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On the Coupling of Electron Transfer to Proton Transfer at Electrified Interfaces
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-06-23 , DOI: 10.1021/jacs.0c03472
Aimin Ge 1 , Georg Kastlunger 2 , Jinhui Meng 1 , Per Lindgren 2 , Jia Song 1 , Qiliang Liu 1 , Alexander Zaslavsky 2 , Tianquan Lian 1 , Andrew A Peterson 2
Affiliation  

Many electrochemical processes are governed by the transfer of protons to the surface, which can be coupled with electron transfer; this electron transfer is in general non-integer and unknown a priori, but is required to hold the potential constant. In this study, we employ a combination of surface spectroscopic techniques and grand-canonical electronic-structure calculations in order to rigorously understand the thermodynamics of this process. Specifically, we explore the protonation/deprotonation of 4-mercaptobenzoic acid as a function of the applied potential. Using grand-canonical electronic-structure calculations, we directly infer the coupled electron transfer, which we find to be on the order of 0.1 electron per proton; experimentally, we also access this quantity via the potential-dependence of the pKa. We show a striking agreement between the potential-dependence of the measured pKa and that calculated with electronic-structure calculations. We further employ a simple electrostatics-based model to show that this slope can equivalently be interpreted to provide information on the degree of coupled electron transfer or the potential change at the point of the charged species.

中文翻译:

关于带电界面处电子转移与质子转移的耦合

许多电化学过程是由质子转移到表面控制的,这可以与电子转移相结合;这种电子转移通常是非整数和先验未知的,但需要保持电位恒定。在这项研究中,我们结合了表面光谱技术和正则电子结构计算,以严格理解这一过程的热力学。具体来说,我们探索了 4-巯基苯甲酸的质子化/去质子化作为应用电位的函数。使用正则电子结构计算,我们直接推断出耦合电子转移,我们发现每个质子大约有 0.1 个电子;通过实验,我们还通过 pKa 的潜在依赖性来访问这个数量。我们显示测量的 pKa 的电位依赖性与通过电子结构计算计算的电位依赖性之间存在惊人的一致性。我们进一步采用一个简单的基于静电学的模型来表明该斜率可以等效地解释为提供有关耦合电子转移程度或带电物种点处的电位变化的信息。
更新日期:2020-06-23
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