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用于从水中的二氧化碳和硝酸盐进行尿素电合成的氧化物衍生核壳Cu@Zn纳米线

Oxide-Derived Core-Shell Cu@Zn Nanowires for Urea Electrosynthesis from Carbon Dioxide and Nitrate in Water.

作者信息

Meng Nannan, Ma Xiaomin, Wang Changhong, Wang Yuting, Yang Rong, Shao Jiang, Huang Yanmei, Xu Yue, Zhang Bin, Yu Yifu

机构信息

Department of Chemistry, Institute of Molecular Plus, School of Science, Tianjin University, Tianjin 300072, China.

Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Key Laboratory of Systems Bioengineering (Ministry of Education), Tianjin University, Tianjin 300072, China.

出版信息

ACS Nano. 2022 Jun 28;16(6):9095-9104. doi: 10.1021/acsnano.2c01177. Epub 2022 Jun 3.

Abstract

Urea electrosynthesis provides an intriguing strategy to improve upon the conventional urea manufacturing technique, which is associated with high energy requirements and environmental pollution. However, the electrochemical coupling of NO and CO in HO to prepare urea under ambient conditions is still a major challenge. Herein, self-supported core-shell Cu@Zn nanowires are constructed through an electroreduction method and exhibit superior performance toward urea electrosynthesis CO and NO contaminants as feedstocks. Both H NMR spectra and liquid chromatography identify urea production. The optimized urea yield rate and Faradaic efficiency over Cu@Zn can reach 7.29 μmol cm h and 9.28% at -1.02 V RHE, respectively. The reaction pathway is revealed based on the intermediates detected through attenuated total reflection Fourier transform infrared spectroscopy and online differential electrochemical mass spectrometry. The combined results of theoretical calculations and experiments prove that the electron transfer from the Zn shell to the Cu core can not only facilitate the formation of *CO and *NH intermediates but also promote the coupling of these intermediates to form C-N bonds, leading to a high faradaic efficiency and yield of the urea product.

摘要

尿素电合成提供了一种改进传统尿素制造技术的有趣策略,传统技术存在高能量需求和环境污染问题。然而,在环境条件下将NO和CO在水中进行电化学偶联合成尿素仍然是一个重大挑战。在此,通过电还原方法构建了自支撑核壳结构的Cu@Zn纳米线,其对以CO和NO污染物为原料的尿素电合成表现出优异性能。1H NMR光谱和液相色谱均鉴定出有尿素生成。在-1.02 V(相对于可逆氢电极)时,优化后的Cu@Zn上的尿素产率和法拉第效率分别可达7.29 μmol cm-2 h-1和9.28%。基于通过衰减全反射傅里叶变换红外光谱和在线差分电化学质谱检测到的中间体揭示了反应途径。理论计算和实验的综合结果证明,电子从Zn壳层转移到Cu核不仅有助于形成CO和NH中间体,还促进这些中间体偶联形成C-N键,从而导致尿素产物具有高法拉第效率和产率。

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