Characterization of Prussian blue and its thermal decomposition products |
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Authors: | H. Inoue T. Nakazawa T. Mitsuhashi T. Shirai E. Fluck |
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Affiliation: | (1) Department of Applied Chemistry, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, 223 Yokohama, Japan;(2) Gmelin-Institut der Max-Planck-Gesellschaft, Varrentrappstr. 40/42, D-6000 Frankfurt am Main 90, FRG |
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Abstract: | The mixed-valence state of Prussian blue and its thermal decomposition products has been studied by Mössbauer and infrared spectra, and X-ray powder diffraction and conductivity measurements. The57Fe Mössbauer spectra have revealed that the coordination environment of Prussian blue is not changed by the heat-treatment at lower than 200°C while the flipping of the cyano ligands takes place when the heat-treatment temperature exceeds 250°C. The electrical conductivity of the Prussian blue samples heat-treated in vacuo at 300 and 350°C is higher than that of the samples heat-treated at lower temperatures. All the spectral measurements have demonstrated that a new mixed-valence state is produced in Prussian blue by thermally flipping the cyano ligand and quenching the flipped cyano ligand to liquid nitrogen temperature. |
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