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MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid

Author

Listed:
  • Yanan Li

    (Xiamen University
    Chinese Academy of Sciences)

  • Huan Liu

    (Chinese Academy of Sciences)

  • Jun Mao

    (Xiamen University
    Chinese Academy of Sciences)

  • Meng Gao

    (University of Chinese Academy of Sciences)

  • Yunlong Zhang

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Qiao Zhao

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Meng Liu

    (University of Chinese Academy of Sciences
    Chinese Academy of Sciences)

  • Yao Song

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Jingting Hu

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Wangwang Zhang

    (Xiamen University)

  • Rui Huang

    (Chinese Academy of Sciences)

  • Wu Zhou

    (University of Chinese Academy of Sciences)

  • Kaifeng Wu

    (University of Chinese Academy of Sciences
    Chinese Academy of Sciences)

  • Wei Liu

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Liang Yu

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Xiaoju Cui

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Dehui Deng

    (Xiamen University
    Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

Abstract

Direct carbonylation of CH4 to CH3COOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH4 activation and controllable C–C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven carbonylation of CH4 with CO and O2 to CH3COOH is achieved over MoS2-confined Rh-Zn atomic-pair in conjunction with TiO2. It delivers a high CH3COOH productivity of 152.0 μmol gcat.−1 h−1 and turnover frequency of 62.0 h−1 with a superior selectivity of 96.5%, outperforming previous photocatalytic CH4 carbonylation processes. Mechanistic investigations disclose the key effect of Rh-Zn synergy in combination with photo-excited electrons from TiO2 for CH3COOH formation. The active OH species produced from O2 photoreduction on the Zn site through proton-coupled electron transfer promotes CH4 dissociation to CH3 species, which then facilely couples with adsorbed CO on the adjacent Rh site forming the key CH3CO intermediate for CH3COOH formation.

Suggested Citation

  • Yanan Li & Huan Liu & Jun Mao & Meng Gao & Yunlong Zhang & Qiao Zhao & Meng Liu & Yao Song & Jingting Hu & Wangwang Zhang & Rui Huang & Wu Zhou & Kaifeng Wu & Wei Liu & Liang Yu & Xiaoju Cui & Dehui D, 2025. "MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-024-54061-z
    DOI: 10.1038/s41467-024-54061-z
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    References listed on IDEAS

    as
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    2. Junjun Shan & Mengwei Li & Lawrence F. Allard & Sungsik Lee & Maria Flytzani-Stephanopoulos, 2017. "Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts," Nature, Nature, vol. 551(7682), pages 605-608, November.
    3. Daniel Laudenschleger & Holger Ruland & Martin Muhler, 2020. "Identifying the nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3 catalysts," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
    4. Shunji Xie & Zebin Shen & Jiao Deng & Pu Guo & Qinghong Zhang & Haikun Zhang & Chao Ma & Zheng Jiang & Jun Cheng & Dehui Deng & Ye Wang, 2018. "Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol," Nature Communications, Nature, vol. 9(1), pages 1-7, December.
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