Surface engineering on bulk Cu<sub>2</sub>O for efficient electrosynthesis of urea.

Dai, Zechuan; Chen, Yanxu; Zhang, Huaikun; Cheng, Mingyu; Zhang, Bocheng; Feng, Pingyi; Feng, Yafei; Zhang, Genqiang · Nat Commun · 2025

basic_science · Level V

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Abstract

Electrochemical urea synthesis has recently emerged as a fascinating energy-efficient alternative route, while it remains challenging to achieve simultaneously high production rate and Faradaic efficiency. Herein, we realize an energy-favorable electrochemical C-N coupling path through CO<sub>2</sub> and NO<sub>3</sub><sup>-</sup> co-reduction at the heterointerfaces of Cu/Cu<sub>2</sub>O microparticles, generated by in-situ electrochemical engineering on bulk Cu<sub>2</sub>O. We achieve urea production rate of 632.1 μg h<sup>-1</sup>mg<sub>cat.</sub><sup>-1</sup> with a corresponding Faradaic efficiency of 42.3% at -0.3 V (versus RHE) under ambient conditions. Operando synchrotron radiation-Fourier transform infrared spectroscopy, along with theoretical calculations, reveals the coupling of intermediates NOH* and CO* at the heterointerfaces, benefiting from the modified electronic structure. This work provides a practical route for catalyst design and insights into urea electrosynthesis systems.