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

doi:10.1021/j150609a026

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

Physics and Astronomy

Research output: Contribution to journal › Article › peer-review

452 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 (K_1/3Fe(Fe^III(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 language	English (US)
Pages (from-to)	1225-1231
Number of pages	7
Journal	Journal of physical chemistry
Volume	85
Issue number	9
DOIs	https://doi.org/10.1021/j150609a026
State	Published - 1981

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Engineering(all)
Physical and Theoretical Chemistry

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@article{5035828602fe41be84bdfc0069adaa4e,

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

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.",

author = "D. Ellis and M. Eckhoff and Neff, {V. D.}",

year = "1981",

doi = "10.1021/j150609a026",

language = "English (US)",

volume = "85",

pages = "1225--1231",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Electrochromism in the mixed-valence hexacyanides. 1. Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian blue

AU - Ellis, D.

AU - Eckhoff, M.

AU - Neff, V. D.

PY - 1981

Y1 - 1981

N2 - 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.

AB - 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.

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