Electrosynthesis of formamide from methanol and ammonia under ambient conditions.

Meng, Nannan; Shao, Jiang; Li, Hongjiao; Wang, Yuting; Fu, Xiaoli; Liu, Cuibo; Yu, Yifu; Zhang, Bin · Nat Commun · 2022

basic_science · Level V

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Abstract

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<sup>-2</sup> 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 NH<sub>3</sub> 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).