Influence of 1-butyl-3-methylimidazolium on the electron transfer kinetics associated with the [SVW11O40]3 −/4 − (VV/IV) and [SVW11O40]4 −/5 − (WVI/V) processes in dimethylformamide

Jiezhen Li, Cameron Bentley, Alan Bond, Jie Zhang, Tadaharu Ueda

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Fourier transformed large amplitude alternating current voltammetry has been used to determine the heterogeneous electron-transfer kinetics (k0 and α values) associated with the vanadium [SVW11O40]3 −/4 − (VV/IV) and tungsten [SVW11O40]4 −/5 − (WVI/V) processes at glassy carbon (GC), platinum (Pt), gold (Au) and boron-doped diamond (BDD) electrodes in dimethylformamide (DMF) containing 0.5 M 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. In comparison with data reported previously in DMF containing 0.5 M tetrabutylammonium hexafluorophosphate, the k0 values at Pt, Au and BDD electrodes, were found to be larger by a factor of 2 to 4 for the VV/IV process and 10 to 100 fold for the WVI/V process. At a GC electrode, the rate of the VV/IV process was too fast to be measured under the experimental conditions used (frequency = 34 Hz) and k0 for the WVI/V process was found to be insensitive to the identity of the supporting electrolyte cation. The origins of these observations are considered in terms of contributions from ion-pairing, surface functional groups on the GC electrode, the double layer effect, and the inner-sphere nature of the WV/IV process.

Original languageEnglish
Pages (from-to)67-74
Number of pages8
JournalJournal of Electroanalytical Chemistry
Publication statusPublished - 15 Oct 2016


  • Electron transfer kinetics
  • Fourier transformed alternating current voltammetry
  • Ionic liquids
  • Polyoxometalates

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