Visualizing On-Surface Decomposition Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy
Visualizing On-Surface Decomposition Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy
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DOI：
10.1021/acs.jpclett.2c01112
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发表时间：
2022-06-09
影响因子：
5.7
通讯作者：
Zenobi, Renato
中科院分区：
文献类型：
--
作者：
Cai, Zhen-Feng;Kiser, Timon;Zenobi, Renato
固液界面分子分解过程的化学成像是实现机理理解的一个长期存在的问题。传统的分析工具无法满足这一挑战，因为在纳米尺度上缺乏所需的化学灵敏度和特异性。在这项工作中，我们表明，高分辨率的高光谱尖端增强拉曼光谱（TERS）成像可以是一个强大的分析工具，研究在纳米尺度上的表面分解化学。具体来说，我们提出了一个基于TERS的高光谱方法来可视化的表面分解过程的吡啶-4-硫醇自组装单层原子级平坦的Au（111）表面在环境条件下。参与降解过程的活性中间体以5 nm的空间分辨率进行光谱检测。通过支持密度泛函理论模拟，可以将关键物种分配给二硫化物反应中间体。这项工作开辟了一个新的应用领域，定量研究表面分解化学和相关的动力学在固-液界面与纳米空间分辨率。
Chemical imaging of molecular decomposition processes at solid-liquid interfaces is a long-standing problem in achieving mechanistic understanding. Conventional analytical tools fail to meet this challenge due to the lack of required chemical sensitivity and specificity at the nanometer scale. In this work, we demonstrate that high-resolution hyperspectral tip-enhanced Raman spectroscopy (TERS) imaging can be a powerful analytical tool for studying on-surface decomposition chemistry at the nanoscale. Specifically, we present a TERS-based hyperspectral approach to visualize the on-surface decomposition process of a pyridine-4-thiol self-assembled monolayer on atomically flat Au(111) surfaces under ambient conditions. Reactive intermediates involved in the degradation process are spectroscopically detected with 5 nm spatial resolution. With supporting density functional theory simulations, a key species could be assigned to the disulfide reaction intermediate. This work opens a new application area for studying on-surface decomposition chemistry and related dynamics quantitatively at solid-liquid interfaces with nanometer spatial resolution.