4.6 Article

Anion effect on the redox properties of copper ions in ionic liquids and deep eutectic solvents

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 25, Issue 6, Pages 4854-4861

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp04389k

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This study investigates the influence of different salt anions and solvent anions on copper's redox properties. The results show that the solvent anion has a greater impact than the salt anion. Despite different starting salts, the copper species remain the same, except for copper(i) salt and copper(ii) acetate system that show concentration dependence.
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.

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