Anion effect on the redox properties of copper ions in ionic liquids and deep eutectic solvents.
Anion effect on the redox properties of copper ions in ionic liquids and deep eutectic solvents.
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阴离子对离子液体和低共熔溶剂中铜离子氧化还原性质的影响。
DOI：
10.1039/d2cp04389k
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Daskalopoulou E
中科院分区：
文献类型：
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作者：
Daskalopoulou E
长期以来，人们一直认为DES或IL的阴离子对控制金属离子的氧化还原性质至关重要。在本研究中，我们考察了不同的盐阴离子对铜氧化还原性能和形态的影响，并与不同溶剂阴离子的影响进行了比较，当单一的铜盐在不同的溶剂中使用时。结果表明，溶剂型阴离子比盐型阴离子对氧化还原性能的影响更为显著。还发现，尽管起始盐不同，铜物种仍然是相同的四氯化铜物种。铜(I)盐和醋酸铜(II)体系是一个例外，前者形成线性二氯化物物种，后者表现出浓度依赖性。当离子液体的阴离子改变时，铜物种随着溶剂阴离子的配位强度发生相应的变化，导致氧化还原响应的差异较大，这是由于存在的物种不同所致。因此，这些形态差异可以用来修饰溶液中的氧化还原电位。
It has long been claimed that the anion of the DES or IL is critical for controlling the redox properties of metal ions. In this study we investigate the effect of different salt anions on the copper redox properties and speciation, and compare that with the effect of the different solvent anions, when a single copper salt is used in a range of solvents. It is shown that the effect of the solvent anion is much more significant than that of the salt anion on the redox properties. It is also found that copper species remain the same copper tetrachloride species despite the starting salt. An exception is seen for the copper(I) salt, which makes linear dichloride species, as well as the copper(II) acetate system, which displays concentration dependence. When the anion of the ionic liquid is changed, the copper species change correspondingly with the coordinating strength of the solvent anion, leading to a greater difference in redox response, which is due to the different species present. Thus, these speciation differences can be used to modify the redox potentials in the solution.