Dielectric-dependent electron transfer behaviour of cobalt hexacyanides in a solid solution of sodium chloride. Issue 11 (30th July 2015)

• Record Type: Journal Article
• Authors: Huang, Di; Zhu, Yiliang; Su, Ya-Qiong; Zhang, Jie; Han, Lianhuan; Wu, De-Yin; Tian, Zhong-Qun; Zhan, Dongping
• Is Part Of: Chemical science. Volume 6:Issue 11(2015:Nov.)
• Page Start: 6091
• Page End: 6096
• Publication Date: 2015-07-30
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5sc02153g
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The electron transfer behavior of cobalt hexacyanide is obtained in a solid solution of sodium chloride due to the low dielectric environment. 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)6 3− ) into single microcrystals of sodium chloride (NaCl), for the first time, we obtained the direct electrochemical behavior of Co(CN)6 3− which is hardly ever obtained in either aqueous or conventional nonaqueous solutions. DFT calculations elucidate that, as the Co(CN)6 3− anions occupy the lattice units of NaCl6 5− in the NaCl microcrystal, the redox energy barrier of Co(CN)6 3−/4− is decreased dramatically due to the low dielectric constant of NaCl. Meanwhile, the low-spin Co(CN)6 4− 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.