Electrochemical Charge Transfer Kinetics of Ferrocene in the Light of Different Working Electrodes

Abstract Ferrocene is an accidentally discovered organometallic compound that serves as a crucial redox probe in investigating electrochemical charge transfer dynamics. Besides solution phase studies, ferrocene derivatives are well‐explored in molecular thin films, including self‐assembled monolayers on various electrodes for understanding on‐surface redox behavior, molecular electronics, and charge storage applications. Heterogeneous charge transfer is an imperative parameter for efficient charge transport in spin‐dependent electrochemistry, photoelectrochemistry, and molecular electronic devices. In this work, we aim to study the electrochemical charge transfer of ferrocene on various electrodes such as commercially obtained glassy carbon, graphite rod, indium tin oxide (ITO), and as‐prepared gold, and nickel to determine the impact of the nature of the working electrode on the electron transfer rate, diffusion coefficient, and reversibility of the redox process. Both the direct current and alternating current‐based electrochemical experiments are performed, followed by digitization of the experimental results. The kinetics of electron transfer and electrochemical reversibility reveal a strong dependence on the nature of the working electrode, as the electrochemically driven oxidation and reduction of the material of interest are directly related to the Fermi energy and electronic structure of the working electrode.