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。
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.
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.