MoS<sub>2</sub>-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39779679.
- Also identified by DOI 10.1038/s41467-024-54061-z and PMC identifier 11711459.
- Licence recorded as CC BY-NC-ND.
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Abstract
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.