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Issue 11, 2015
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Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride

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Abstract

Here we emphasise the importance of the dielectric environment on the electron transfer behavior in interfacial electrochemical systems. Through doping cobalt hexacyanide (Co(CN)63−) into single microcrystals of sodium chloride (NaCl), for the first time, we obtained the direct electrochemical behavior of Co(CN)63− which is hardly ever obtained in either aqueous or conventional nonaqueous solutions. DFT calculations elucidate that, as the Co(CN)63− anions occupy the lattice units of NaCl65− in the NaCl microcrystal, the redox energy barrier of Co(CN)63−/4− is decreased dramatically due to the low dielectric constant of NaCl. Meanwhile, the low-spin Co(CN)64− anions are stabilized in the lattices of the NaCl microcrystal. The results also show that the NaCl microcrystal is a potential solvent for solid-state electrochemistry at ambient temperature.

Graphical abstract: Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride

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Publication details

The article was received on 17 Jun 2015, accepted on 20 Jul 2015 and first published on 21 Jul 2015


Article type: Edge Article
DOI: 10.1039/C5SC02153G
Citation: Chem. Sci., 2015,6, 6091-6096
  • Open access: Creative Commons BY license
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    Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride

    D. Huang, Y. Zhu, Y. Su, J. Zhang, L. Han, D. Wu, Z. Tian and D. Zhan, Chem. Sci., 2015, 6, 6091
    DOI: 10.1039/C5SC02153G

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