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

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

doi:10.1038/s41467-024-54061-z

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

Nat Commun. 2025 Jan 8;16(1):487. doi: 10.1038/s41467-024-54061-z.

Authors

Yanan Li^#^{1

2}, Huan Liu^#², Jun Mao^#^{1

2}, Meng Gao³, Yunlong Zhang^{2

4}, Qiao Zhao^{2

4}, Meng Liu^{4

5}, Yao Song^{2

4}, Jingting Hu^{2

4}, Wangwang Zhang¹, Rui Huang², Wu Zhou³, Kaifeng Wu^{4

5}, Wei Liu^{2

4}, Liang Yu^{6

7}, Xiaoju Cui^{8

9}, Dehui Deng^{10

11

12}

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
² State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
³ School of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, China.
⁴ University of Chinese Academy of Sciences, Beijing, China.
⁵ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
⁶ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. [email protected].
⁷ University of Chinese Academy of Sciences, Beijing, China. [email protected].
⁸ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. [email protected].
⁹ University of Chinese Academy of Sciences, Beijing, China. [email protected].
¹⁰ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. [email protected].
¹¹ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. [email protected].
¹² University of Chinese Academy of Sciences, Beijing, China. [email protected].

^# Contributed equally.

PMID: 39779679
DOI: 10.1038/s41467-024-54061-z

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 g_cat.^-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.

Abstract

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