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Structure of Cobalt Hexacyanoferrate Films Synthesized from a Complex Electrolyte

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Abstract

Films of cobalt hexacyanoferrate (CHCF) are produced under potentiodynamic conditions (E= –0.25 to 0.6 V, v= 0.05 V s–1) from a 2 mM K3Fe(CN)6+ 2 mM Na3Co(NO2)6+ 0.5 M Na2SO4solution. According to scanning electron microscopy, the thick CHCF film initially obtained during the synthesis has a heavily porous structure unusual for films of hexacyanoferrates of transition metals, the size of its crystallites is 200–600 nm. A thinner film has a more compact structure and its crystallites are smaller. The X-ray diffraction pattern for a reduced film shows rhombohedral distortion of the fcc lattice with parameters a= 1.035 nm and α = 91.43°. The patterns for partially and completely oxidized films nicely fit an fcc crystalline lattice typical for hexacyanoferrates (ais 1.006 and 0.993 nm, respectively). The assumption that both hexacyanoferrate and cobalt ions are electroactive in this particular case is confirmed by the IR and X-ray photoelectron spectroscopy techniques.

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Authors and Affiliations

  1. St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199164, Russia

    M. M. Kaplun, Yu. E. Smirnov & V. V. Malev

  2. Center for Materials Study, Tallinn Technical University, Tallinn, Estonia

    V. Mikli

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  1. M. M. Kaplun
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  2. Yu. E. Smirnov
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  3. V. Mikli
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  4. V. V. Malev
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Kaplun, M.M., Smirnov, Y.E., Mikli, V. et al. Structure of Cobalt Hexacyanoferrate Films Synthesized from a Complex Electrolyte. Russian Journal of Electrochemistry 37, 914–924 (2001). https://doi.org/10.1023/A:1011992109433

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