电化学（中英文）2026，Vol.32Issue(7)：27-37,封3,12.DOI:10.61558/2993-074X.3614
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
In Situ STM Visualization of Molecular Structural Evolution during Electrochemical Oxidation Coupling of Para-Aminothiophenol on Au(111)
摘要
Abstract
Para-aminothiophenol(PATP)is not only a widely-used probe molecule in the field of surface-enhanced Raman spec-troscopy(SERS),but also an important model molecule for interfacial reactions,exhibiting distinct photo-and electro-oxi-dation pathways,so that PATP is selectively activated under different external fields.The evolution of products and inter-mediates 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).T he 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 ob-served in the STM images.Finally,the coverage on the Au(111)surface decreased and a √3×4√6 structure was formed.Accordingly,the oxidation reaction product 4′-mercapto-N-phenylquinone diimine(NPQD)would adopt the arrangement of mixed adsorption sites of bridge and hollow sites on Au(111).By determining the adsorption structure evolution of PATP during the electrooxidation process on the gold surface,the mechanism of interfacial electrochemical oxidation coupling reaction is revealed from a spatial perspective.This lays the foundation for further modulation and design of the interfacial reaction of aromatic amine molecules.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Key words
In situ electrochemical scanning tunneling microscopy/Para-aminothiophenol(PATP)/4′-mercapto-N-phenylquinone diimine/Electrochemical surface-enhanced Raman spectroscopy引用本文复制引用
马子为,吴德印,吴泰锐,郑安妮,陈来科,肖远辉,陈招斌,郑轻娜,周剑章,颜佳伟..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（中英文）,2026,32(7):27-37,封3,12.基金项目
We acknowledge support from the National Nat-ural Science Foundation of China(NSFC)(22302163,22032004,92372124,and 22372140),the Chinese Min-istry of Science and Technology(2024YFA1210800),and Funds of Fujian Science and Technology Office. （NSFC）
