Visible-light-driven and selective methane conversion to oxygenates with air on a halide-perovskite-based photocatalyst under mild conditions

Abstract

Activation and catalytic transformation of C–H bonds under mild conditions has long been a great challenge for the chemical industry. Herein, we report a halide-perovskite-based photocatalyst composed of manganese-doped CsPbBr₃ decorated on BiVO₄ for the efficient and selective transformation of nonpolar CH₄ to oxygenates using air as an oxidant. At room temperature and atmospheric pressure, the yield and selectivity of oxygen-containing hydrocarbons (CH₃OH and HCHO) from photocatalytic CH₄ oxidation are as high as 533.5 μmol g⁻¹ h⁻¹ and 94.8%, respectively. Moreover, transient intermediate capture and isotope labeling experiments demonstrate that the oxygen sources of products for this heterojunction are mainly from O₂, which contrasts with that from water in pristine BiVO₄, owing to the difference in the pathway of O₂ reduction induced by the increased thermodynamic driving force. This work provides an effective strategy for the design and development of a cost-effective catalyst system for CH₄ conversion in a mild manner.