Abstract

Nano-sized metal hexacyanoferrates of the formula KxMy[Fe(CN)6]z·qH2O, where M = Co, Ni or Cu (and x, y, z and q are stoichiometric numbers), were prepared by reverse emulsion. The resulting nano-materials were characterized utilizing physico-chemical and spectroscopic methods. Evaluation of Fourier-transformed infrared absorption peaks located in the C≡N stretching frequency area 2050–2200 cm−1 confirmed the presence of the metal-cyano-chains with mixed oxidation states for both metals in the samples (FeII/III–C≡N–MII/III). Ratios of the different oxidation states of each metal could be calculated from the X-ray photoelectron spectroscopy data, Co 1.12 II /Co 0.56 III :Fe 0.44 II /Fe 0.56 III , Ni 0.52 II /Ni 0.46 III :Fe 0.46 II /Fe 0.54 III and Cu 0.65 II /Cu 1.26 III :Fe 0.50 II /Fe 0.50 III . After modification of glassy carbon and carbon paste electrodes with the metal hexacyanoferrates, the electrochemical properties of these modified electrodes were investigated by means of cyclic voltammetry. The potential application of these electrodes as electrocatalysts for the oxidation of hydrazine was investigated. Lastly, the use of the metal hexacyanoferrates as potential heterogeneous catalysts for the solvent-free oxidation of benzyl alcohol using the environmentally friendly oxidant, H2O2, was explored.

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