对氨基硫酚在Au（111）上电化学氧化偶联过程中分子结构演变的原位扫描隧道显微镜可视化研究
收稿日期: 2026-03-03
修回日期: 2026-04-18
录用日期: 2026-05-09
网络出版日期: 2026-05-09
In Situ STM Visualization of Molecular Structural Evolution during Electrochemical Oxidation Coupling of Para-Aminothiophenol on Au(111)
Zi-Wei Ma and Tai-Rui Wu was responsible for the experimental design, implementation, data analysis, and writing of the original draft. An-Ni Zheng, Lai-Ke Chen, Yuan-Hui Xiao and Zhao-Bin Chen assisted in experimental implementation and data analysis. Qing-Na Zheng, Jian-Zhang Zhou, Jia-Wei Yan and De-Yin Wu supervised the research and revised the manuscript.
#These authors are contributed equally to this work.
Received date: 2026-03-03
Revised date: 2026-04-18
Accepted date: 2026-05-09
Online published: 2026-05-09
对巯基苯胺不仅是表面增强拉曼光谱领域中广泛应用的探针分子，而且是界面反应的重要模型分子，具有独特的光氧化和电氧化途径，因此对巯基苯胺在不同的外加电场下被选择性激活。电化学氧化偶联过程中产物和中间产物的演变尚不清楚。采用循环伏安法、电化学表面增强拉曼光谱和原位电化学扫描隧道显微镜研究了对巯基苯胺在Au(111)表面的动态电化学氧化过程。结果表明，在酸性溶液中，对巯基苯胺在Au(111)表面形成不饱和吸附覆盖。当电位正移到氧化电位范围时，对巯基苯胺氧化产生的阳离子自由基与其分子交替排列。当偶联反应发生时，扫描隧道显微镜得到的图像中证实交替排列的吸附结构转变为条带结构。最后，Au(111)表面覆盖率降低，形成
关键词： 原位电化学扫描隧道显微镜; 对巯基苯胺; 4′-巯基-N-苯醌二亚胺; 电化学表面增强拉曼光谱
马子为 , 吴泰锐 , 郑安妮 , 陈来科 , 肖远辉 , 陈招斌 , 郑轻娜 , 周剑章 , 颜佳伟 , 吴德印 . 对氨基硫酚在Au（111）上电化学氧化偶联过程中分子结构演变的原位扫描隧道显微镜可视化研究[J]. 电化学, 2026 , 32(7) : 2603031 . DOI: 10.61558/2993-074X.3614
Para-aminothiophenol (PATP) is not only a widely-used probe molecule in the field of surface-enhanced Raman spectroscopy (SERS), but also an important model molecule for interfacial reactions, exhibiting distinct photo- and electro-oxidation pathways, so that PATP is selectively activated under different external fields. The evolution of products and intermediates during electrochemical oxidative coupling remains unknown. In this study, we have investigated the dynamic electrochemical oxidation process of PATP on the Au(111) surface using cyclic voltammetry, electrochemical (EC)-SERS, and in situ electrochemical scanning tunneling microscopy (EC-STM). The results showed that PATP forms an unsaturated adsorption coverage on Au(111) in an acidic solution. When the potential was positively shifted to the oxidation potential range, the cation radical generated by PATP oxidation alternated with PATP molecules in arrangement. Once the coupling reaction occurred, the adsorption structure of alternating arrangement was transformed into the stripe structure as observed in the STM images. Finally, the coverage on the Au(111) surface decreased and a
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