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Synthesis and Properties of Hexacyanoferrate Interlayered in Hydrotalcite. I. Hexacyanoferrate(II)

Published online by Cambridge University Press:  28 February 2024

Hans Christian Bruun Hansen  and
Christian Bender Koch
Hans Christian Bruun Hansen
Affiliation:
Chemistry Department, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, 1871, Copenhagen V, Denmark
Christian Bender Koch
Affiliation:
Physics Department, Building 307, Technical University of Denmark, DK-2800 Lyngy, Denmark
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Abstract

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Hydrotalcite (HT) interlayered with hexacyanoferrate(II) ions ([Mg4.62Al1.52(OH)12][(Fe(CN)6)0.30-(CO3)0.29]) has been synthesized from the carbonate-HT ([Mg4.52Al1.50(OH)12][(CO3)0.77]) through double ion exchange reactions, and the products have been studied by chemical and physical methods. Mössbauer spectroscopy shows that hexacyanoferrate(II) is held rigidly in the interlayer by electrostatic forces and is characterized by a singlet at 0.01 mm s−1 at 80 K. X-ray diffraction shows an increase of the basal spacing (d003 from 0.78 to 1.1 nm following exchange. Hexacyanoferrate(II) in the interlayer was oxidized to hexacyanoferrate(III) (up to 20%) by dioxygen on dehydrating the interlayer either by drying at 70°C or by washing with nonaqueous solvents like acetone or ethanol. The CN (ν6) band of hexacyanoferrate(II) and (III) is found at 2036 cm−1 and 2112 cm−1, respectively. The presence of an absorption band at 2080 cm−1, assigned to free cyanide anions in the interlayer, suggests that the hexacyanoferrate(II,III) complexes are not inert in the interlayer, cyanide ligands being substituted with either water or hydroxyls. Oxidation and ligand exchange of the hexacyanoferrate(II) are also indicated by Mössbauer spectroscopy.

Keywords

Anion exchangeFTIR spectroscopyHexacyanoferrate(II)HydrotalciteInterlayer chemistryLayered double hydroxidesMössbauer spectroscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 2 , April 1994 , pp. 170 - 179
Copyright
Copyright © 1994, Clay Minerals Society

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