物理化学学报 >> 2015, Vol. 31 >> Issue (7): 1219-1230.doi: 10.3866/PKU.WHXB201505071

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欠电位沉积研究现状——I.欠电位沉积理论

许振1, 陈宇2, 张昭1, 张鉴清1   

  1. 1 浙江大学化学系, 杭州310027;
    2 浙江大学材料科学与工程学系, 杭州310027
  • 收稿日期:2015-03-23 修回日期:2015-05-06 发布日期:2015-07-08
  • 通讯作者: 张昭 E-mail:eaglezzy@zjuem.zju.edu.cn
  • 基金资助:

    国家自然科学基金(21273199, 21073162)和教育部博士点基金(20130101110047)项目资助

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 E-mail:eaglezzy@zjuem.zju.edu.cn
  • 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).

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摘要：

欠电位沉积(upd)具有重要的理论和应用价值, 一直是电化学领域的研究热点. upd 过程理论研究的实质主要为围绕沉积基体、沉积物种和阴离子(或其他有机添加剂)三者在upd过程中的相互作用关系和规律的研究. 本文从upd 过程热力学和动力学两个方面出发, 系统地概述了近年来国内外在upd 理论研究方面的进展.在upd过程热力学方面, 从欠电位位移(ΔEupd)、upd电吸附价(γ)、温度对upd的影响和电化学吸附等温线四个方面进行了阐述, 概括和分析了upd 过程热力学研究中涉及的相关数学表达式及其应用; 在其动力学方面, 主要概述了upd成核和生长过程动力学, 总结介绍了借助相关数学模型在分析upd过程动力学特征方面的研究. 此外, 简单介绍了计算化学在upd 研究中的应用成果; 最后, 总结了upd 的理论研究现状并展望了upd 的未来研究方向.

关键词: 电化学, 欠电位沉积, 热力学, 动力学, 计算化学

Abstract:

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