Yueji Wu, Han Lin, Qiqi Mao, Hongjie Yu, Kai Deng, Jianguo Wang, Liang Wang, Ziqiang Wang, Hongjing Wang
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引用次数: 0
Abstract
The electrochemical C─N coupling of carbon dioxide (CO2) and nitrate(NO3-) 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-Cu0.1CoBx metallene) is designed for urea synthesis via electrochemical C─N coupling. The a-Cu0.1CoBx metallene can drive electrocatalytic C─N coupling of CO2 and NO3− for urea synthesis in CO2-saturated 0.1 m KNO3 electrolyte, with 27.7% of FE and 312 µg h−1 mg−1cat. 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 偶联是尿素合成传统高能耗工业途径的替代策略,迫切需要设计高效催化剂以实现高产率和法拉第效率(FE)。本文设计了非晶态低含量铜掺杂钴茂金属硼化物(a-Cu0.1CoBx metallene),用于通过电化学 C─N 偶联合成尿素。在二氧化碳饱和的 0.1 m KNO3 电解质中,a-Cu0.1CoBx 茂金属能驱动 CO2 和 NO3- 的电催化 C─N 偶联合成尿素,在-0.5 V 时的 FE 为 27.7%,产率为 312 µg h-1 mg-1cat.,并且具有优异的循环稳定性。原位傅立叶变换红外光谱和理论计算显示,Cu、Co 和 B 之间的电子效应导致 Cu 和 Co 成为双活性位点,促进了反应物的吸附。此外,引入的痕量 Cu 降低了 C─N 偶联的反应能垒,从而促进了尿素的合成。这项工作为优化 Co 基金属烯通过 C─N 偶联电合成尿素提供了一条可行的途径。
期刊介绍:
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