Electrochemical Properties of Keggin-Structure Polyoxometalates in Acetonitrile: Effects of Countercation, Heteroatom, and Framework Metal Exchange
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© 2016 American Chemical Society. The electrochemical characteristics of several Keggin-type polyxometalates (POMs) in acetonitrile were investigated by cyclic voltammetry. The effects of three types of substitutions (countercation, heteroatom, and framework metal element) were investigated. The spectra for group IA or IIA POM salts showed three redox couples, with only slightly different peak positions (±0.1 V). Lithium salts were selected for exploration of other POM compositions in order to prevent H2 evolution in electrochemical experiments. CV spectra of heteroatom-exchanged POMs showed that the overall charge on the POM affects reduction potentials. Substitution of the framework metal atoms (Mo, W, and V) had the greatest effect on reduction potentials. The results of this study demonstrate that reduction potentials in water may provide a useful guide to relative reduction potentials for POMs in nonaqueous media.
author list (cited authors)
Chen, J., & Barteau, M. A.