Estudo teórico da interação de ânions tereftalato na estrutura de compostos tipohidrotalcita modificados

Abstract

First principles calculations based on Density Functional Theory (DFT) were used to investigate the structural and electronic properties of Layered Double Hydroxides (LDH) of Mg-Al-terephthalate and Mg-Al-CO3 composition with molar ratios, x, of 0.25, 0.33 and 0.50. The structural analysis was based on total energy angular mapping of terephthalate (TA) and NMR calculations of carbon 13C, which demonstrated the existence of preferred orientations in the interlayer region. The charge density differences demonstrated greater load transfer of water molecules than the anion with the layer being more pronounced in Mg-Al-TA with x = 0.50. The calculated ΔG of formation demonstrated that the synthesis of Mg-Al-CO3 with x = 0.50 is not spontaneous at room temperature, unlike the Mg-Al-TA. Although the ratio between the areas occupied by the anion and water molecules per positive charge area permit the accommodation in the layer structure, it was found that there is a competition for the layer sites. The lower energy geometry optimization showed the preference of the water molecules to form hydrogen bonds with the hydroxyl groups of the layer, displacing the carbonate of Mg-Al-CO3. This ion then will adopt an inclined position regarding to the layer, shown by the Gibbs free energy formation to be unfavorable. The Mg-Al-TA dehydration reaction simulated found an excellent agreement with experimental values. A measurable change in the 13C chemical shift of the carbon nuclei was verified in the new position of the TA in the dehydrated structure. The influence of divalent cation was verified by substitution of Mg2+ by Zn2+ or Ni2+. Differences were observed in geometric parameters related to differences in the ionic radii. Charge analysis based on Bader criteria indicated no significant variation in oxygen atoms of TA and water molecules by the type of divalent cation chosen.