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

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 c...

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Main Authors: 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
Format: Article
Language:English
Published: Nature Portfolio 2025-01-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54061-z
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Summary: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.
ISSN:2041-1723