Carbon Nitride With Abundant Nitrogen Vacancies for Methane Oxidation Under Mild Conditions

ABSTRACT Direct methane oxidation to oxygenates under mild conditions is challenging due to the inert C─H bond in methane, especially for nonmetal catalytic systems. In this study, we report that nitrogen vacancy‐rich graphitic carbon nitride (g‐C 3 N 4 ) serves as an effective catalyst for methane oxidation using H 2 O 2 as the oxidant. Under optimized conditions (3 MPa CH 4 , 70°C, 1 h), the g‐C 3 N 4 catalyst with the highest nitrogen vacancy concentration ( V N ‐rich CN) achieved an oxygenates yield of 13.42 µmol. Comprehensive characterization and mechanistic studies revealed that nitrogen vacancies in g‐C 3 N 4 facilitate H 2 O 2 decomposition into hydroxyl radicals (·OH), which subsequently activate methane to form oxygenates. Notably, the catalytic activity exhibited a positive correlation with nitrogen vacancy concentration, demonstrating the critical role of these defects in the oxidation process.