Wu Yueji, Lin Han, Mao Qiqi, Yu Hongjie, Deng Kai, Wang Jianguo, Wang Liang, Wang Ziqiang, Wang Hongjing
State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.
Small. 2024 Dec;20(51):e2407679. doi: 10.1002/smll.202407679. Epub 2024 Oct 12.
The electrochemical C─N coupling of carbon dioxide (CO) and nitrate(NO ) is an alternative strategy to the traditional high-energy industrial pathway for urea synthesis, which urgently requires the design of efficient catalysts to achieve high yield and Faraday efficiency (FE). Here, amorphous low-content copper-doped cobalt metallene boride (a-CuCoB metallene) is designed for urea synthesis via electrochemical C─N coupling. The a-CuCoB metallene can drive electrocatalytic C─N coupling of CO and NO for urea synthesis in CO-saturated 0.1 m KNO electrolyte, with 27.7% of FE and 312 µg h mg of yield at -0.5 V, as well as superior cycling stability. The in situ Fourier transform infrared and theoretical calculations reveal that electronic effect between Cu, Co, and B causes Cu and Co as dual active sites to promote the adsorption of reactants. Furthermore, the introduced trace Cu reduces the reaction energy barrier of the C─N coupling to facilitate urea synthesis. This work provides a promising route for the optimization of Co-based metallene for the electrosynthesis of urea through C─N coupling.
二氧化碳（CO₂）和硝酸盐（NO₃⁻）的电化学C─N偶联是传统高能耗工业尿素合成途径的一种替代策略，这迫切需要设计高效催化剂以实现高产量和法拉第效率（FE）。在此，设计了非晶态低含量铜掺杂钴金属硼化物（a-CuCoB金属烯）用于通过电化学C─N偶联合成尿素。a-CuCoB金属烯可在CO饱和的0.1 m KNO₃电解液中驱动CO₂和NO₃⁻的电催化C─N偶联以合成尿素，在-0.5 V时法拉第效率为27.7%，产率为312 μg h⁻¹ mg⁻¹，并且具有优异的循环稳定性。原位傅里叶变换红外光谱和理论计算表明，Cu、Co和B之间的电子效应使Cu和Co作为双活性位点促进反应物的吸附。此外，引入的微量Cu降低了C─N偶联的反应能垒，便于尿素合成。这项工作为通过C─N偶联电合成尿素优化钴基金属烯提供了一条有前景的途径。
