Comment on: Temperature-dependent conductivity in room temperature ionic liquids. The relative importance of diffusional and exchange mechanisms. [Simonis ED, Blanchard GJ (2026) J Solid State Electrochem. https://doi.org/10.1007/s10008-025–06512-w]

IF 3.1 4区化学 Q3 ELECTROCHEMISTRY

Journal of Solid State Electrochemistry Pub Date : 2026-03-17 DOI:10.1007/s10008-026-06554-8

Kenneth R. Harris

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Abstract

Simonis and Blanchard have reported tracer diffusion coefficients for the cationic chromophore rhodamine B in four ionic liquids (IL), using a Fluorescence Recovery After Photobleaching (FRAP) technique and employing a Stokesian hydrodynamic argument to deduce the self-diffusion coefficients of the constituent ions. The latter are used to calculate the Nernst-Einstein approximation to the conductivity which is compared to literature experimental data. Contrary to considerable experimental and computational evidence in the literature for the ILs examined, and statistical mechanics treatments of ion transport, they find that the conductivity exceeds the Nernst-Einstein estimate and suggest “exchange-mediated ion-transport” as a possible explanation for their observation. Examination of the data shows that their technique considerably underestimates the ion self-diffusion diffusion coefficients as conventionally measured by both steady and pulsed gradient spin-echo NMR and misestimates their temperature dependence. It is concluded that the FRAP technique and the Simonis-Blanchard treatment of the data give erroneous low estimates for ion self-diffusion in ionic liquids are the conclusion that additional mechanisms for charge transport beyond ionic vehicular motion is unwarranted.

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评论：室温离子液体中随温度变化的电导率。扩散机制和交换机制的相对重要性。[J]，刘建军，张建军，等。固态电化学研究进展[J]。https://doi.org/10.1007/s10008 - 025 - 06512 - w)

Simonis和Blanchard报道了阳离子发色团罗丹明B在四种离子液体（IL）中的示踪剂扩散系数，使用光漂白后荧光恢复（FRAP）技术并采用斯托克流体动力学参数来推导组成离子的自扩散系数。后者用于计算电导率的能斯特-爱因斯坦近似，并与文献实验数据进行了比较。与文献中大量的实验和计算证据以及离子传输的统计力学处理相反，他们发现电导率超过了能斯特-爱因斯坦的估计，并建议“交换介导的离子传输”作为他们观察的可能解释。对数据的检查表明，他们的技术大大低估了离子自扩散扩散系数，这是由稳定和脉冲梯度自旋回波核磁共振常规测量的，并且错误地估计了它们的温度依赖性。结论是，FRAP技术和Simonis-Blanchard对数据的处理给出了离子液体中离子自扩散的错误低估计，结论是离子载体运动之外的电荷传输机制是没有根据的。

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来源期刊

Journal of Solid State Electrochemistry 工程技术-电化学

CiteScore

4.80

自引率

4.00%

发文量

227

审稿时长

4.1 months

期刊介绍： The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry. The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces. The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis. The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.