Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride |
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| Authors: | Di Huang Yiliang Zhu Ya-Qiong Su Jie Zhang Lianhuan Han De-Yin Wu Zhong-Qun Tian Dongping Zhan |
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| Affiliation: | a State 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 . Email: |
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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. |
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