Enhanced Urea Electrosynthesis Driven by Electron‐Deficient Zn Through Optimized Metal–Support Interactions
Ping Chen, Qing Xu, Heyu Zhang, Yaxuan Wang, Xinchen Zhang, Boran Dong, Mingzhiyuan Bao, Yanshen Zhou, Minmin Liu, Hong Li, Shengjuan HuoABSTRACT
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.