The Determination of the Charge-Transfer Rate at Ultra-Micro Film-Coated Electrodes by Using Super Fast Pulse Voltammetry

超快脉冲伏安法测定超微米薄膜电极的电荷转移速率

• 批准号: 62470071
• 负责人: OYAMA Noboru
• 金额: $ 3.71万
• 依托单位: Tokyo University of Agriculture and Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470071/
• 关键词: Ultra-micro electrode; Film coated electrode; Electrochemical kinetics; Super fast pulse voltammetry; 電極反応速度定数; 薄膜被覆電極; 微小酵素センサ

The purpose of the present work is to establish the determination procedures of the charge-transfer rate at ultra-micro film-coated electrodes by using super fast pulse and sweep voltammetries (SFV) and to characterize the features of the use of these electrodes.The advantageous features of the use of microelectrodes in SFV are the elimination of iR drop effect due to very low cell current and the enhanced ratios of faradaic/non-faradaic response due to much diminished charging currents of electrical double layer. Thus, using SFV at microelectrodes, where scan rates of potential up to ca 10^5Vs^<-1>and step rates of potential up to ca 1 sec are attainable, it has become possible to examine straightforwards and reliably fast electrochemical kinetics, the determination of which was very difficult or impossible with a conventionally sized electrode. We here succeeded in the determination of the heterogeneous electron-transfer rate constants of metal complexes (Mo(CN)^<4-/3->_ , W(CN)^<4-/3->_ , Os(CN)^<4-/3->_ etc.). We have studied the kinetics and thermodynamics of the electrode reactions at polymer-coated electrodes where the above-mentioned multi-valent anionic complexes are confined electrostatically in cationic polymer films on electrode surfaces. A kinetic examination of the charge-transport processes at electroactive electropolymerized films-coated electrodes has also been conducted by SFV, which proved to be useful as described above.In this research, there have been many interesting developments in attempting to unravel the charge-transfer processes on polymer-coated electrodes. These advances have opened up whole new areas of investigation which combine modern aspects of electrochemistry, polymer chemistry, organic chemistry, inorganic chemistry, biochemistry, physics, etc.

本工作的目的是建立超快脉冲和扫描伏安法（SFV）测定超微膜涂覆电极的电荷转移速率的方法，并表征这些电极的使用特点。微电极用于SFV的优点是消除了由于极低的电池电流而产生的iR下降效应，以及由于电双层充电电流的大大减小而提高了法拉第/非法拉第响应比。因此，在微电极上使用SFV，可以实现高达10^ 5v ^<-1>的扫描速率和高达1秒的步进速率，从而可以直接可靠地快速检测电化学动力学，而传统尺寸的电极很难或不可能确定这一点。本文成功地测定了金属配合物Mo(CN)^<4-/3->_、W(CN)^<4-/3->_、Os(CN)^<4-/3->_等的非均相电子转移速率常数。我们研究了上述多价阴离子配合物静电限制在电极表面的阳离子聚合物薄膜上的聚合物包覆电极上电极反应的动力学和热力学。用SFV对电活性电聚合膜涂覆电极上的电荷输运过程进行了动力学检查，这证明了上述方法的有用性。在这项研究中，在试图揭示聚合物涂层电极上的电荷转移过程方面取得了许多有趣的进展。这些进展开辟了一个全新的研究领域，它结合了电化学、聚合物化学、有机化学、无机化学、生物化学、物理学等现代方面。

项目成果

小山昇: "現代電気化学法-基礎マニアル" 講談社サイエンティフィック, (1988)

小山升：《现代电化学方法 - 基本手册》讲谈社科学，（1988）

Noboru Oyama: "Molecular Design of Electrode Surfaces." John Wiley,

Noboru Oyama：“电极表面的分子设计。”

Noboru Oyama: J.Chem.Soc.,Chem.Commun.1133-1134 (1987)

小山升：J.Chem.Soc.，Chem.Commun.1133-1134 (1987)

Noboru Oyama: "Molecular Design of Electrode Surfaces." John Wiley, (1989)

Noboru Oyama：“电极表面的分子设计。”

Noboru Oyama: Anal.Chem.60. 2534-2536 (1988)

小山升：Anal.Chem.60。