Efficient Urea Electrosynthesis on a Cu 3 Molecular Catalyst with Dynamically Adaptive Intercopper Spacings

作者：Mengqiu Xu, Yuanyuan Xue, Zhengzheng Liu, Ximeng Lv, Qing Han, Gengfeng Zheng · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c15109 · 被引用次数：20 · 研究领域：CO2 Reduction Techniques and Catalysts、Ammonia Synthesis and Nitrogen Reduction、Electrocatalysts for Energy Conversion

Electrocatalytic urea synthesis from carbon monoxide (CO) and nitrate ions (NO 3 – ) represents a promising alternative to the conventional energy-intensive industrial methods, while this approach is strongly limited by the kinetically sluggish C–N coupling process and the competing side reactions. Herein, we report a trinuclear-copper molecular catalyst (denoted as Cu 3 -flex) that can enable dynamic and self-adaptive intercopper spacings among those triangular-shaped Cu 3 adjacent sites upon the binding of two *CO and one *NO 3 – . The dynamic variation of the intercopper spacings induced by the bridged *CO adsorption allows us to promote the first C–N coupling of *CO and *N to form the key *NCO intermediate, as well as the subsequent capturing of another *NO 3 – and the second C–N coupling to produce urea. The Cu 3 -flex catalyst exhibited a high urea electrosynthesis performance for the coreduction of CO and NO 3 –, including a urea production rate of 122 mmol·g cat. –1 ·h –1, a Faradaic efficiency of 69%, and a notable electrochemical stability of >125 h.