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Journal of the Electrochemical Society, Vol.162, No.9, H727-H733, 2015
Interfacial Role of Cesium in Prussian Blue Films
The simultaneous measurement of current, mass, motional resistance and absorbance magnitudes allows the electrochemical cation insertion process to be explained during successive voltammograms around the Prussian Blue reversible arrow Everitt's Salt system in CsCl aqueous acid solutions. Two different ways for the entrance of cesium to the porous structure of Prussian Blue have been observed. Firstly, Cs+ is spontaneously absorbed as CsCl into the interstitial cluster of water of the channels formed by the Fe(II)(low) (spin) -CN-Fe(III)(high spin) structural units of the crystal. This chemical absorption involves a spontaneous substitution of inner water molecules of the interstitial water cluster. Finally, Cs+ can act as a counter-ion during electrochemical stabilization process of Prussian Blue by means of successive voltammograms. (C) 2015 The Electrochemical Society. All rights reserved.