EDX, Spectroscopy, and Composition Studies of Electrochromic Iron(III) Hexacyanoferrate(II) Deposition
Authors:
- 1 January 2003
- journal article
- Published by The Electrochemical Society in Journal of the Electrochemical Society
- Vol. 150 (9) , C641-C645
Abstract
Persistent questions regarding the electrochromic ferric-ferrocyanide chromophore, Prussian blue (PB), are addressed and definitively resolved by detailed chemical and energy-dispersive X-ray analyses and spectroscopy: (i) What is the nature of the initially deposited film? (ii) Restructuring of freshly deposited PB that occurs in the first voltammetric cycle in KCl(aq): why is only one-third of the maximum possible K+K+ taken up? (iii) Is the presence of KCl in the electrodeposition solution beneficial or destructive? and (iv) What underlies the appreciable spectroscopic shifts of the charge-transfer peak at ∼700 nm, that depend on which alkali-metal ion M+M+ is incorporated in PB? The KCl-cycled PB after electrodeposition is shown to be K0.33+Fe0.332+Fe3+[Fe(CN)64−]K0.33+Fe0.332+Fe3+[Fe(CN)64−] in a mechanism explaining the limited (0.33) uptake of K+.K+. Similar compositions are found with other M+M+ except Cs+,Cs+, which interacts exceptionally. © 2003 The Electrochemical Society. All rights reserved.Keywords
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