Electrochemical Oxidation of Methane to Methylamine

The electrochemical methane (CH4) oxidation reaction under ambient conditions is a promising approach for natural gas utilization. However, the highly stable nature of CH4 restrains efficient cleavage of the C-H bond without overoxidation. To this end, we proposed a coupled oxidative strategy for converting CH4 to value-added products via NH2 intermediates. The ammonia-oxidation-driven anodic reaction facilitates the formation of NH2 species and activates CH4 through nucleophilic attack to achieve C-N bond formation. Further the generated methylamine could be protected from overoxidation in the ammonia-based anolyte. Under such conditions, a methylamine productivity of 3.8 mmol g-1cat h-1 at 1.55 V vs a reversible hydrogen electrode is reported. This work provides new insights into electrocatalytic C-N coupling based on the ammonia oxidation reaction, which could extend to other alkane or alkene conversions.