Electrosynthesis of formamide from methanol and ammonia under ambient conditions

Electrochemical conversion of abundant carbon- and nitrogen-containing small molecules into high-valued organonitrogen compounds is alluring to reducing current dependence on fossil energy. Here we report a single-cell electrochemical oxidation approach to transform methanol and ammonia into formamide under ambient conditions over Pt electrocatalyst that provides 74.26% selectivity from methanol to formamide and a Faradaic efficiency of 40.39% at 100 mA cm^-2 current density, gaining an economic advantage over conventional manufacturing based on techno-economic analysis. A 46-h continuous test performed in the flow cell shows no performance decay. The combined results of in situ experiments and theoretical simulations unveil the C-N bond formation mechanism via nucleophilic attack of NH₃ on an aldehyde-like intermediate derived from methanol electrooxidation. This work offers a way to synthesize formamide via C-N coupling and can be extended to substantially synthesize other value-added organonitrogen chemicals (e.g., acetamide, propenamide, formyl methylamine).