Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Phys Chem Chem Phys. 2013 Jul 7;15(25):10321-5. doi: 10.1039/c3cp51083b. Epub 2013 May 24.
Electrochemical reaction rates can strongly depend on pH, and there is increasing interest in electrocatalysis in alkaline solution. To date, no method has been devised to address pH in atomic scale simulations. We present a simple method to determine the atomic structure of the metal|solution interface at a given pH and electrode potential. Using Pt(111)|water as an example, we show the effect of pH on the interfacial structure, and discuss its impact on reaction energies and barriers. This method paves the way for ab initio studies of pH effects on the structure and electrocatalytic activity of electrochemical interfaces.
电化学反应速率强烈依赖于 pH 值，因此人们对碱性溶液中的电催化作用越来越感兴趣。迄今为止，还没有设计出在原子尺度模拟中处理 pH 值的方法。我们提出了一种简单的方法来确定给定 pH 值和电极电势下金属-溶液界面的原子结构。以 Pt(111)|水为例，我们展示了 pH 值对界面结构的影响，并讨论了其对反应能量和势垒的影响。该方法为 pH 值对电化学界面结构和电催化活性的从头计算研究铺平了道路。
