Influence of experimental conditions on electrochemical behavior of Prussian blue type nickel hexacyanoferrate film

Electrochemical properties of thin films and microcrystalline precipitates of nickel(II) hexacyanoferrate(II, 111), NiHCNFe, are strongly dependent on the method of their preparation and experimental conditions of their investigation. The films have been generated on both inert (gold) and parent metal (nickel) substrates. Interpretation of voltammetric responses of nickel hexacyanoferrate microstructures on electrodes is supported with the data of elemental analysis estimations obtained using atomic absorption and surface examination based on X-ray energy dispersive spectroscopy. Both electrodeposited films and mechanically-attached precipitates of nickel hexacyanoferrate constitute mixed structures in which the relative ratios of K and Ni to Fe reflect composition of a solution for modification, choice of the deposition potential and time, and the time and potential limits of exposure of the system to voltammetric potential cycling in potassium salt supporting electrolyte. We demonstrate here that the more positive set of peaks of nickel hexacyanoferrate is related to the electroactivity of the form containing relatively larger amount of potassium and smaller of nickel. On the other hand, the more negative set of the system's peaks shall be attributed to the form that is largely potassium depleted and containing more nickel relative to iron. In this context, the use of the previously proposed approximate formulas, K2Ni[Fe-II(CN)(6)] and KNi1.5[Fe-II(CN)(6)], for the predominant nickel hexacyanoferrate (reduced) forms is justified. (C) 2003 Elsevier Ltd. All rights reserved.