金属/聚电解质界面的原位电化学表面增强拉曼光谱

doi:10.1016/S1872-2067(21)64041-X

催化学报 ›› 2022, Vol. 43 ›› Issue (11): 2820-2825.DOI: 10.1016/S1872-2067(21)64041-X

金属/聚电解质界面的原位电化学表面增强拉曼光谱

吴丽文^†, 黄茉莉^†, 杨云霄, 黄逸凡^*()

上海科技大学物质科学与技术学院, 上海 201210

收稿日期:2022-05-28 接受日期:2022-07-03 出版日期:2022-11-18 发布日期:2022-10-20
通讯作者: 黄逸凡
作者简介:^† 共同第一作者
基金资助:
国家自然科学基金(21991152);国家自然科学基金(21991150);国家自然科学基金(21872094);上海科技大学启动经费

In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces

Li-Wen Wu^†, Mo-Li Huang^†, Yun-Xiao Yang, Yi-Fan Huang^*()

School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China

Received:2022-05-28 Accepted:2022-07-03 Online:2022-11-18 Published:2022-10-20
Contact: Yi-Fan Huang
About author:^† Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21991152);National Natural Science Foundation of China(21991150);National Natural Science Foundation of China(21872094);ShanghaiTech University Starting-Up grant

摘要/Abstract

摘要：

聚合物电解质(聚电解质)在电催化反应器中的应用日益广泛. 理解电极/聚电解质界面的结构和性质有助于从本质上理解并指导优化基于采用聚电解质的电催化过程. 因此, 有必要发展应用于电极/聚电解质界面研究的原位谱学表征方法. 目前, 主要的原位谱学方法是基于X射线的光谱技术, 若能发展原位分子光谱技术, 直接表征电极/聚电解质界面的物种, 特别是电化学反应过程中产生的新物种, 将有助于研究反应机理.

本文报道了一种采用三电极体系的表面增强拉曼光谱测试方法, 用于原位表征电极/聚电解质界面. 这种方法将整套电极/聚电解质膜系统置于密闭的、充满高纯Ar气的电解质之中. 通过层层堆叠的方式, 将石英窗片、工作电极、聚电解质膜和对电极组合在一起. 参比电极靠在聚电解质膜的表面, 工作电极为透明碳薄膜, 用于担载电催化剂, 聚电解质膜可以为酸性、碱性或中性, 对电极为Pt片. Au电极的循环伏安实验表明这套体系能够像在电解质溶液里一样正常工作.

为了在多种聚电解质中应用此方法, 在酸性和碱性聚电解质中分别采用Ag/AgCl和Ag/Ag₂O电极作为参比电极. 在酸性和碱性电解质溶液的测试表明, Ag/AgCl Ag/Ag₂O vs. Hg/Hg的电极电势可以稳定8 h以上, 这保证了电极体系在拉曼光谱测试的时间范围内稳定正常地工作.

为了验证该方法的可行性, 首先原位表征了吸附在Au和Pt表面的对甲基苯硫酚分子(为了获得Pt表面的表面增强拉曼活性, 使用Au@Pt核壳纳米粒子进行实验), 结果表明, Au和Pt表面获得的表面增强拉曼光谱为对甲基苯硫酚分子的特征谱峰. 随着电极电势的变化, 这些特征谱峰的频率轻微移动, 可归因于振动Stark效应(当分子所处环境中的偶极静电场发生变化时, 分子的键长、键角等发生了轻微的变化, 由于分子振动的非简谐性, 振动频率随键长、键角变化而变化), 因此, 原位表面增强拉曼光谱谱峰频率随电极电势变化而变化的现象表明金属/聚电解质界面的电势降受施加电势的调制.

为进一步验证该方法应用于研究电催化反应的可行性, 原位表征了Au在酸性聚电解质膜上的电化学氧化过程. 对比Au在0.1 mol/L HClO₄水溶液中的结果可以确定, 当工作电极的电势恒定于电化学氧化的电势时, 获得了Au表面氧化物的特征谱峰, 该结果也与循环伏安的一致. 综上, 本文方法能够成为一种研究电极/聚电解质界面电催化的有力工具.

关键词: 聚电解质, 原位电化学表征, 表面增强拉曼光谱, 三电极体系, 金氧化

Abstract:

Polyelectrolyte becomes more and more popular in electrocatalysis. The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis. Herein, we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces. The Ag/AgCl and Ag/Ag₂O electrodes are used as the reference electrode in the acidic and the alkaline systems, respectively. The working electrode is made of a transparent carbon thin film which loads the electrocatalysts. The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes. The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.

Key words: Polyelectrolyte, In-situ electrochemical characterization, Surface-enhanced Raman spectroscopy, Three-electrode cell, Au oxidation

吴丽文, 黄茉莉, 杨云霄, 黄逸凡. 金属/聚电解质界面的原位电化学表面增强拉曼光谱[J]. 催化学报, 2022, 43(11): 2820-2825.

Li-Wen Wu, Mo-Li Huang, Yun-Xiao Yang, Yi-Fan Huang. In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces[J]. Chinese Journal of Catalysis, 2022, 43(11): 2820-2825.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64041-X

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图/表 4

Fig. 1. Schematic of the EC-SERS measurement of electrode/polyelectrolyte interface by using a three-electrode cell.

Fig. 2. (a) Voltammograms of Au electrode and Au mesh on Nafion polyelectrolyte membranes and Au electrode in 0.1 mol/L HClO4 solution. (b) Time-dependent potentials of Ag/AgCl vs. Hg/Hg2SO4 and Ag/Ag2O vs. Hg/HgO.

Fig. 3. Potential dependent SERS spectra of PMTP adsorbed on Au nanoparticles on Nafion (a,b) and QAPPT (c,d) and Au@Pt nanoparticles on Nafion (e,f) membranes.

Fig. 4. Potential-dependent SERS spectra of the electrochemical oxidation of Au on Nafion polyelectrolyte membrane (a) and in 0.1 mol/L HClO4 solution (b).

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金属/聚电解质界面的原位电化学表面增强拉曼光谱

In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces

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