The regulation mechanism of transition metal doping on Hg0 adsorption and oxidation on Ce/TiO2(001) surface: A DFT study

The mercury oxidation performance of Ce/TiO2 catalyst can be further enhanced by transition metal modifications. This study employed density functional theory (DFT) calculations to investigate the adsorption and oxidation mechanisms of Hg0 on Ce/TiO2(001) and its transition metal modified surfaces. According to the calculation results, Ru-, Mo-, Nb-, and Mn-doping increased the affinity of the Ce/TiO2(001) surface towards Hg0 and HCl, thereby facilitating the efficient capture and oxidation of Hg0. The increased adsorption energy (Eads) of the intermediate HgCl on the modified surfaces could promote its conversion to the final product HgCl2. The modification of transition metals impeded the desorption of the final products HgCl2 and HgO, but it did not serve as the rate-determining step. The oxidation of Hg0 by lattice oxygen and HCl followed the Mars-Maessen and Langmuir-Hinshelwood mechanisms, respectively. HCl exhibited higher mercury oxidation ability than lattice oxygen. The reactivity of lattice oxygen could be further improved by doping transition metals, their promotion order was Ru > Nb > Mo > Mn. In a HCl atmosphere, Mn modification could significantly reduce the energy barrier for HCl activation and HgCl2 formation, providing the optimal enhancement for the mercury oxidation ability of Ce/TiO2 catalyst. The screening method of transition metal modified components based on surface adsorption reaction and oxidation energy barrier was proposed in this study, which provided theoretical guidance for the development of CeTi based catalysts with high mercury oxidation activity.