Surface electrode processes in the light of implicit anodic and cathodic current components

IF 2.6 4区 化学 Q3 ELECTROCHEMISTRY
Valentin Mirceski, Mihaela Puiu, Rubin Gulaboski, Sławomira Skrzypek, Camelia Bala
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引用次数: 0

Abstract

A recently introduced methodology (Sci Rep 14:17314) for estimating the implicit anodic and cathodic current components of a net, experimentally measured current at a given potential is applied to surface-confined, diffusionless electrode processes. Under the simplest conditions of a voltammetric experiment with a linear potential sweep, the conventional voltammogram is deconstructed into genuine anodic and cathodic current components. These components exhibit high sensitivity to electrode kinetics, offering an alternative perspective on electrochemical reversibility compared to conventional cyclic voltammetry. To calculate the implicit current components, prior knowledge of the formal potential of the redox couple is required, along with integration of the net current. Once determined, these current components allow independent estimation of the electrode kinetic parameters, i.e., standard rate constant and the electron transfer coefficient, either through Tafel-like analysis or by employing a novel form of differential current. In the kinetic regime of very fast, seemingly electrochemically reversible electrode reactions—where the net current becomes independent of electrode kinetics—the implicit current components remain highly sensitive to these kinetics. The theoretical considerations are supported by experiments on the reduction of methylene blue, covalently immobilized on a gold electrode via the self-assembly of a mixed peptide-thiol layer.

根据隐式阳极和阴极电流分量的表面电极加工
最近介绍了一种方法(Sci Rep 14:17 . 314),用于估计网络的隐式阳极和阴极电流成分,实验测量给定电位下的电流被应用于表面受限的无扩散电极过程。在线性电位扫描伏安实验的最简单条件下,传统的伏安图被分解成真正的阳极和阴极电流分量。这些成分对电极动力学具有高灵敏度,与传统的循环伏安法相比,提供了电化学可逆性的另一种观点。为了计算隐式电流分量,需要事先了解氧化还原对的形式电位,以及净电流的积分。一旦确定,这些电流分量允许独立估计电极动力学参数,即标准速率常数和电子传递系数,要么通过类似塔菲尔的分析,要么通过采用一种新的差分电流形式。在非常快的,看似电化学可逆的电极反应的动力学体系中,净电流变得与电极动力学无关,隐电流分量对这些动力学仍然高度敏感。通过混合肽-硫醇层的自组装在金电极上共价固定亚甲基蓝的实验支持了理论上的考虑。
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来源期刊
CiteScore
4.80
自引率
4.00%
发文量
227
审稿时长
4.1 months
期刊介绍: The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry. The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces. The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis. The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.
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