Derivative-extremum analysis of current-potential curves showing electrochemical kinetics in the full reversibility range

作     者：Fengjun Yin Hong Liu Fengjun Yin;Hong Liu

作者机构：Chongqing Institute of Green and Intelligent TechnologyChinese Academy of SciencesChongqing 400714China Key Laboratory of Reservoir Aquatic EnvironmentChinese Academy of SciencesChongqing 400714China China University of Chinese Academy of SciencesBeijing 100049China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2023年第34卷第1期

页      面：544-549页

核心收录：

学科分类：07[理学] 0703[理学-化学] 0701[理学-数学] 070101[理学-基础数学] 

基　　金：financially supported by the National Natural Science Foundation of China (Nos. 52131003  52170059  51808526  51727812) 

主　　题：Reversibility Electrochemical kinetics Half-wave potential Derivative-extremum analysis Parameter determinations 

摘      要：Derivative-extremum analysis(DEA) of j-E curves is a newly proposed method of half wave potential(E1/2) and activation feature extraction from steady-state voltammetry. Here, the DEA is demonstrated to be valid in the full range of reversibility using numerical simulations with a derived universal electrode equation, providing a novel perspective of electrochemical kinetics in the reversibility domain. The results reveal that E1/2is a better choice of the reference potential instead of equilibrium potential(Eeq) in electrode equations, especially since Eeqis meaningless in an irreversible case. The equations referenced with standard potential, E1/2and Eeq, are summarized in three tables, and their applications in parameter determinations are specified. Finally, reversibility is proved to be a relative measure between kinetic slowness and mass transport of electroactive species, and the reversibility classifications are proposed according to the DEA feature in the reversibility domain. This work, based on the DEA principle, refines the electrode equation forms and generalizes their applicability in the full range of reversibility.