The thermal decomposition of Mg-Al hydrotalcites: effects of interlayer anions and characteristics of the final structure.

The thermal decomposition of hydrotalcites (HTs) with different interlayer anions in the 298-523 K region has been investigated by using transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and IR, 27Al MAS-NMR and X-ray absorption near-edge structure (XANES) spectroscopy. The thermal stability of the HT with interlayer oxalate was remarkably higher than that of HTs with interlayer carbonate; the onset temperatures for decomposition were 523 K and 473 K, respectively. It is proposed that the basicity of the interlayer anion is the key factor in the onset of dehydroxylation of the brucite-like layers: the lower the basicity, the more thermally stable the HT compound. After heat treatment at 723 K, small Mg(Al)O domains (approximately 5 nm) within the HT crystallites cause broadening of the XRD reflections. The electron diffraction pattern consists of spots and rings, due to nonrandomly oriented crystalline material. Formation of disordered bonds, caused by nonideal packing between the decomposing adjacent cation layers in the (111) direction, could explain the expanded d value in the resulting MgO-like phase observed with XRD and electron diffraction. The orientation of the Mg(Al)O domains in the heat-treated material may be crucial for the so-called "memory effect" of HTs.