Mercury/oxygen reaction mechanism over CuFe2O4 catalyst

CuFe2O4 is regarded as a promising candidate of catalyst for Hg0 oxidation in industrial flue gas. However, the microcosmic reaction mechanism governing mercury oxidation on CuFe2O4 remains elusive. Herein, experiments and quantum chemistry calculations were conducted for understanding the chemical reaction mechanism of oxygen-assisted mercury oxidation on CuFe2O4. CuFe2O4 shows the optimal catalytic activity towards mercury oxidation at 150 ºC. The reactivity difference of different lattice oxygen species is associated with its atomic coordination environment. The lattice oxygen coordinating with two octahedral Cu atoms and a tetrahedral Fe atom shows higher catalytic activity towards mercury oxidation than other lattice oxygen atoms. The inverse spinel structure of CuFe2O4 is favorable for O2 activation due to the Jahn-Teller effect, thereby promoting mercury oxidation. O2 molecule preferably adsorbs on iron active site and dissociates into active oxygen species. Hg0 oxidation is a three-step reaction process: Hg0 adsorption, Hg(ads) → HgO(ads), and HgO desorption. The energy barrier of mercury oxidation by chemisorbed oxygen is lower than that of mercury oxidation by lattice oxygen. The chemisorbed oxygen preserves higher reactivity towards mercury oxidation than lattice oxygen. Hg(ads) → HgO(ads) is the rate-determining step of mercury oxidation by chemisorbed oxygen because of the higher energy barrier of 116.94 kJ/mol. This work could provide the theoretical guidance for the diversified structure design of highly-efficient catalysts used for elemental mercury oxidation. [Display omitted] •Hg0 oxidation by oxygen species over CuFe2O4 was studied by quantum chemistry.•The reactivity of lattice oxygen is related to its atomic coordination environment.•Hg0 oxidation by chemisorbed oxygen over CuFe2O4 is a three-step reaction process.•Hg0 oxidation shows similar kinetics in the presence and absence of gaseous oxygen.