Nitrogen Vacancy-Rich C3Nx-Confined Fe–Cu Diatomic Catalysts for the Direct Selective Oxidation of Methane at Low Temperature

The catalytic conversion of methane to high-value-added products is a crucial process, but achieving both high activity and high selectivity poses a significant challenge. Here, we present a nitrogen vacancy-rich C 3 N x -confined heteronuclear diatomic Fe and Cu center (Fe 1 /Cu 1 –C 3 N x ) catalyst that demonstrates high activity. The catalyst shows a C1 oxygenate productivity of 9.43 mol g Fe+Cu –1 h –1 at 80 °C and almost 100% selectivity, with a highly impressive turnover frequency of 543.09 h –1 in generating oxygenates. Detailed experimental characterizations and density functional theory (DFT) calculations reveal that the heteronuclear diatomic Fe 1 /Cu 1 –C 3 N x catalyst has the charge redistribution to provide more charge to H 2 O 2 and to form stronger metal–oxygen interactions to significantly promote H 2 O 2 activation. Meanwhile, the generated Cu–O–Fe active species have moderate methane activation properties, resulting in a good overall reaction performance for the direct selective oxidation of methane at low temperatures.