Electrocatalytic Upgrading of Plastic and Biomass‐Derived Polyols to Formamide under Ambient Conditions

Abstract Electrocatalytic upgrading of wasted plastic and renewable biomass represents a sustainable method to produce chemicals but is limited to carbohydrates, leaving other value‐added chemicals, such as organonitrogen compounds, being scarcely explored. Herein, we reported an electrocatalytic oxidation strategy to transform polyethylene terephthalate (PET) plastic‐derived ethylene glycol (EG) and biomass‐derived polyols into formamide, in the presence of ammonia (NH 3 ) over a tungsten oxide (WO 3 ) catalyst. Taking EG‐to‐formamide as an example, we achieved a high formamide productivity of 537.7 μmol cm −2 h −1 with FE of 43.2 % at a constant current of 100 mA cm −2 in a flow electrolyzer with 12‐h test, representing a more advantageous performance compared with previous reports for formamide electrosynthesis. Mechanistic understanding revealed that the cleavage of the C−C bond in the EG was facilitated by nucleophilic attack of in situ formed nitrogen radicals from NH 3 , with resultant C−N bond construction and eventually formamide production. Furthermore, this strategy can be extended to transformation of PET bottle and a series of biomass‐derived polyols with carbon number from three (glycerol) to six (glucose), producing formamide with high efficiencies. This work demonstrates a sustainable upgrading strategy of plastic and biomass that may have implications to more value‐added chemicals production beyond carbohydrates.