Oxide-Derived Core-Shell Cu@Zn Nanowires for Urea Electrosynthesis from Carbon Dioxide and Nitrate in Water

Urea electrosynthesis provides an intriguing strategy to improve upon the conventional urea manufacturing technique, which is associated with high energy requirements and environmental pollution. However, the electrochemical coupling of NO₃^- and CO₂ in H₂O to prepare urea under ambient conditions is still a major challenge. Herein, self-supported core-shell Cu@Zn nanowires are constructed through an electroreduction method and exhibit superior performance toward urea electrosynthesis via CO₂ and NO₃^- contaminants as feedstocks. Both ¹H NMR spectra and liquid chromatography identify urea production. The optimized urea yield rate and Faradaic efficiency over Cu@Zn can reach 7.29 μmol cm^-2 h^-1 and 9.28% at -1.02 V vs RHE, respectively. The reaction pathway is revealed based on the intermediates detected through in situ attenuated total reflection Fourier transform infrared spectroscopy and online differential electrochemical mass spectrometry. The combined results of theoretical calculations and experiments prove that the electron transfer from the Zn shell to the Cu core can not only facilitate the formation of *CO and *NH₂ intermediates but also promote the coupling of these intermediates to form C-N bonds, leading to a high faradaic efficiency and yield of the urea product.