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Electrochemical properties of (Co,Fe)CN, cobaltous Prussian blue analogue

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Abstract

A Prussian blue analogue (Co,Fe)CN with Fe and Co ions linked by CN– ions was synthesized; the synthesis was aimed at obtaining cobalt hexacyanoferrate (CoHCF). However, X-ray phase analysis showed the resemblance of (Co,Fe)CN to sodium iron hexacyanocobaltate (FeHCC) Na0.108Fe[Co(CN)6]. The electron paramagnetic resonance (EPR) spectra do not agree with the transition of CoHCF to the latter compound, but do not exclude the possibility of only partial re-coordination of the cyanide ions. At the same time, EPR also excludes formation of the targeted CoHCF. The Fourier transform infrared spectra also indicate that (Co,Fe)CN differs from CoHCF and FeHCC.

The (Co,Fe)CN electrochemistry has been studied by cyclic voltammetry. (Co,Fe)CN is electroactive in solutions of alkali metal salts, from Li to Cs, and ammonium salts. The shape of (Co,Fe)CN cyclic voltammograms is unique and does not resemble the curves of CoHCF and FeHCC. It should be noted that the electrode process of CoHCF is blocked in solutions of rubidium, cesium, and ammonium salts, while (Co,Fe)CN is electroactive in these solutions. (Co,Fe)CN produces one pair of peaks in a heavy alkali metal salt solution, whereas in the presence of light alkali metals, it produces two to three pairs of peaks. Electrochemical data also reveal the difference between (Co,Fe)CN and CoHCF and are one more argument in favor of the partial CN– ion linkage isomerization. Unfortunately, all the evidence for the re-coordination of cyanide ions gained in this work is only indirect.

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Acknowledgements

The author is grateful to Dr. Mikhail Yu. Skripkin for the fruitful discussion.

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  1. Institute of Chemistry, St. Petersburg State University, 7-9 Universitetskaya Emb., St. Petersburg, 199034, Russia

    Vladimir D. Ivanov

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Ivanov, V.D. Electrochemical properties of (Co,Fe)CN, cobaltous Prussian blue analogue. J Solid State Electrochem 27, 2419–2432 (2023). https://doi.org/10.1007/s10008-023-05519-5

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