Catalytic degradation of chlorinated volatile organic compounds (CVOCs) over Ce-Mn-Ti composite oxide catalysts

Abstract

Developing industrially moldable catalysts with harmonized redox performance and acidity is of great significance for the efficient disposal of chlorinated volatile organic compounds (CVOCs) in actual exhaust gasses. Here, commercial TiO2, typically used for molding catalysts, was chosen as the carrier to fabricate a series of Ce0.02Mn0–0.24TiOx materials with different Mn doping ratios and employed for chlorobenzene (CB) destruction. The introduction of Mn remarkedly facilitated the synergistic effect of each element via the electron transfer processes: Ce3++Mn4+/3+↔Ce4++Mn3+/2+ and Mn4+/3++Ti4+↔Mn3+/2++Ti3+. These synergistic interactions in Ce0.02Mn0.04–0.24TiOx, especially Ce0.02Mn0.16TiOx, significantly elevated the active oxygen species, oxygen vacancies and redox properties, endowing the superior catalytic oxidation of CB. When the Mn doping amount increased to 0.24, a separate Mn3O4 phase appeared, which in turn might weaken the synergistic effect. Furthermore, the acidity of Ce0.02Mn0.04–0.24TiOx was decreased with the Mn doping, regulating the balance of redox property and acidity. Notably, Ce0.02Mn0.16TiOx featured relatively abundant B-acid sites. Its coordinating redox ability and moderate acidity promoted the deep oxidation of CB and RCOOH- intermediates, as well as the rapid desorption of Cl species, thus obtaining sustainable reactivity. In comparison, CeTiOx owned the strongest acidity, however, its poor redox property was not sufficient for the timely oxidative decomposition of the easier adsorbed CB, resulting in its rapid deactivation. This finding provides a promising strategy for the construction of efficient commercial molding catalysts to decompose the industrial-scale CVOCs.