Enhanced Urea Electrosynthesis Driven by Electron‐Deficient Zn Through Optimized Metal–Support Interactions

ABSTRACT The electrocatalytic synthesis of urea under ambient conditions from nitrate ions and carbon dioxide (CO 2 ) offers a sustainable pathway to turn waste into valuable products. However, its development is hindered by the difficulty in synchronizing multi‐proton/electron reaction to promote C─N coupling and hydrogenation. Herein, we report a metal–support interaction (MSI) strategy by constructing electron‐deficient Zn as active center in the activated Zn|ZnMoO 4 ─CNT composite catalyst to drive the co‐reduction of CO 2 and to urea. The as‐developed catalyst achieves a urea Faradaic efficiency (FE) of 59.10 ± 2.12% and yield of 228.41 ± 1.69 µg·h −1 ·mg −1 , outperforming most reported Mo‐ and Zn‐based electrocatalysts. Replacing the anodic oxygen evolution reaction (OER) with ethylene glycol oxidation (EGOR), the urea||EGOR system reduces energy consumption by over 20% and achieves high urea and formate yields. Mechanistic studies show the synergistic MSI between electron‐deficient Zn and electron‐rich Mo boosts catalytic performance. Electron‐deficient Zn facilitates generation of the key *CO 2 NH 2 intermediate from *CO 2 and *NO 2 , promotes C─N coupling, and accelerates hydrogenation via enhanced proton supply, ultimately leading to superior urea selectivity. This work provides a new perspective for enhancing electrocatalytic urea synthesis and extending C─N coupling for high‐value compounds.