Molecular assembly in synthesised hydrotalcites of formula CuxZn6-xAl2(OH)16(CO3) . 4H2O-a vibrational spectroscopic study

Abstract

Infrared and Raman spectroscopy have been used to characterize synthetic hydrotalcites of formula CuxZn6-xAl2(OH)16(CO3).4H2O . The spectra have been used to assess the molecular assembly of the cations in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features based (a) upon the carbonate anion (b) the hydroxyl units (c) water units. The Raman spectra of the hydroxyl-stretching region enable bands to be assigned to the CuOH, ZnOH and AlOH units. It is proposed that in the hydrotalcites with minimal cationic replacement that the cations are arranged in a regular array. For the CuxZn6-xAl2(OH)16(CO3).4H2O hydrotalcites, spectroscopic evidence suggests that 'islands' of cations arte formed in the structure. In a similar fashion the bands assigned to the interlayer water suggest that the water molecules are also in a regular well-structured arrangement. Bands are assigned to the hydroxyl stretching vibrations of water. Three types of water are identified (a) water hydrogen bonded to the interlayer carbonate ion (b) water hydrogen bonded to the hydrotalcite hydroxyl surface and (c) interlamellar water. It is proposed that the water is highly structured in the hydrotalcite as it is hydrogen bonded to both the carbonate anion and the hydroxyl surface.