Zhang Zengming, Huang Jun
Institute of Energy Technologies, IET-3: Theory and Computation of Energy Materials, Forschungszentrum Jülich GmbH, Jülich 52425, Germany.
Theory of Electrocatalytic Interfaces, Faculty of Georesources and Materials Engineering, RWTH Aachen University, Aachen 52062, Germany.
JACS Au. 2025 Jun 17;5(7):3453-3467. doi: 10.1021/jacsau.5c00508. eCollection 2025 Jul 28.
While the traditional Gouy-Chapman-Stern (GCS) model can well describe the differential doublelayer capacitance ( ) near the potential of zero charge with several empirical parameters, it is insufficient to capture the profile in a wide potential range and changes in the profiles with varying electrolyte cations, anions, and solvent, even for the atomistically smooth Mercury-solution interfaces. The extended data set of at mercury is then analyzed using modified semiclassical, density-potential functional theoretical (DPFT) models. Our analysis highlights the importance of potential-dependent short-range metal-solvent interactions and ion partial desolvation at highly charged surfaces. With the aid of the modified model, the impact of electrolyte cation, anion, and solvent on the EDL structure can be interpreted in an inherent framework. These insights gleaned from the mercury electrodes have crucial implications for the EDLs at gold, silver, and copper, which are usually highly charged in important electrocatalytic reactions like electrochemical CO reduction.
虽然传统的古依-查普曼-斯特恩（GCS）模型可以通过几个经验参数很好地描述零电荷电位附近的微分双层电容（ ），但即使对于原子级光滑的汞-溶液界面，它也不足以捕捉宽电位范围内的 分布以及 分布随电解质阳离子、阴离子和溶剂变化的情况。然后使用改进的半经典密度势泛函理论（DPFT）模型分析汞的扩展 数据集。我们的分析突出了电位依赖的短程金属-溶剂相互作用以及高电荷表面上离子部分去溶剂化的重要性。借助改进后的模型，可以在一个内在框架中解释电解质阳离子、阴离子和溶剂对双电层结构的影响。从汞电极获得的这些见解对于金、银和铜的双电层具有至关重要的意义，在诸如电化学CO还原等重要的电催化反应中，这些金属通常带有高电荷。
