Selective Urea Electrosynthesis from Nitrate and CO₂ on Isolated Copper Alloyed Ruthenium

Urea electrosynthesis by coelectrolysis of NO 3 – and CO 2 (UENC) represents a promising method to enable efficient and sustainable urea production. In this work, isolated Cu alloyed Ru (Cu 1 Ru) is developed as a highly active and selective UENC catalyst. Combined theoretical computations and in situ spectroscopic measurements reveal the synergistic effect of the Cu 1 –Ru site and the Ru–Ru site on Cu 1 Ru to promote the UENC via a tandem catalysis pathway, in which the Cu 1 –Ru site drives *NO 2 /CO 2 coupling and followed the *CO 2 NO 2 -to-*CO 2 NH step. The formed *CO 2 NH then migrates from the Cu 1 –Ru site to the adjacent Ru–Ru site which promotes the *CO 2 NH⃗*CO 2 NH 2 → *COOHNH 2 steps toward urea generation. Impressively, Cu 1 Ru achieves a high UENC performance in flow cell, exhibiting the urea yield rate of 21.04 mmol h –1 g cat –1 and Faradaic efficiency of 51.27% at −0.6 V, outperforming most reported UENC catalysts.