电催化界面和反应的电化学阻抗谱研究：经典永不褪色

本文章综述了电催化领域电化学阻抗谱（EIS）的相关研究. 首先概述了从二十世纪初到现在这一专业领域的发展历史. 然后介绍了电催化阻抗理论的几个里程碑. 其中,着重介绍了目前分析电催化EIS数据的主流模型——Dolin-Ershler模型. 之后,具体讨论了铂金单晶的双电层电容,特别是围绕这一基础课题的实验和理论上的挑战. 我们质疑采用Dolin-Ershler模型获取稀溶液中双电层电容的合理性. 因为在稀溶液中,双电层效应使得双电层电容具有频散特性,因而双电层电容的低频部分在分析过程中可能被遗失了. 未来,我们期待看到新的实验去证明或反驳一个最近的理论预测,即铂电极在氧化物生成电位区域中具有非单调表面电荷关系和负双电层电容.

Electrochemical Impedance Spectroscopy for Electrocatalytic Interfaces and Reactions:Classics Never Die

This review article recapitulates electrochemical impedance spectroscopy(EIS)studies in the field of electrocatalysis.The history of this specialized field,ranging from the beginning of the twentieth century to now,is outlined.We then chronicle milestones of the impedance theory.Special emphases are put on the Dolin-Ershler model,the prevailing model for analyzing adsorption impedance data.Afterwards,we narrow into a very specific and fundamental topic,the double-layer capacitance at platinum(Pt)single crystals.We discuss the challenges in experimentation and theoretical understanding thereof.We cast doubts into the validity of using the Dolin-Ershler model to obtain the double-layer capacitance in dilute solutions,in which case diffuse charge effects become important and the low-frequency part of double-layer capacitance is lost.We wish to see future progress in proving or disproving the recent theoretical prediction that Pt electrode possesses a non-monotonic surface charging relation and negative double-layer capacitances in the oxide formation region.