Reactivity of MgeAl hydrotalcites in solid and delaminated forms in ammonium carbonate solutions

摘要

Treatment of MgeAl hydrotalcites (LDHs, layered double hydroxides) in aqueous (NH4)_2CO_3 at 298 K leads to composites of dawsonite, hydrotalcite, and magnesium ammonium carbonate. The mechanism and kinetics of this transformation, ultimately determining the relative amounts of these components in the composite, depend on the treatment time (from 1 h to 9 days), the Mg/Al ratio in the hydrotalcite (2- 4), and on the starting layered double hydroxide (solid or delaminated form). The materials at various stages of the treatment were characterized by inductive coupled plasma-optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, infrared spectroscopy, thermogravimetry, and nitrogen adsorption at 77 K. The progressive transformation of hydrotalcite towards crystalline dawsonite and magnesium ammonium carbonate phases follows a dissolutioneprecipitation mechanism. A gradual decrease of the Mg/Al ratio in the resulting solids was observed in time due to magnesium leaching in the reacting medium. Dawsonite-hydrotalcite composite formation is favored at high aluminum contents in the starting hydrotalcite, while the formation of magnesium ammonium carbonate is favored at high Mg/Al ratios. The synthetic strategy comprising hydrotalcite delamination in formamide prior to aqueous (NH4)_2CO_3 treatment is more reactive towards composite formation than starting from the bulk solid hydrotalcite.