关键词: 固液界面双电层, 周期性均匀介质溶剂化模型, 第一性原理, 微分电容, 电荷转移系数, Tafel动力学

Abstract:

Solid/liquid double layer is of fundamental importance in electrochemistry. It has been a challenge and focus to understand the equilibrium and the dynamic phenomena (e.g., chemical reactions) at the electrode/electrolyte double layer in a unified theoretical framework. In recent years, rapid expansion and development have been done in the application of first principles density function theory (DFT) simulation on the double layer. This article reviews the current theoretical methods for electrochemistry modeling, such as reaction center model, thermodynamic method and double reference model. The progress in the computation procedures based on first principles periodic continuum solvation method (DFT/CM-MPB) for obtaining the differential capacitance, surface phase, charge transfer coefficient (CTC) and deducing the potential-dependent reaction rate are summarized in detail. Representative reactions, namely, hydrogen evolution reactions, are selected to illustrate how the theoretical methods are applied to compute quantitatively the kinetics of multiple-step electrochemical reactions.

Key words: electrode/electrolyte double layer, periodic continuum solvation method, first principles calculations, differential capacitance, charge transfer coefficient, Tafel kinetics