物理化学学报 >> 2024, Vol. 40 >> Issue (3): 2304040.doi: 10.3866/PKU.WHXB202304040

所属专题: 电化学前沿

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电化学谱学表征方法的应用与发展

朱越洲1, 王琨1, 郑世胜2, 汪弘嘉1, 董金超1, 李剑锋1   

  1. 1 厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 福建 厦门 361005;
    2 北京大学深圳研究生院, 新材料学院, 广东 深圳 518000
  • 收稿日期:2023-04-24 修回日期:2023-05-19 发布日期:2023-05-31
  • 通讯作者: 李剑锋,Email:Li@xmu.edu.cn;郑世胜,Email:1801213268@pku.edu.cn E-mail:Li@xmu.edu.cn;1801213268@pku.edu.cn
  • 基金资助:
    国家重点研发计划(2020YFB1505800)和国家自然科学基金(21925404, 22075099, 21991151)资助项目

Application and Development of Electrochemical Spectroscopy Methods

Yue-Zhou Zhu1, Kun Wang1, Shi-Sheng Zheng2, Hong-Jia Wang1, Jin-Chao Dong1, Jian-Feng Li1   

  1. 1 State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, China;
    2 School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen 518000, Guangdong Province, China
  • Received:2023-04-24 Revised:2023-05-19 Published:2023-05-31
  • Supported by:
    The project was supported by the National Key Research and Development Program of China (2020YFB1505800) and the National Natural Science Foundation of China (21925404, 22075099, 21991151).

摘要: 经历两个多世纪的发展,电化学表征方法的理论和实验研究不断完善,在表界面精细结构表征、电化学反应机理研究等方面起到重要作用。电化学谱学表征技术的出现,填补了传统电化学表征方法在分子水平上鉴定电化学反应活性位点及中间物种的空白。本文总结了近年来红外光谱(IR)、表面增强拉曼光谱(SERS)及和频振动光谱(SFG)三种经典分子振动光谱电化学表征技术的研究进展。首先介绍了三种光谱的基本原理和电化学联用电解池的设计,然后从基础电化学理论出发,介绍其在模型单晶体系及界面水机理研究中的应用,进一步重点介绍了其在锂离子电池和燃料电池领域的相关研究进展,最后展望了电化学谱学表征技术的未来发展方向。

关键词: 光谱电化学, 傅里叶变换红外光谱, 表面增强拉曼光谱, 和频振动光谱

Abstract: The theoretical and experimental technologies used for electrochemical characterization methods, which are essential for determining surface structures and elucidating electrochemical reaction mechanisms, have been significantly improved after more than two centuries of development. Traditional chemical methods like cyclic voltammetry (CV) can provide the exact electrochemical reaction rate in different potential ranges, which is beneficial for identifying the electrochemical performance of electrocatalytic materials. However, traditional chemical methods alone are often inadequate when it comes to achieving a deep understanding of reaction mechanisms. In this regard, spectroscopic methods, which are powerful tools to identify the active sites and intermediate species during electrochemical reactions, are widely applied to elucidate the electrochemical mechanism at a molecular or even atomic level. In this review, three molecular-vibration-spectroscopy-based electrochemical characterization technologies, viz., infrared (IR) spectroscopy, surface-enhanced Raman spectroscopy (SERS), and sum frequency generation (SFG) spectroscopy, are comprehensively reviewed and discussed. IR, SERS, and SFG are all non-destructive spectroscopic techniques with ultra-high surface sensitivity and are indispensable when detecting surface species during electrochemical reactions. Consequently, researchers have strived to combine these spectroscopic techniques with basic electrochemical instruments. In fundamental electrochemical research, detecting electrochemical reactions in model single-crystal systems and determining the structure of interfacial water molecules have been two major research topics in recent years. Single-crystal surfaces are important in fundamental electrochemical research because of their defined atom arrays and energy states, serving as model systems to help bridge experimental results and theoretical calculations. Meanwhile, the structure of interfacial water influences most electrochemical reaction processes, and as such, probing interfacial water structures is a challenging but valuable target in fundamental electrochemical research. Additionally, the application of electrochemical spectroscopic methods to analyze fuel cells has become important, and this review covers recent SERS studies of oxygen reduction reactions (ORR) and hydrogen oxidation reactions (HOR) in hydrogen fuel cells. Concurrently, electrochemical IR and SFG studies on the electrooxidation of small organic molecules are discussed. Finally, owing to the significance of lithium-ion batteries, studies of electrochemical spectroscopic methods on solid electrolyte interphase (SEI) and cathode-electrolyte interface (CEI) are becoming increasingly important and are introduced here. In conclusion, recent advances and the future developments of electrochemical spectroscopy methods are summarized in this review article.

Key words: Electrochemical spectroscopy, Fourier transform infrared spectroscopy, Surface enhanced Raman spectroscopy, Sum-frequency generation spectroscopy