Olson Eric J, Boswell Paul G, Givot Bradley L, Yao Letitia J, Bühlmann Philippe
Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA).
J Electroanal Chem (Lausanne). 2010 Feb 15;639(1-2):154-160. doi: 10.1016/j.jelechem.2009.12.006.
This work demonstrates the first cyclic voltammetry in a perfluorocarbon solvent without use of a cosolvent. The novel electrolyte tetrabutylammonium tetrakis[3,5-bis(perfluorohexyl)phenyl]borate (NBu(4)BArF(104); 80 mM) allows for voltammetry of ferrocene in perfluoro(methylcyclohexane) by lowering the specific resistance to Ω268 k cm at 20.8 °C. Despite significant solution resistance, the resulting voltammograms can be fitted quantitatively without difficulty. The thus determined standard electron transfer rate constant, k°, for the oxidation of ferrocene in perfluoro(methylcyclohexane) is somewhat smaller than for many solvents commonly used in electrochemistry, but can be explained readily as the result of the viscosity and size of the solvent using Marcus theory. Dielectric dispersion spectroscopy verifies that addition of NBu(4)BArF(104) does not significantly raise the overall polarity of the solution over that of neat perfluoro(methylcyclohexane).
这项工作展示了在不使用共溶剂的全氟碳溶剂中的首次循环伏安法。新型电解质四丁基铵四[3,5-双（全氟己基）苯基]硼酸盐（NBu(4)BArF(104)；80 mM）通过在20.8°C下将比电阻降低到268 kΩ·cm，使得二茂铁在全氟（甲基环己烷）中能够进行伏安法测定。尽管溶液电阻很大，但所得的伏安图仍可轻松进行定量拟合。由此确定的二茂铁在全氟（甲基环己烷）中氧化的标准电子转移速率常数k°比许多电化学常用溶剂中的要小一些，但使用马库斯理论可以很容易地解释为溶剂粘度和尺寸的结果。介电色散光谱证实，添加NBu(4)BArF(104)不会使溶液的整体极性比纯全氟（甲基环己烷）显著提高。
