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

基本信息

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

项目摘要

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.

本工作的目的是通过使用超快速脉冲和扫描伏安（SFV）来建立在超微米薄膜涂层电极下电荷转移速率的确定程序，并表征使用这些电极的特征。在SFV中使用微电极的使用范围是不高的范围，而远不足的范围是远不足的范围，并且远不足的范围是远不足的范围。由于电气双层的充电电流大大减少。因此，在微电极处使用SFV，其中可以实现扫描电位的扫描速率至Ca 10^5vs^<-1>，并且可以实现高达Ca 1 sec的电位速率，因此可以直接检查和可靠地检查快速的电化学动力学，而对于常规尺寸的电极来说，确定很难或不可能确定这些动力学。我们在这里成功地确定了金属配合物的异质电子转移速率常数（Mo（Cn）^<4-/3-> _，W（Cn）^（Cn）^<4-/3-> _，OS（Cn）^<4-/3-> _等）。我们研究了在聚合物涂层电极上电极反应的动力学和热力学，其中上述多价阴离子复合物在电极表面上的阳离子聚合物膜中固定在静电上。 SFV还对电活性膜涂层电极进行了对电荷传输过程的动力学检查，事实证明，该电极很有用。在这项研究中，试图在聚合物涂层的电极上揭示电荷转移过程时已经有许多有趣的发展。这些进步开辟了全新的调查领域，结合了电化学，聚合物化学，有机化学，无机化学，生物化学，物理学等的现代方面。