Ionic Liquid Microenvironment Modulation for Promoting Electrocatalytic C–N Coupling and Urea Synthesis over Zn@Cu

Urea electrosynthesis is a promising way to upgrade traditional urea production, which is characterized by high energy consumption and significant CO 2 emissions. However, its practical implementation is hindered by the relatively low production rate as well as Faradaic efficiency (FE) toward urea. Herein, a strategy to boost the electrocatalytic urea production is proposed by using a surface-anchored ionic liquid (IL) to stabilize the C–N coupling reaction intermediates via a hydrogen bond. A urea yield of 25.7 μmol h –1 cm –2 and an FE of 30.2% at –1.1 V vs Ag/AgCl are reached over [BIm]NTf 2 -Zn@Cu using CO 2 and NO 2 – as feedstocks, which outperforms the recently reported similar catalysts in the literature. In situ infrared spectroscopy and theoretical calculations reveal that the IL creates an electron-rich microenvironment and enriches the existence of activated CO 2 and NO 2 – near the surface. The lower energy barriers for the formation of key intermediates *CO and *NH 2 facilitate C–N coupling to produce urea in both high productivity and selectivity.