Transient cyclic voltammetry: new theoretical challenges to bring up to date a famous electrochemical lady
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FEATURE ARTICLE
Transient cyclic voltammetry: new theoretical challenges to bring up to date a famous electrochemical lady Alexander Oleinick 1 & Irina Svir 1,2 & Christian Amatore 3,1 Received: 6 March 2020 / Revised: 6 March 2020 / Accepted: 11 March 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Cyclic voltammetry has proven its versatile popularity compared with most other electroanalytical methods for investigating electrochemical mechanisms and kinetics. Many textbooks provide clues for understanding and quantify the main features displayed in a voltammogram, but this is unfortunately not often useful when confronted to intricate mechanisms as those presently investigated. This brief opinion article discloses a few theoretical challenges that need to be solved to investigate issues associated with modern applications of cyclic voltammetry.
Cyclic voltammetry has proven its invaluable analytical performance especially since the introduction of microelectrodes [1] followed by that of nanoelectrodes [2] has permitted rapid measurements of concentrations and other electrochemical parameters of importance in still solutions, polymers [3], living materials [4], etc. One of the reasons why cyclic voltammetry supplanted the main other electrochemical methods is that, in addition to classical electrochemical data, it offers a wealth of information about mechanistic pathways initiated by electron transfers to or from an electrode surface [5]. Many textbooks and articles exist to provide useful hints for solving elementary mechanistic situations and extract quantitative data about the thermodynamics and kinetics of the few steps whose nature(s) and magnitude(s) influence the voltammetric data [5–7]. However, most mechanistic problems considered in molecular electrochemistry nowadays involve complex competitive and entangled reactions that occur indifferently in solutions and onto the surface of electrodes, quite often with Dedicated to our esteemed friend and colleague, Prof. Dr. Fritz Scholtz, at the occasion of his 65th birthday. * Christian Amatore [email protected] 1
PASTEUR, Departement de Chimie, Ecole Normale Superieure, PSL University, Sorbonne University, CNRS, 75005 Paris, France
2
Design Automation Department, Kharkiv National University of Radioelectronics, Nauky Avenue, 14, Kharkiv 61166, Ukraine
3
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
a series of entwined surface solution sequences. When confronted to such problems, the classical views result inefficient. For example, we recently introduced and investigated what is now termed the “Laviron-Amatore” paradox in the case of the electrocatalyzed reduction of benzyl chloride at silver cathodes [8]. Although the critical steps are essentially heterogeneous, involving adsorbed and chemisorbed intermediates, the voltammetric trace displayed none of the expected corresponding features. Conversely, the voltamme
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