Intercalation of hydrotalcites with hexacyanoferrate(II) and (III)—a thermoRaman spectroscopic study

• Published in: Journal of solid state chemistry 2005-06, Vol.178 (6), p.1940-1948
• Main Authors: Frost, Ray L., Musumeci, Anthony W., Bouzaid, Jocelyn, Adebajo, Moses O., Martens, Wayde N., Theo Kloprogge, J.
• Format: Article
• Language: English
• Subjects: Brucite; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Hexacyanoferrate(III); Hydrotalcite; Materials science; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Physics; Potassium hexacyanoferrate(II); Raman microscopy
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2005.03.045

Raman spectroscopy using a hot stage indicates that the intercalation of hexacyanoferrate(II) and (III) in the interlayer space of a Mg, Al hydrotalcites leads to layered solids where the intercalated species is both hexacyanoferrate(II) and (III). Raman spectroscopy shows that depending on the oxidation state of the initial hexacyanoferrate partial oxidation and reduction takes place upon intercalation. For the hexacyanoferrate(III) some partial reduction occurs during synthesis. The symmetry of the hexacyanoferrate decreases from O h existing for the free anions to D 3d in the hexacyanoferrate interlayered hydrotalcite complexes. Hot stage Raman spectroscopy reveals the oxidation of the hexacyanoferrate(II) to hexacyanoferrate(III) in the hydrotalcite interlayer with the removal of the cyanide anions above 250 °C. Thermal treatment causes the loss of CN ions through the observation of a band at 2080 cm −1. The hexacyanoferrate (III) interlayered Mg, Al hydrotalcites decomposes above 150 °C. Intercalation of hydrotalcites with hexacyanoferrate(II) and (III)—a ThermoRaman spectroscopic study