Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (7): 1219-1230.doi: 10.3866/PKU.WHXB201505071

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Progress of Research on Underpotential Deposition—— I. Theory of Underpotential Deposition

XU Zhen1, CHEN Yu2, ZHANG Zhao1, ZHANG Jian-Qing1   

  1. 1 Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China;
    2 Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, P. R. China
  • Received:2015-03-23 Revised:2015-05-06 Published:2015-07-08
  • Contact: ZHANG Zhao
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21273199, 21073162) and Specialized Research Fund for the Doctoral Program of Higher Education, China (20130101110047).


Underpotential deposition (upd) has been a hotspot in the field of electrochemical research throughout the years owing to its significant theoretical and applied research value. Theoretical research on upd primarily centers around the relations and rules of interaction among deposition substrates, deposition species, and anions (or other organic additives) during upd process. In this paper, the developments in theoretical research in recent years on upd on both the local and international levels are systematically summarized mainly from two viewpoints, namely, thermodynamics and kinetics. With regard to the thermodynamics of upd process, introductory comments and mathematical formulas are summarized from four aspects, i.e., underpotential shift (ΔEupd), electrosorption valency (γ), influence of temperature, and electrochemical adsorption isotherms. The applications and analyses of those related mathematical formulas are also presented in detail. In terms of the kinetics of upd process, nucleation and growth phenomena are mainly presented. We summarize the relevant mathematical models, and additionally introduce research studies on the characteristics of upd kinetics based on these mathematical models. Furthermore, this paper presents an outline of computational chemistry methods and application achievements concerning upd research. Finally, the theoretical research status of upd is presented, giving an overall view of the development trend.

Key words: Electrochemistry, Underpotential deposition, Thermodynamics, Kinetics, Computational chemistry