Dual‐Site NiO/Bi3O4Br Heterojunction Catalyst for High‐Efficiency CO2‐to‐CH4 Conversion

Abstract Solar light‐driven conversion of CO2 into chemicals with high calorific value is regarded as an upcoming carbon utilization technology for alleviating the energy crisis. This technique faces the challenge of low CO2 conversion and product yield due to charge recombination in the catalyst. In this paper, a dual‐reaction site heterojunction catalyst was designed and fabricated by combining NiO with Bi3O4Br nanosheets, for the separation of CO2 reduction and H2O oxidation semireactions, which effectively promoted electrons and holes separation. The resulting catalyst exhibited a high CH4 production rate (8.12 µmol/g) and selectivity (94.69%). Electron distribution and band structure were investigated to explain the satisfactory catalytic performance. In addition, combining the in‐situ DRIFTS results, a formic acid‐intermediated CO2‐to‐CH4 reaction pathway was proposed. This work aims to pave the way for CH4 production via CO2 photoreduction with high efficiency and selectivity.