Nitrogen Vacancy-Rich C3N x ‑Confined Fe–Cu Diatomic Catalysts for the Direct Selective Oxidation of Methane at Low Temperature

• Published in: ACS catalysis 2024-07, Vol.14 (14), p.10689-10700
• Main Authors: Li, Wencui, Li, Zhi, Shen, Hengfang, Cai, Jiaxin, Jing, Hongyu, Xin, Shigang, Cao, Zengwen, Xie, Zean, Li, Dong, Zhang, Hang, Zhao, Zhen
• Format: Article
• Language: English
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.4c01328

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 C3N x -confined heteronuclear diatomic Fe and Cu center (Fe1/Cu1–C3N x ) catalyst that demonstrates high activity. The catalyst shows a C1 oxygenate productivity of 9.43 mol gFe+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 Fe1/Cu1–C3N x catalyst has the charge redistribution to provide more charge to H2O2 and to form stronger metal–oxygen interactions to significantly promote H2O2 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.