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

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.