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Dehydration-Induced Charge Transfer in Ni3[Fe(CN)6]2ź15H2Oe T

Liu M., Bian X. F., Xia Y. F., Bao Z., Xu M. X.

Polish Journal of Chemistry

2009

Vol. 83, nr 10

1729-1735

Molecular magnet nickel(II) hexacyanoferrate(III), powder Ni3[Fe(CN)6]2ź15H2O, was prepared by coprecipitation method. The coprecipitated powder was annealed in vacuum at different temperatures of 80, 100, 120, and 140 graduate C. Water molecules contained in Prussian blue analogues were removed by heating. The effects of dehydration on its charge transfer properties were studied by Fourier-transform infrared and Mössbauer measurements. It was found that the FeIII–CN–NiII state is the major structure in the coprecipitated form, while the FeII–CN–NiIII bond is formed in the annealed samples. The dehydration of NiII ferricyanide above 80°C induces an inner charge transfer from NiII towards FeIII to form the mixed valence system Ni(II) Ni(III) ferri-ferro-cyanide.

Two-Layer Structures of Ultra-Thin Metal Hexacyanoferrate Films: Charge Trapping Possibility of Application to Corrosion Protection

Miecznikowski K., Chojak M., Steplowska W., Makowski O., Kulesza P., Adamczyk L., Malik M., Gałkowski M., Bala H.

Polish Journal of Chemistry

2004

Vol. 78 / nr 9

1183-1193

The possibility of fabrication of ultra-thin films of metal hexacyanoferrates, Prussian Blue, PB, and nickel hexacyanoferrate, NiHCNFe, by multiple sequential attachment of metal cations (self-assembled on 4-aminobenzoic acid monolayer) and hexacyanoferrate anions, has been demonstrated. These films can form a bilayer arrangement on glassy carbon when PB and NiHCNFe are deposited as inner and outer films, respectively. To avoid mixing of the NiHCNFe and PB redox sites, we introduce an polymer interlayer from poly(4-vinylpyridine) and Nafion. Since the outer NiHCNFe film is physically separated from the electrode surface, and it undergoes redox reactions at potentials characteristic of the inner PB film, an effect of the reversible charge state trapping (bistable switching) is observed. Astable bilayer structure can also be deposited on stainless steel. The whole concept may be of importance to corrosion protection since charge accumulated in the oxidized bilayer film tends to stabilize corrosion potential within passive range.