How Do Liquid-Junction Potentials and Medium Polarity at Electrode Surfaces Affect Electrochemical Analyses for Charge-Transfer Systems?
How Do Liquid-Junction Potentials and Medium Polarity at Electrode Surfaces Affect Electrochemical Analyses for Charge-Transfer Systems?
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DOI：
10.1021/acs.jpcb.2c07983
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发表时间：
2023-02-16
影响因子：
3.3
通讯作者：
Vullev, Valentine I.
中科院分区：
文献类型：
--
作者：
Mayther, Maximillian F.;O'Mari, Omar;Flacke, Paul;Bhatt, Dev;Andrews, Samantha;Vullev, Valentine I.
电化学分析对电荷传递科学的重要性怎么强调也不为过。电化学电池中的界面在解释和分析的实用性方面提出了一定的挑战。本出版物的重点是：(1)氧化还原物质在电极表面经历的介质极性小于散装介质中的极性；(2)不同有机溶剂（即二氯甲烷、苯腈和乙腈）的界面电解质溶液的液结电位。具有相似结构的电子给受体对芳烃（即1-萘胺和1-硝基萘，10-甲基吩噻嗪和9-硝基蒽，1-氨基芘和1-硝基芘）作为本研究的氧化还原分析物。利用氧化给体和受体的还原电位之差消除了液体结对电荷转移热力学分析的影响。该分析还提供了一种方法来评估氧化还原物质在工作电极表面所经历的介质极性以及液体结对所测还原电位的影响。二氯甲烷和乙腈溶液的液结电位约为90 mV，而苯腈-乙腈溶液的液结电位仅为30 mV左右。所提出的分析施主和受主电化学特性的方法为改进电荷传递体系的热力学评价提供了一种手段。
The importance of electrochemical analysis for charge-transfer science cannot be overstated. Interfaces in electrochemical cells present certain challenges in the interpretation and the utility of the analysis. This publication focuses on: (1) the medium polarity that redox species experience at the electrode surfaces that is smaller than the polarity in the bulk media and (2) the liquid-junction potentials from interfacing electrolyte solutions of different organic solvents, namely, dichloromethane, benzonitrile, and acetonitrile. Electron-donor–acceptor pairs of aromatics with similar structures (i.e., 1-naphthylamine and 1-nitronaphthalene, 10-methylphenothiazine and 9-nitroanthracene, and 1-aminopyrene and 1-nitropyrene) serve as redox analytes for this study. Using the difference between the reduction potentials of the oxidized donors and the acceptors eliminates the effects of the liquid junctions on the analysis of charge-transfer thermodynamics. This analysis also offers a means for evaluating the medium polarity that the redox species experience at the surface of the working electrode and the effects of the liquid junctions on the measured reduction potentials. While the liquid-junction potentials between the dichloromethane and acetonitrile solutions amount to about 90 mV, for the benzonitrile-acetonitrile junctions, the potentials are only about 30 mV. The presented methods for analyzing the measured electrochemical characteristics of donors and acceptors illustrate a means for improved evaluation of the thermodynamics of charge-transfer systems.
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DOI：
10.1039/d0cp01556c
发表时间：
2020-10-14
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
Derr JB ;Tamayo J ;Clark JA ;Morales M ;Mayther MF ;Espinoza EM ;Rybicka-Jasińska K ;Vullev VI
通讯作者：
Vullev VI
影响因子：
3.3
作者：
Bao, Duoduo;Ramu, Sangeetha;Vullev, Valentine I.
通讯作者：
Vullev, Valentine I.
影响因子：
7.4
作者：
Bond, AM;Oldham, KB;Snook, GA
通讯作者：
Snook, GA
影响因子：
7.4
作者：
CHATTEN, LG;HARRIS, LE
通讯作者：
HARRIS, LE
影响因子：
4
作者：
ABE, T
通讯作者：
ABE, T