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基于不同工作电极的二茂铁电化学电荷转移动力学

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

作者信息

Kaur Rajwinder, Ghoshal Abhik, Galav Prachi, Mondal Prakash Chandra

机构信息

Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, 208 016, India.

Department of Chemistry, Janki Devi Bajaj Government Girls College, Kota, Rajasthan, 324 001, India.

出版信息

Chem Asian J. 2024 Nov 4;19(21):e202400744. doi: 10.1002/asia.202400744. Epub 2024 Sep 24.

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.

摘要

二茂铁是一种偶然发现的有机金属化合物,在研究电化学电荷转移动力学中作为关键的氧化还原探针。除了溶液相研究外,二茂铁衍生物在分子薄膜中也得到了充分探索,包括在各种电极上的自组装单分子层,用于理解表面氧化还原行为、分子电子学和电荷存储应用。异质电荷转移是自旋依赖电化学、光电化学和分子电子器件中有效电荷传输的一个重要参数。在这项工作中,我们旨在研究二茂铁在各种电极上的电化学电荷转移,如市售的玻碳、石墨棒、氧化铟锡(ITO)以及制备的金和镍,以确定工作电极的性质对电子转移速率、扩散系数和氧化还原过程可逆性的影响。进行了基于直流和交流的电化学实验,随后对实验结果进行数字化处理。电子转移动力学和电化学可逆性显示出对工作电极性质的强烈依赖性,因为感兴趣材料的电化学驱动氧化和还原与工作电极的费米能和电子结构直接相关。

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