The hydrogen-bonding dynamics of water to a nitrile-functionalized electrode is modulated by voltage according to ultrafast 2D IR spectroscopy.
The hydrogen-bonding dynamics of water to a nitrile-functionalized electrode is modulated by voltage according to ultrafast 2D IR spectroscopy.
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DOI：
10.1073/pnas.2314998120
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发表时间：
2023-12
影响因子：
11.1
通讯作者：
Matthew J Ryan;Nan Yang;Kijeong Kwac;Kiera B. Wilhelm;Benjamin K Chi;D. Weix;M. Cho;M. Zanni
中科院分区：
文献类型：
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作者：
Matthew J Ryan;Nan Yang;Kijeong Kwac;Kiera B. Wilhelm;Benjamin K Chi;D. Weix;M. Cho;M. Zanni
重要性关键反应，如小分子的转化，在电化学表面催化。溶剂重定向影响反应自由能景观，但很少有人知道如何施加电场影响溶剂动力学在表面。在这里，我们使用表面增强的二维红外光谱测量光谱特征的时间演变从表面结合的腈标签，其CN拉伸模式报告的本地氢键环境。我们发现，与负电位相比，在正电位下与腈基的氢键断裂和形成的速度要慢2至3倍。这些结果揭示了在电极-水界面处施加电场的动力学后果。
Significance Critical reactions, such as transformations of small molecules, are catalyzed at electrochemical surfaces. Solvent reorientation influences reaction-free energy landscapes, yet little is known about how an applied electric field impacts solvent dynamics at a surface. Here, we use surface-enhanced two-dimensional infrared spectroscopy to measure the temporal evolution of spectroscopic features from a surface-bound nitrile label, whose CN stretching mode reports on the local hydrogen-bonding environment. We find that hydrogen bonds to nitrile groups break and form 2 to 3 times more slowly under positive potential compared to negative potential. These results reveal the dynamical consequences of an applied electric field at the electrode–water interface.