Dual-Function Reaction Center for Simultaneous Activation of CH₄ and O₂ via Oxygen Vacancies during Direct Selective Oxidation of CH₄ into CH₃OH

The direct oxidation of methane (CH₄) to methanol (CH₃OH) has been a focus of global concern and is quite challenging due to the thermodynamically stable CH₄ and uncontrolled overoxidation of the products. Here, we provided a new viewpoint on the role of oxygen vacancies that induce a dual-function center in enhancing the adsorption and activation of both CH₄ and O₂ reactants for the subsequent selective formation of a CH₃OH liquid fuel on two-dimensional BiOCl photocatalysts at atmospheric pressure. The key for the favorable activity lies in the simultaneous ability of the electron-trapped Bi atom in activating CH₄ and the formation of ^•O₂^- radicals due to the activation of O₂ at the adjacent oxygen vacancy site, which immediately attack the activated CH₄ to directly produce CH₃OH, in initiating the oxidation reaction. What is more, the relatively low reaction barriers and the easy desorption of CH₃OH concertedly facilitate the highly selective conversion of CH₄ up to 85 μmol of CH₃OH, with a small amount of CO₂ and CO as the byproducts over the BiOCl nanosheets with an oxygen vacancy concentration of 2.4%. This work could broaden the avenue toward the application of oxygen-defective metal oxides in the photocatalytic selective conversion of CH₄ to CH₃OH and offer a disparate perspective on the role of oxygen vacancy acting as the surface electron transfer channel in enhancing the photocatalytic performance.