The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents.
The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents.
复制标题
DOI：
10.1371/journal.pone.0144235
复制
发表时间：
2015
期刊：
影响因子：
3.7
通讯作者：
Brandon N
中科院分区：
文献类型：
--
作者：
Bahadori L;Chakrabarti MH;Manan NS;Hashim MA;Mjalli FS;AlNashef IM;Brandon N
研究了几种含氨基盐和氢键供体（多元醇型）的深度共晶溶剂（DESs）的密度、动态粘度和离子电导率与温度的关系。利用瓦尔登法则将温度依赖性电解质粘度作为摩尔电导率的函数进行了关联。采用循环伏安法和电位步长计时电流法研究了二茂铁（Fc/Fc+）在不同温度下的氧化和钴镉（Cc+/Cc）的还原。对于大多数DESs，时间电流瞬态被证明符合arrhenius型关系，可以给出不同温度下氧化还原偶扩散的活化能。DES1和DES2电导率的温度依赖性与Vogel-Tamman-Fulcher方程有较好的相关性。在298 ~ 338k的温度范围内研究了Fc/Fc+和Cc+/Cc电化学体系的动力学。然后用对数分析方法计算了在不同温度下的非均相电子转移速率常数。甘油基DES （DES5）似乎适合在电化学储能装置中进行进一步的测试。
The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden’s rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices.