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循环可再生液态银汞齐膜电极上 In(III)离子电还原的动力学和机理:In(III)-乙酰唑胺活性配合物的意义。

Kinetics and Mechanism of In(III) Ions Electroreduction on Cyclically Renewable Liquid Silver Amalgam Film Electrode: Significance of the Active Complexes of In(III)-Acetazolamide.

机构信息

Department of Analytical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska Sq. 3, 20-031 Lublin, Poland.

Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.

出版信息

Molecules. 2023 Mar 25;28(7):2942. doi: 10.3390/molecules28072942.

Abstract

The results of kinetic measurements revealed an accelerating effect of acetazolamide (ACT) on the multistep In(III) ions electroreduction in chlorates(VII) on a novel, cyclically renewable liquid silver amalgam film electrode (R-AgLAFE). The kinetic and thermodynamic parameters were determined by applying the DC polarography, square-wave (SWV) and cyclic voltammetry (CV), as well as electrochemical impedance spectroscopy (EIS). It was shown that ACT catalyzed the electrode reaction ("cap-pair" effect) by adsorbing on the surface of the R-AgLAFE electrode. The catalytic activity of ACT was explained as related to its ability to form active In(III)- acetazolamide complexes on the electrode surface, facilitating the electron transfer process. The active complexes constitute a substrate in the electroreduction process and their different structures and properties are responsible for differences in the catalytic activity. The determined values of the activation energy ΔH≠ point to the catalytic activity of ACT in the In(III) ions electroreduction process in chlorates(VII). Analysis of the standard entropy values ΔS0 confirm changes in the dynamics of the electrode process.

摘要

动力学测量结果表明,新型循环可再生液态银汞齐膜电极(R-AgLAFE)上,唑来膦酸(ACT)对氯酸根(VII)中多步 In(III)离子电化学还原具有加速作用。通过应用直流极谱法、方波(SWV)和循环伏安法(CV)以及电化学阻抗谱(EIS)确定了动力学和热力学参数。结果表明,ACT 通过在 R-AgLAFE 电极表面吸附来催化电极反应(“盖帽对”效应)。ACT 的催化活性可归因于其在电极表面形成活性 In(III)-唑来膦酸配合物的能力,从而促进电子转移过程。活性配合物构成电还原过程中的底物,其不同的结构和性质导致催化活性的差异。确定的活化能ΔH≠值表明 ACT 在氯酸根(VII)中 In(III)离子电化学还原过程中的催化活性。标准熵值ΔS0的分析证实了电极过程动力学的变化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e1d8/10095755/b1635e308bee/molecules-28-02942-g001.jpg

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