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Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride
Di Huang1, Yiliang Zhu1, Ya-Qiong Su1
1State Key Laboratory of Physical Chemistry of Solid Surfaces , Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , 422 Siming South Road , Xiamen 361005 , China .
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.
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