Cyclic and normal pulse voltammetric studies of 2,3,6,7,10,11-hexaphenylhexazatriphenylene using a benzonitrile thin layer-coated glassy carbon electrode
Cyclic and normal pulse voltammetric studies of 2,3,6,7,10,11-hexaphenylhexazatriphenylene using a benzonitrile thin layer-coated glassy carbon electrode
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DOI：
10.1021/jp0305281
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发表时间：
2003-09
影响因子：
3.3
通讯作者：
Rong Wang;T. Okajima;F. Kitamura;N. Matsumoto;T. Thiemann;S. Mataka*;T. Ohsaka
中科院分区：
文献类型：
--
作者：
Rong Wang;T. Okajima;F. Kitamura;N. Matsumoto;T. Thiemann;S. Mataka*;T. Ohsaka
采用在玻碳电极表面和水溶液之间插入一薄层不溶混有机溶剂（苯甲腈，BN）的方法，研究了一种高疏水性有机分子2，3，6，7，10，11-六苯基六氮杂苯并菲（HAT）的电极反应。在N2饱和的2 MHClO 4水溶液中，在BN薄层涂层电极上观察到4对HAT的氧化还原峰。通过循环伏安法、方波伏安法和正常脉冲伏安法，测定了热力学和动力学参数（即，计算了HAT多步氧化还原反应的形式电位、标准速率常数和阴极转移系数，并计算了HAT的扩散系数。实验结果表明，用所得到的动力学和热力学参数计算得到的脉冲伏安图与实测值吻合较好，说明所得到的动力学和热力学参数是合理的，该方法可用于疏水反应物多步氧化还原反应的动力学研究。提出了HAT整个氧化还原反应的可能反应机理。
The method of interposing a thin layer of immiscible organic solvent (benzonitrile, BN) between a glassy carbon electrode surface and an aqueous solution has been successfully applied to study the electrode reaction of a highly hydrophobic organic molecule, 2,3,6,7,10,11-hexaphenylhexazatriphenylene (HAT). Four couples of well-defined redox peaks of HAT were observed at the BN thin layer-coated electrode in N 2 -saturated 2 M HClO 4 aqueous solution. By cyclic voltammetry, square-wave voltammetry, and normal pulse voltammetry, the thermodynamic and kinetic parameters (i.e., the formal potential, standard rate constant, and cathodic transfer coefficient) for the multistep redox reaction of HAT and its diffusion coefficient were evaluated. The good agreement between the observed normal pulse voltammograms and the calculated one with use of the obtained kinetic and thermodynamic parameters demonstrated that the evaluated parameters are reasonable and that the present approach is useful in the kinetic study of the multistep redox reaction of hydrophobic reactants. A probable reaction mechanism for the whole redox reaction of HAT was also proposed.