A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface

作者：Xiaojin Tu, Xiaorong Zhu, Shuowen Bo, Xiaoran Zhang, Ruping Miao, Guobin Wen, Chen Chen, Jing‐Feng Li, Yangyang Zhou, Qinghua Liu, Dawei Chen, Huaiyu Shao, Dafeng Yan, Yafei Li, Jianfeng Jia, Shuangyin Wang · 发表于：Angewandte Chemie International Edition · 年份：2023 · DOI：10.1002/anie.202317087 · 被引用次数：92 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、CO2 Reduction Techniques and Catalysts

Abstract Electrocatalytic C−N coupling process is indeed a sustainable alternative for direct urea synthesis and co‐upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C−N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C−N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li + <Na + <Cs + <K + . In the presence of K + , a world‐record performance was achieved with a urea yield rate of 212.8±10.6 mmol h −1 g −1 on a single‐atom Co supported TiO 2 catalyst at −0.80 V versus reversible hydrogen electrode. Theoretical calculations and operando synchrotron‐radiation Fourier transform infrared measurements revealed that the energy barriers of C−N coupling were significantly decreased via K + mediated intermediate assembly. By applying this strategy to various catalysts, we demonstrate that intermediate assembly at the electrode/electrolyte interface is a universal approach to boost sustainable urea synthesis.