Modeling Electrified Pt(111)-H(ad)/Water Interfaces from Ab Initio Molecular Dynamics.
Modeling Electrified Pt(111)-H(ad)/Water Interfaces from Ab Initio Molecular Dynamics.
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从头算分子动力学模拟带电 Pt(111)-Had/水界面
DOI：
10.1021/jacsau.1c00108
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发表时间：
2021-05-24
期刊：
影响因子：
8
通讯作者：
Cheng J
中科院分区：
文献类型：
--
作者：
Le JB;Chen A;Li L;Xiong JF;Lan J;Liu YP;Iannuzzi M;Cheng J
揭示带电界面双电层的原子结构对于理解电催化反应机理和合理设计性能更好的电极材料具有重要意义。尽管过去做出了许多努力，但仍然缺乏对EDL的分子水平的理解。结合最先进的从头算分子动力学（AIMD）和最近开发的计算标准氢电极（cSHE）方法，可以在明确定义的电化学条件下真实地模拟EDL。在这项工作中，我们报告了广泛的AIMD计算的带电Pt（111）-Had/水界面在饱和覆盖的吸附氢（Had）对应于典型的析氢反应条件。利用cSHE方法计算了一系列不同表面电荷密度的EDL模型的电极电势，并进一步得到了与实验相符的亥姆霍兹电容。此外，AIMD模拟允许对带电界面进行详细的结构分析，例如吸附物Had的分布以及界面水和抗衡离子的结构，这反过来可以解释计算的界面水的介电性质。我们的计算为带电界面提供了有价值的分子见解，并为了解EDL内部发生的各种电化学过程提供了坚实的基础。
Unraveling the atomistic structures of electric double layers (EDL) at electrified interfaces is of paramount importance for understanding the mechanisms of electrocatalytic reactions and rationally designing electrode materials with better performance. Despite numerous efforts dedicated in the past, a molecular level understanding of the EDL is still lacking. Combining the state-of-the-art ab initio molecular dynamics (AIMD) and recently developed computational standard hydrogen electrode (cSHE) method, it is possible to realistically simulate the EDL under well-defined electrochemical conditions. In this work, we report extensive AIMD calculation of the electrified Pt(111)-Had/water interfaces at the saturation coverage of adsorbed hydrogen (Had) corresponding to the typical hydrogen evolution reaction conditions. We calculate the electrode potentials of a series of EDL models with various surface charge densities using the cSHE method and further obtain the Helmholtz capacitance that agrees with experiment. Furthermore, the AIMD simulations allow for detailed structural analyses of the electrified interfaces, such as the distribution of adsorbate Had and the structures of interface water and counterions, which can in turn explain the computed dielectric property of interface water. Our calculation provides valuable molecular insight into the electrified interfaces and a solid basis for understanding a variety of electrochemical processes occurring inside the EDL.
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影响因子：
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