Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK.
Analyst. 2013 Sep 21;138(18):5444-52. doi: 10.1039/c3an01092a. Epub 2013 Jul 25.
We report a simple and facile methodology for constructing gold macrodisc and platinum microband electrodes for use in room temperature ionic liquids (RTILs). To validate the use of gold macrodisc electrodes, the voltammetry of Ru(NH3)6(3+) was studied in 0.1 M aqueous KCl. The Randles-Ševčík equation was used to calculate the diffusion coefficient, giving excellent agreement with literature values, suggesting that the gold macrodisc electrode is capable of performing quantitative electroanalysis in aqueous media. Gold macrodisc electrodes were used to study oxidation of ferrocene in N-butyl-N-methylpyrrolidinium bis(fluoromethylsulfonyl)imide ([C4mpyrr][NTf2]) using cyclic voltammetry. The diffusion coefficient of ferrocene, (2.43 ± 0.07) × 10(-11) m(2) s(-1), was obtained. This value is very close to the literature value, indicating good performance of gold electrodes in RTILs. Platinum microband electrodes were tested in 1-propyl-3-methylimidazolium bis-trifluoromethylsulfonylimide ([Pmim][NTf2]) containing decamethylferrocene. Diffusion coefficients and electron transfer rates were obtained by fitting relevant simulations to the experimental data. For comparison, analogous experiments and analyses were performed on a commercial platinum microdisc, where the results obtained from both microdisc and microband agree well, further suggesting that the platinum microband electrode is suitable to be used in RTILs. Finally, gold macrodisc and platinum microband electrodes were used for oxygen detection. Gold macrodisc electrodes were used to find the peak currents of oxygen at each volume percentage analysed. Platinum microband electrodes showed steady-state currents of different volumes of oxygen. These two results are compared which resulted in excellent agreement. This is further confirmed by studying Henry's law constants obtained from both electrodes. The excellent behaviour of these two fabricated electrodes suggests that they are suitable for quantitative measurements and practicable for real world applications.
我们报告了一种简单易行的方法，用于构建金宏观盘和铂微带电极，用于室温离子液体（RTILs）。为了验证金宏观盘电极的使用，研究了 Ru(NH3)6(3+)在 0.1 M 水溶液 KCl 中的伏安行为。使用 Randles-Ševčík 方程计算扩散系数，与文献值吻合良好，表明金宏观盘电极能够在水溶液中进行定量电化学分析。金宏观盘电极用于研究在 N-丁基-N-甲基吡咯烷双（氟甲基磺酰基）亚胺([C4mpyrr][NTf2])中使用循环伏安法氧化二茂铁。获得了二茂铁的扩散系数，(2.43 ± 0.07)×10(-11) m(2) s(-1)。该值非常接近文献值，表明 RTILs 中金电极性能良好。铂微带电极在 1-丙基-3-甲基咪唑双三氟甲基磺酰亚胺([Pmim][NTf2])中含十甲基二茂铁进行了测试。通过将相关模拟拟合到实验数据，获得扩散系数和电子转移速率。为了比较，在商业铂微盘中进行了类似的实验和分析，从微盘和微带获得的结果非常吻合，进一步表明铂微带电极适合在 RTILs 中使用。最后，金宏观盘和铂微带电极用于氧气检测。金宏观盘电极用于在分析的每个体积百分比下找到氧气的峰值电流。铂微带电极显示出不同体积氧气的稳态电流。这两个结果进行了比较，结果非常吻合。通过研究从两个电极获得的亨利定律常数进一步证实了这一点。这两个制备电极的优异性能表明它们适用于定量测量，并且适用于实际应用。
