Chinese Journal of Catalysis

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Cu single atoms on defective carbon nitride for photocatalytic oxidation of methane to methanol with selectivity over 92%

Bo Fenga, Danning Fenga, Yan Peia, Baoning Zongb,*, Minghua Qiaoa,*, Wei Lia,*   

  1. aDepartment of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Porous Materials for Separation and Conversion, Fudan University, Shanghai 200433, China;
    bState Key Laboratory of Petroleum Molecular & Process Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
  • Received:2025-03-26 Accepted:2025-05-03
  • Contact: * E-mail: weilichem@fudan.edu.cn (W. Li), mhqiao@fudan.edu.cn (M. Qiao), zongbn.ripp@sinopec.com (B. Zong).
  • Supported by:
    State Key Research and Development Project of China (2021YFA1501404), the National Natural Science Foundation of China (22272030, U21A20329, U24A20488), and the Science and Technology Commission of Shanghai Municipality (2024DZSYS02).

Abstract: The photocatalytic oxidation of methane to methanol using oxygen directly is an attractive catalytic reaction, but designing catalysts to avoid over-oxidation remains a significant challenge. Herein, Cu single atoms anchored on the defective carbon nitride structure (Cu SA/Def-CN) is designed for selective photocatalytic oxidation of methane into methanol using O2 under mild conditions. The Cu SA/Def-CN catalyst exhibits a high methanol selectivity of 92.8% under optimized conditions. Mechanistic studies reveal a synergistic effect between Def-CN and Cu SA, where Def-CN is responsible for the in-situ generation of hydrogen peroxide, which is subsequently decomposed by the Cu SA sites to produce ·OH radicals that play a key role in the rate-determining step of methane activation to form methanol. Additionally, the presence of Cu SA not only enhances the electron-hole separation efficiency and improves the transfer efficiency of the photo-generated charges, but also increases the active sites for methane adsorption and activation. These insights provide valuable guidance for designing efficient catalysts for the highly selective photocatalytic oxidation of methane to methanol.

Key words: Methane, Photocatalysis, Cu single atoms, Defective carbon nitride, Hydrogen peroxide