Comparative X-ray diffraction and infrared spectroscopy study of Zn–Al layered double hydroxides : vanadate vs nitrate

Abstract

Zn–Al layered double hydroxides (LDH) are promising as nanocontainers of corrosion inhibitors in self-healing corrosion protection coatings. Zn(2)Al–vanadate (Zn/Al=2:1) is prepared by anion exchange from the parent composition Zn(2)Al–nitrate at pH∼8. Crystal structure and vibrational spectra of both LDHs have been studied in comparison. Their interlayer distances are rather larger than those corresponding to the most compact arrangement of the intercalated anions. Nevertheless, no sign of a turbostratic disorder has been detected in these LDH. Based on the analysis of the spectroscopic data in combination with the XRD results, it has been shown that vanadate anion, which substitutes nitrate at the anion exchange, is pyrovanadate, V2O74-. The observed disorder in the hydroxide layers in Zn(2)Al–V2O7 is likely to result from strong interactions between V5+ and Zn2+/Al3. Although Zn(2)Al–NO3 is less disordered than Zn(2)Al–V2O7, it exhibits no long-range order in arrangement of cations in the hydroxide layers.