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痕量铜诱导的非晶态钴硼烯化物上的低C─N偶联势垒用于促进电化学尿素生产

Trace Cu-Induced Low C─N Coupling Barrier on Amorphous Co Metallene Boride for Boosting Electrochemical Urea Production.

作者信息

Wu Yueji, Lin Han, Mao Qiqi, Yu Hongjie, Deng Kai, Wang Jianguo, Wang Liang, Wang Ziqiang, Wang Hongjing

机构信息

State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, P. R. China.

出版信息

Small. 2024 Dec;20(51):e2407679. doi: 10.1002/smll.202407679. Epub 2024 Oct 12.

Abstract

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.

摘要

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。

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