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.
Graphical Abstract
Keywords
electrode/electrolyte double layer, periodic continuum solvation method, first principles calculations, differential capacitance, charge transfer coefficient, Tafel kinetics
Publication Date
2020-02-28
Online Available Date
2019-12-10
Revised Date
2019-01-29
Received Date
2019-01-07
Recommended Citation
Ya-hui FANG, Zhi-pan LIU.
Insight into the Important Solid/Liquid Double Layer from First-Principles Calculations[J]. Journal of Electrochemistry,
2020
,
26(1): 32-40.
DOI: 10.13208/j.electrochem.181243
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol26/iss1/9
