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Charge Polarization Boosting Electrochemical Urea Synthesis by Co‐Reduction of CO<sub>2</sub> and Nitrite in Dilute Concentrations with a Unity Carbon Selectivity

Zhihao Feng, Lu‐Hua Zhang, Lu‐Hua Zhang, Yabo Guo, Jiangyi Guo, Fei Li, Fengshou Yu, Fengshou Yu

2025Angewandte Chemie International Edition20 citationsDOI

Abstract

Abstract Synthesis of urea through electrocatalytic coupling reaction of CO 2 with nitrite (NO 2 − ) represents a sustainable means to substitute the conventional energy‐intensive urea synthetic protocol. The direct conversion of dilute NO 2 − in real wastewaters to urea with high efficiency is still a significant challenge, as C‐intermediates tend to go through an extensive reduction achieving mostly C‐containing productions due to the lack of N‐intermediates, originating from slow diffusion rate of NO 2 − . Herein, we report the charge‐polarized Fe δ− ‐Cu δ+ dual sites in metal/carbon heterojunction material (Cu@Fe−N−C) for co‐reduction of CO 2 and dilute NO 2 − solution (100 ppm NO 2 − ‐N). The electron‐rich single Fe atoms dispersed N‐doped carbon (Fe−N−C) restrain *CO desorption, and the electron‐deficient Cu nanoparticles (Cu) promote the deep reduction of NO 2 − to *NH 2 . As a result, the obtained Cu@Fe−N−C exhibits a high Faradaic efficiency for urea of 50.05 % with a yield of 850.57 mg h −1 g −1 at −0.35 V ( vs . RHE) in a flow cell. Moreover, C urea‐selectivity reaches to 100 % and a near‐unity selectivity for the value‐added urea and NH 3 is realized. The present results provide a valuable reference for the design of new catalysts for efficient synthesis of C−N compounds in dilute NO 2 − solution.

Topics & Concepts

SelectivityUreaChemistryInorganic chemistryElectrochemistryNitriteCatalysisElectrodeNitratePhysical chemistryOrganic chemistryAmmonia Synthesis and Nitrogen ReductionCO2 Reduction Techniques and CatalystsAdvanced Photocatalysis Techniques