Unveiling the Function of Oxygen Vacancy on Facet-Dependent CeO2 for the Catalytic Destruction of Monochloromethane: Guidance for Industrial Catalyst Design.

Secondary pollution remains a critical challenge for the catalytic destruction of chlorinated volatile organic compounds (CVOCs). By employing experimental studies and theoretical calculations, we provide valuable insights into the catalytic behaviors exhibited by ceria rods, cubes, and octahedra for monochloromethane (MCM) destruction, shedding light on the elementary reactions over facet-dependent CeO2. Our findings demonstrate that CeO2 nanorods with the (110) facet exhibit the best performance in MCM destruction, and the role of vacancies is mainly to form a longer distance (4.63 Å) of frustrated Lewis pairs (FLPs) compared to the stoichiometric surface, thereby enhancing the activation of MCM molecules. Subsequent molecular orbital analysis showed that the adsorption of MCM mainly transferred electrons from the 3σ and 4π* orbitals to the Ce 4f orbitals, and the activation was mainly caused by weakening of the 3σ bonding orbitals. Furthermore, isotopic experiments and theoretical calculations demonstrated that the hydrogen chloride generated is mainly derived from methyl in MCM rather than from water, and the primary function of water is to form excess saturated H on the surface, facilitating the desorption of generated hydrogen chloride.