卫星单原子铜簇接力催化强化尿素电合成研究。

IF 16.9 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Xinyue Ma, Baoguang Mao, Zeqiang Yu, Prof. Dan Wang, Jing Xia, Jianhua Hou, Prof. Xiangmin Meng, Husitu Lin, Prof. Chuangang Hu
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引用次数: 0

摘要

在偶联反应中,接力催化在缓解不同反应物之间的竞争方面表现出显著的效果。然而,对尿素电合成中继电催化反应机理的全面理解仍然具有挑战性。在此,我们开发了一种催化剂(CuAC-CuSA@NC),该催化剂由Cu原子团簇(CuAC)和卫星Cu- n4单原子(CuSA)位点组成,位于氮掺杂的多孔互连碳骨架(NC)上,从而阐明了CO2和NO3-共还原的接力催化过程。所设计的CuAC-CuSA@NC催化剂在-1.3 V / RHE下的尿素产率比CuSA@NC高出约三倍。非原位实验结果和原位衰减全反射表面增强红外吸收光谱分析表明,CuAC-CuSA@NC上的*NH2和*NH2CO具有还原电位增大的形成顺序。结合理论计算进一步阐明了接力催化途径包括“CuAC”位点促进*NO3转化为*NOx,然后“CuSA”位点促进水解离与*H加氢生成*NH2,随后与*CO2偶联生成尿素。这项工作为偶联反应的研究提供了新的见解,但不限于尿素合成。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis

Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis

Relay catalysis represents significant efficacy in alleviating competition among different reactants during coupling reactions. However, a comprehensive understanding of the reaction mechanism underlying relay catalysis for the urea electrosynthesis remains challenging. Herein, we have developed a catalyst (CuAC-CuSA@NC) comprising Cu atomic clusters (CuAC) with satellite Cu─N4 single atoms (CuSA) sites on the nitrogen-doped porous interconnected carbon skeleton (NC), enabling elucidation of a relay catalysis process for co-reduction of CO2 and NO3. The designed CuAC-CuSA@NC catalyst exhibits an approximately threefold higher urea yield rate compared to that of CuSA@NC at −1.3 V versus RHE. Ex-situ experimental results and in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis reveal a formation sequence between the *NH2 and *NH2CO species on CuAC-CuSA@NC with increasing reduction potential. The combination of theoretical calculations further elucidates that the relay catalysis pathway involves “CuAC” sites facilitating the conversion of *NO3 to *NOx, followed by a hydrogenation process to form *NH2 with *H from water dissociation promoted by “CuSA” sites, which subsequently couples with *CO2 to produce urea. This work provides novel insights into the investigation of coupling reactions, but not limit to, urea synthesis.

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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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