电催化有机反应机理的原位拉曼光谱研究进展

doi:10.12461/PKU.DXHX202406117

摘要/Abstract

摘要： 近年来电催化有机合成愈发受到人们的关注，其低污染、高原子效率等优点使其较传统有机合成方法具有巨大优势，符合绿色化学的社会要求。从分子水平去检测电极界面上的反应过程和关键中间体，对理解反应机理和设计更高效催化剂有着重要的指导意义。拉曼光谱是一种无损、不受水干扰的振动光谱，特别是表面增强拉曼光谱具有超高表界面灵敏度，它可以提供关于催化剂表面结构、吸附物种以及反应过程中表面中间体等关键信息，为探索反应机制提供可靠平台。本文综述了近年来利用原位拉曼光谱探究电催化有机反应过程和机理的研究进展，具体阐述了电催化加氢、C―O键活化、C―X (X = F, Cl, Br, I)键活化、C―H键活化、C―C键活化等几类有机化学反应中，拉曼光谱揭示的重要中间体、活性物质及其反应途径。通过分析具体案例，旨在帮助学生了解有机电合成的研究前沿，激发探究2023年度IUPAC“化学领域十大新兴技术”之一的合成电化学兴趣。

关键词: 拉曼光谱, 有机电化学合成, 电催化, 反应机理

Abstract: In recent years, electrocatalytic organic synthesis has attracted increasing attention. Its advantages such as low pollution and high atomic efficiency give it a huge advantage over traditional organic synthesis methods and meet the social requirements of green chemistry. Therefore, detecting the reaction process and key intermediates at the electrode interface from the molecular level has important guiding significance for understanding the reaction mechanism and designing more efficient catalysts. Raman spectroscopy is a type of vibrational spectroscopy that is non-destructive and uninterrupted by water. In particular, surface-enhanced Raman spectroscopy has ultra-high surface sensitivity. It can provide key information on the catalyst surface structure, adsorbed substances and intermediates during the reaction, and provide a reliable platform for exploring the reaction mechanism. This article reviews the recent advances in electrocatalytic organic reaction mechanisms probed by in-situ Raman spectroscopy. Specifically, Raman spectroscopy reveals important intermediates, active substances and reaction pathways in electrocatalytic hydrogenation, activations of C―O, C―X (X = F, Cl, Br, I) and C―H bonds. By analyzing specific cases, it aims to help students understand the research frontiers of organic electrosynthesis and stimulate interest in exploring synthetic electrochemistry, one of IUPAC’s “Top Ten Emerging Technologies in Chemistry” in 2023.

Key words: Raman spectroscopy, Organic electrochemical synthesis, Electrocatalysis, Reaction mechanism

李佳杰, 马骁聪, 郑菊芳, 万强, 周小顺, 王亚浩. 电催化有机反应机理的原位拉曼光谱研究进展[J]. 大学化学, 2025, 40(4): 261-276.

Jiajie Li, Xiaocong Ma, Jufang Zheng, Qiang Wan, Xiaoshun Zhou, Yahao Wang. Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms[J]. University Chemistry, 2025, 40(4): 261-276.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202406117

https://www.dxhx.pku.edu.cn/CN/Y2025/V40/I4/261

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