Continuous Coupling Mechanism for High Rate Electrosynthesis of Urea on Sulfur‐Coordinated Adjacent Copper Sites

Abstract The co‐electrolysis of nitrate (NO 3 − ) and carbon dioxide (CO 2 ) to synthesize urea can satisfy the comprehensive needs of carbon footprint closure, waste valorization, and sustainable urea production. However, designing efficient electrocatalysts to promote the electrocatalytic C─N coupling process and achieve efficient urea production remains a challenge. Here, we design a copper (Cu)‐based coordination polymer catalyst, which can achieve the dual function of promoting C─N coupling and protonation through sulfur (S)‐coordinated adjacent Cu sites. Through the unique Continuous Coupling Mechanism (CCM) of low Gibbs free energy of reaction intermediates (*CO 2 + *NO to *CO 2 NO to *ONCO 2 NO), the resulting catalyst achieved ultra‐high Faradaic efficiency (FE) (84.9 ± 3.1%) and production rate (0.34 ± 0.012 mol h −1 g −1 ). Moreover, the FE and production rate of urea did not change noticeably during at least 90 cycles of testing.