Redox Behavior and Ion-Pairing Thermodynamics of Ferrocene and Its Derivatives in the Organic Phase
Redox Behavior and Ion-Pairing Thermodynamics of Ferrocene and Its Derivatives in the Organic Phase
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DOI：
10.1021/jp909326n
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发表时间：
2010-01
影响因子：
3.7
通讯作者：
Debo Xiang;Guo-Yu Gao;H. Shao;Hu-lin Li;Hao‐Li Zhang;Hua-Zhong Yu
中科院分区：
文献类型：
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作者：
Debo Xiang;Guo-Yu Gao;H. Shao;Hu-lin Li;Hao‐Li Zhang;Hua-Zhong Yu
本文研究了二茂铁及其衍生物（二甲基二茂铁和十甲基二茂铁）在石墨电极和电解质水溶液之间的硝基苯（NB）薄膜中的氧化还原行为和离子对热力学。我们已经表明，有机相中支持电解质的存在使其氧化还原行为复杂化，即，氧化电位和峰面积均随时间显著变化。在NB相中不存在支持电解质的情况下，当水相中支持电解质（NaClO 4或HClO 4）的浓度变化时，二茂铁分子的氧化还原电位也发生变化。考虑到液-液交界电位的影响，已经证实这种电位偏移是由电化学产生的铁阳离子和有机相中的抗衡阴离子之间形成离子对决定的。在测定NB膜中阴离子（ClO 4 −）浓度的基础上，我们对NB膜进行了分析。
The redox behavior and ion-pairing thermodynamics of ferrocene and its derivatives (dimethylferrocene and decamethylferrocene) in a nitrobenzene (NB) thin film imposed between a graphite electrode and an aqueous electrolyte solution have been studied. We have shown that the presence of supporting electrolytes in the organic phase complicates their redox behavior, i.e., both the oxidation potential and peak area change significantly with time. In the absence of supporting electrolytes in the NB phase, the redox potential of the ferrocene molecules also shifts when the concentration of the supporting electrolytes (NaClO4 or HClO4) in the aqueous phase varies. It has been confirmed upon considering the influence of liquid−liquid junction potential that such a potential shift is dictated by the formation of ion pairs between the electrochemically generated ferricenium cations and the counteranions in the organic phase. On the basis of the determination of anion (ClO4−) concentrations in the NB film, we were a...