Qu Siqi, Guan Jing, Cai Dongqi, Wang Qianshuo, Wang Xiuyun, Song Wei, Ji Wei
School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, China.
Nanomaterials (Basel). 2022 May 11;12(10):1637. doi: 10.3390/nano12101637.
Electrochemical surface-enhanced Raman scattering (EC-SERS) spectroscopy is an ultrasensitive spectro-electrochemistry technique that provides mechanistic and dynamic information on electrochemical interfaces at the molecular level. However, the plasmon-mediated photocatalysis hinders the intrinsic electrochemical behavior of molecules at electrochemical interfaces. This work aimed to develop a facile method for constructing a reliable EC-SERS substrate that can be used to study the molecular dynamics at electrochemical interfaces. Herein, a novel Ag-WO electrochromic heterostructure was synthesized for EC-SERS. Especially, the use of electrochromic WO film suppresses the influence of hot-electrons-induced catalysis while offering a reliable SERS effect. Based on this finding, the real electrochemical behavior of p-aminothiophenol (PATP) on Ag nanoparticles (NPs) surface was revealed for the first time. We are confident that metal-semiconductor electrochromic heterostructures could be developed into reliable substrates for EC-SERS analysis. Furthermore, the results obtained in this work provide new insights not only into the chemical mechanism of SERS, but also into the hot-electron transfer mechanism in metal-semiconductor heterostructures.
电化学表面增强拉曼散射（EC-SERS）光谱是一种超灵敏的光谱电化学技术，可在分子水平上提供有关电化学界面的机理和动态信息。然而，等离子体介导的光催化阻碍了电化学界面上分子的固有电化学行为。这项工作旨在开发一种简便的方法来构建可靠的EC-SERS基底，该基底可用于研究电化学界面上的分子动力学。在此，合成了一种用于EC-SERS的新型Ag-WO电致变色异质结构。特别是，电致变色WO薄膜的使用抑制了热电子诱导催化的影响，同时提供了可靠的SERS效应。基于这一发现，首次揭示了对氨基硫酚（PATP）在银纳米颗粒（NPs）表面的真实电化学行为。我们相信，金属-半导体电致变色异质结构可以发展成为用于EC-SERS分析的可靠基底。此外，这项工作获得的结果不仅为SERS的化学机理，也为金属-半导体异质结构中的热电子转移机理提供了新的见解。
