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<p>Direct carbonylation of CH<sub>4</sub> to CH<sub>3</sub>COOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH<sub>4</sub> activation and controllable C–C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven carbonylation of CH<sub>4</sub> with CO and O<sub>2</sub> to CH<sub>3</sub>COOH is achieved over MoS<sub>2</sub>-confined Rh-Zn atomic-pair in conjunction with TiO<sub>2</sub>. It delivers a high CH<sub>3</sub>COOH productivity of 152.0 μmol g<sub>cat.</sub><sup>−1</sup> h<sup>−1</sup> and turnover frequency of 62.0 h<sup>−1</sup> with a superior selectivity of 96.5%, outperforming previous photocatalytic CH<sub>4</sub> carbonylation processes. Mechanistic investigations disclose the key effect of Rh-Zn synergy in combination with photo-excited electrons from TiO<sub>2</sub> for CH<sub>3</sub>COOH formation. The active OH species produced from O<sub>2</sub> photoreduction on the Zn site through proton-coupled electron transfer promotes CH<sub>4</sub> dissociation to CH<sub>3</sub> species, which then facilely couples with adsorbed CO on the adjacent Rh site forming the key CH<sub>3</sub>CO intermediate for CH<sub>3</sub>COOH formation.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月8日

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  • 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 Deng

摘要

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.