Boosting Electrocatalytic Urea Production via Promoting Asymmetric C-N Coupling

Electrocatalytic C-N coupling shows great potential in direct and sustainable urea synthesis. However, the mechanism of interaction between catalytic sites and intermediate species is currently unclear, and explor-ing corresponding strategies to boost urea synthesis is urgent. Herein, we demonstrated that a multihole structure could preserve the Cu+ component of Cu2O spheres under electrochemical reduction conditions. An in situ formed Cu0-Cu+ site thermodynamically and kinetically promoted the asymmetric coupling pro-cess of *CO and *NO, thereby boosting the urea pro-duction. The impressive urea yield rates of 29.2 and 114.0 mmol h-1 g-1 were realized for electrochemical coupling of CO2 with nitrate and nitrite, respectively. The multihole-Cu2O exhibits both superior activity and long-term stability compared to the electrocata-lysts with a reconstructed Cu0-dominated surface. This work provides insights into the identification and design of the active site for C-N coupling and urea synthesis.