Selective\nUrea Electrosynthesis from Nitrate and CO<sub>2</sub> on Isolated\nCopper Alloyed Ruthenium

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