Mild-Condition Conversion of Methane to Acetic Acid over MoS2–Confined Rh–Fe Sites

The oriented conversion of CH 4 to CH 3 COOH at low temperature, even room temperature, is both scientifically significant and industrially applicable for CH 4 utilization, yet it is extremely challenging due to the difficulties associated with efficient CH 4 activation and controllable C–C coupling. In this study, we for the first time achieve the room-temperature conversion of CH 4 to CH 3 COOH using molecular O 2 and CO over MoS 2 -confined Rh–Fe sites, which delivers an unprecedented CH 3 COOH selectivity of 90.3% and a productivity of 26.2 μmol g cat. –1 h –1 at 25 °C. Furthermore, the productivity of CH 3 COOH can be enhanced to 105.6 μmol g cat. –1 h –1 at 80 °C, while maintaining a high selectivity of 95.6%. Comprehensive experimental and theoretical investigation reveal the critical role of Rh–Fe synergy in the selective formation of CH 3 COOH. The confined Fe sites in MoS 2 enable the activation of O 2 to generate highly reactive Fe═O center for CH 4 dissociation to CH 3 species at room temperature, which then readily couple with adsorbed CO on adjacent Rh sites to form the key CH 3 CO intermediate for CH 3 COOH production. The unique structure of Rh–Fe sites offers synergistic catalytic properties that effectively balance C–H activation and C–C coupling, successfully addressing the trade-off between activity and selectivity in the carbonylation of CH 4 to CH 3 COOH under mild conditions.