Catalytic elimination through an oxidative decomposition pathway is the most promising candidate for the purification of chlorinated volatile organic compound (CVOC) pollutants, but the complicated mechanisms and the formation pathways of hydrogenated byproducts still need to be clearly revealed. Herein, W/ZrO2, as a structure-tunable catalyst, is used to catalytically oxidize dichloromethane (DCM) and clarify the formation pathway of monochloromethane (MCM). Crystal engineering of ZrO2 tailors surface WOx species; practically, the predominant Zr-WOx clusters and crystalline WO3 can be obtained on monoclinic (m-ZrO2) and tetragonal (t-ZrO2) phases. Surface Zr-WOx species are highly active due to their distorted structure and abundant Lewis acid sites. In situ DRIFTS reveal that H2O accelerates the cycle between W═O and O═W─Cl as well as replenishes consumed hydroxyls, improving the durability of W/m-ZrO2, and thus a hydrolysis-oxidation mechanism is proposed. Moreover, a hydride transfer pathway for MCM formation as a hydrodechlorinated byproduct is identified. -OCH2O- as the direct hydride donor is generated by the dissociation of DCM on surface active oxygen species or hydroxyls, and then transferred to C+H2Cl species on Lewis acid sites to produce MCM. This work could potentially contribute to developing novel oxidative elimination strategies for CVOCs and the rational design of efficient catalysts.
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