induces structural distortions, whereas, for the second oxygen vacancy, half can be attributed to the large structural relaxation, half can be attributed to the electronic effects. After calculating and discussing about the CH4 activation on CeO2 (110) and Fe/CeO2 (110) surface with (or without) the surface or subsurface oxygen vacancies at the possible adsorption sites, the results show that when the CH4 adsorbed on the Fe/CeO2 (110) with the surface oxygen vacancy at the Ce1 and Ce2 sites, the CH4 decomposed into the CH(ads) and H(ads), its belongs to the chemical absorption, whereas, when the CH4 adsorbed on the other possible sites, the mentioned phenomenon is not occurred, its belongs to the physical absorption. This study reveals the correlation between surface reducibility and catalytic activity for methane oxidation on cerium-based materials, which might be beneficial in developing improved catalysts for methane combustion.