Electrochromism in the mixed-valence hexacyanides. 1. Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian blue

D. Ellis, M. Eckhoff, V. D. Neff*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

462 Scopus citations

Abstract

A thin film of Prussian blue (KFeFe(CN6)), on a platinum or gold substrate, is reduced to Everitt's salt (K2FeFe(CN6)) at 0.195 V (vs. SCE) or is oxidized to Berlin green (K1/3Fe(FeIII(CN)6)2/3(Fe II(CN)6)1/3) at 0.870 V in 1 N KCl or K2SO4 solutions. It is shown that potassium ion migrates into or out of the film during the electrolysis. Both reactions are reversible at sweep rates of <5 mV/s in 1 N potassium ion solutions. Partial oxidation or reduction of Prussian blue leads to the formation of solid solutions. For the reduction reaction the solid solution formed is nonideal, and the voltammograms are explained in terms of the theory of strictly regular solutions with a negative interaction energy. For the oxidation reaction the solid solution appears to be almost ideal, but approximately one-third of the ferrocyanide ions remain unoxidized in the stable form of the completely oxidized compound.

Original languageEnglish (US)
Pages (from-to)1225-1231
Number of pages7
JournalJournal of physical chemistry
Volume85
Issue number9
DOIs
StatePublished - 1981

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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