Mechanism insights into CO oxidation over transition metal modified V₂O₅/TiO₂ catalysts: A theoretical study

The V₂O₅/TiO₂ based selective catalytic reduction (SCR) catalysts possess not only promising capability on the denitrification of nitrogen oxides (NO_x), but also certain effects on the oxidation of carbon monoxide (CO) in the flue gas. Modification of traditional SCR catalysts with certain transition metals can further improve their catalytic oxidation ability of CO. Therefore, it is of great significance to reveal the catalytic oxidation mechanism of CO for developing modified SCR catalysts to achieve the co-removal of CO and NO_x. Theoretical calculations based on density functional theory (DFT) were performed to probe the comprehensive reaction mechanism of CO oxidation on M doped V₂O₅/TiO₂ catalysts (M = Mo, Fe, and Co). The whole CO oxidation cycles include three stages, i.e., the first CO oxidation, the re-oxidation of the surface, and the second CO oxidation. The terminal oxygen and the surface oxygen formed by the adsorbed O₂ all play vital roles in the whole CO oxidation cycles. The activation barriers of the rate-determining steps for CO oxidation on Fe-V₂O₅/TiO₂ and Co-V₂O₅/TiO₂ are much lower than that of Mo-V₂O₅/TiO₂, which indicates Fe and Co dopants can apparently promote the CO oxidation activities of the modified SCR catalysts. Meanwhile, the electronic structure analysis confirms that Fe and Co dopants can cause electron distribution change with strong oxidation ability at the active oxygen sites.