A model of the potential-dependent adsorption of charged redox-active species at the electrode surface
A model of the potential-dependent adsorption of charged redox-active species at the electrode surface
复制标题
带电氧化还原活性物质在电极表面的电位依赖性吸附模型
DOI：
10.1016/j.electacta.2017.10.192
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发表时间：
2018
影响因子：
6.6
通讯作者：
Kenji Kano
中科院分区：
文献类型：
--
作者：
Yuki Kitazumi;Osamu Shirai;Masahiro Yamaomto;Kenji Kano
一个非极化界面的模型被开发和被认为是在特定的吸附带电的氧化还原物种和非特异性吸附的支持电解质。荷电氧化还原物种的吸附系数取决于它们的电荷和内亥姆霍兹平面上的电势。氧化还原物种和支持电解质的吸附量估计使用Frumkin等温线和Gouy-Chapman理论，分别。氧化还原物种的氧化和还原形式中的一种或两种的吸附量的电位依赖性在其标准电位附近最大化。本文重新讨论了外控电位作用下非极化液态金属-溶液界面的电毛细方程。推导出的电毛细方程便于根据吸附离子的量计算非极化界面的电毛细曲线。基于该模型计算的电毛细曲线在氧化还原对的标准氧化还原电位附近可能有一个凹陷部分，这表明界面是电禁戒的。
A model of a non-polarizable interface is developed and considered in terms of the specific adsorption of charged redox species and the nonspecific adsorption of the supporting electrolyte. The adsorption coefficients of charged redox species depend on their charges and the potential at the inner Helmholtz plane. The adsorbed amounts of the redox species and supporting electrolyte are estimated using the Frumkin isotherm and Gouy–Chapman theory, respectively. The potential dependence of the adsorbed amount of either one or both of the oxidized and reduced forms of the redox species is maximized near its standard potential. The electrocapillary equation at a non-polarizable liquid metal–solution interface under an externally controlled potential is revisited. The derived electrocapillary equation facilitates calculating the electrocapillary curve of the non-polarizable interface based on the quantity of adsorbed ions. The electrocapillary curve calculated based on the model may have a concave part, which would indicate that the interface is thermodynamically forbidden, near the standard redox potential of the redox couple.
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