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Changeover during in situ compositional modulation of hexacyanoferrate (Prussian Blue) material
Paulo Roberto Bueno1, David Giménez-Romero, Claude Gabrielli
1Instituto de Química, Departamento de Físico-Química, Universidade Estadual Paulista, 14801-907 Araraquara, São Paulo, Brazil.
Abstract:
This paper describes the importance of (H2O)6 clusters in controlling the properties of hexacyanoferrate (Prussian Blue) materials. A careful in situ study of compositional changes by using electrogravimetric techniques (in ac and dc modes) in hexacyanoferrates containing K+ alkali metals reveals the existence of a changeover in the properties of these films in a narrow potential range. Control of the compositional variation of the changeover is dependent on the K+ stoichiometric number in the compound structure. However, a specific K+ occupation in the compound structure activates the occupation of the (H2O)6 cluster by H3O+ and/or H+, causing the changeover in the properties of hexacyanoferrate film. Thus, the information thus obtained is very useful for understanding the mechanisms involved in the electrochemical reversible switch between ferrimagnetism/paramagnetism, "semiconductor/metal" and electroluminescence/nonelectroluminescence properties of molecular cyanide materials.
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