Electrosynthesis of N,N-dimethylformamide from market-surplus trimethylamine coupled with hydrogen production

N,N-Dimethylformamide (DMF) is a universal solvent with wide applications across various industries. Current industrial synthesis requires high temperature and high pressure, starting from fossil-based carbon monoxide and dimethylamine (DMA). Herein, we report a green and electrochemical strategy to produce DMF under ambient conditions through direct oxidation of trimethylamine (TMA), which is a surplus chemical in DMA manufacturing. DMF production with 80% yield and >50% faradaic efficiency was achieved in an H-cell reactor over a graphite anode, coupled with hydrogen production at the cathode. Mechanistic investigations show that the reaction occurs through two-phase oxidation and that an aminal serves as the key intermediate. To achieve continuous DMF production, we set up a membrane-electrode assembly (MEA) flow reactor (2 cm × 2 cm), achieving a DMF productivity of 25 μmol h⁻¹ and a faradaic efficiency of 40%. To further increase the productivity, we fabricated another membrane-free flow reactor (8 cm × 9 cm), delivering a high formation rate (550 μmol h⁻¹) with high selectivity (>90%) at a constant current of 3 A in a 100-hour test. This study offers a unique opportunity to utilize electricity to drive surplus chemical utilization under ambient conditions, contributing to the sustainability of the chemical industry in the future.