Insights into the Synergistic Catalytic Effect of TiO₂ Supported V‐W Oxides for Selective C−H Bond Oxidation of Cyclohexane to KA Oil

It is urgent to develop an efficient and stable non‐noble metal catalyst for selective C−H bond oxidation of cyclohexane. Herein, a series of V−W oxides supported on TiO 2 catalysts (V−W/TiO 2 ) were fabricated. The V−W/TiO 2 catalysts exhibited much higher catalytic activity for the selective oxidation of cyclohexane to KA oil, compared to that of V/TiO 2 and W/TiO 2 catalysts. The good distribution of active metals and the synergistic effect were responsible for the enhanced catalytic activity. H 2 ‐TPR results disclosed that the presence of V in V−W/TiO 2 affected the reducibility of W 6+ species, and XPS verified that an electronic interaction was formed between them. Such results led to good catalytic reusability of V−W/TiO 2 catalyst during the reactions, and no obvious activity loss was found after six runs. The reaction mechanism was investigated, and the results verified that hydroxyl radicals generated from H 2 O 2 homolysis were the main active oxidative species. Theoretical study revealed that V dopant could regulate electronic structure of adjacent O atom, facilitating the adsorption of cyclohexane, and lower energy was needed for the rate‐limiting step over V−W/TiO 2 during the whole oxidation reaction. This work developed an efficient V−W/TiO 2 catalyst for the selective oxidation of cyclohexane via a synergistic effect.