摘要
原位电化学拉曼光谱是一种重要的光谱电化学技术.基于超微电极的原位电化学拉曼光谱将拉曼光谱反映的结构信息与电极表面的电化学过程从实验上严格对应和关联,为深刻理解电化学反应机理提供依据.本文综述了采用超微电极作为工作电极的原位电化学拉曼光谱的研究方法和应用进展,总结了应用超微电极作为工作电极开展电化学拉曼光谱实验的方法和具有表面增强拉曼活性的超微电极制备方法,展示了如何利用在超微电极表面获得的拉曼光谱与界面电化学过程的严格关联研究单个锌颗粒电化学氧化过程、吡啶分子在Au电极表面的电化学吸附过程,以及如何利用该技术能以高的信噪比和灵敏度同时测量光电流与分子反应这一特性研究对巯基苯胺选择性光氧化反应.采用超微电极作为工作电极的原位电化学拉曼光谱技术极大拓展了拉曼光谱技术的研究范围,有望成为探索(光)电化学反应的有力工具.
In-situ electrochemical Raman spectroscopy is an important spectroelectrochemical technique.Combining ultramicroelectrodes and EC-SERS can strictly correlate the structural and chemical information in Raman spectra with the electrochemical processes on electrode surface,which enable mechanistic analysis.This article reviews the research methods and applications of in-situ electrochemical Raman spectroscopy with ultramicroelectrodes as working electrodes,and summarizes the methods of electrode preparation,and demonstrates the use of the correlation between Raman spectroscopy and electrochemistry obtained at the ultramicroelectrode in studying the surface species in the electrochemical oxidation of a single zinc particle and the electrochemical adsorption of pyridine on Au surface,and elucidating the selective photooxidation reaction of p-aminothiophenol by simultaneously measuring molecular reactions and photocurrents with high signal-to-noise ratio and sensitivity.The in-situ electrochemical Raman spectroscopy with an ultramicroelectrode as the working electrode has greatly expanded the researches of Raman spectroscopy,and is promising to be a powerful tool for studying electrochemical and photoelectrochemical reactions.
作者
刘乃云
吴丽文
黄逸凡
Naiyun Liu;Liwen Wu;Yi-Fan Huang(School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2021年第3期256-263,共8页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(编号:21872094,21991152)
上海市青年科技英才扬帆计划项目(19YF1433400)资助项目
关键词
超微电极
谱学电化学
拉曼光谱
ultramicroelectrodes
spectroelectrochemistry
Raman spectroscopy
