Abstract
Anhydrous nickel, niobium and tantalum chlorides were studied with cyclic voltammetry and X-ray absorption spectroscopy (XAS) in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride (EMIC) ionic liquids. Nickel chloride in an acidic melt displays metal stripping peaks which are not observed in the basic melt. XAS analysis shows that the nickel is tetrahedrally coordinated in the basic melt while in the acidic melt, it is coordinated by 6 chloride ions that are also associated with aluminum ions. For Nb2Cl10, the XAS data shows that the Nb has a coordination shell of 5 in both the acidic and basic melts, indicating that the Nb2Cl10 breaks up into two NbCl5 entities in both melts. For Ta2Cl10 in the acidic melt, the tantalum has five chlorides in its coordination shell. In the basic solution, the tantalum is coordinated by 7 chlorides. This indicates that the Lewis acidity of the tantalum chloride causes the Ta to coordinate differently in the acidic and the basic ionic liquids.
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