Structural and Vibrational Properties of Carboxylates Intercalated into Layered Double Hydroxides: A Joint Computational and Experimental Study.

Layered double hydroxides (LDHs) are fascinating clay-like materials that display versatile properties, making them an extremely fertile playground for diverse applications, ranging from bio-compatible materials to the pharmaceutical industry to catalysis and photocatalysis. When intercalating organic and bio-organic species between the inorganic layers, such materials are named hybrid LDHs. The structure-property relation in these systems is particularly relevant, since most of the properties of the materials may be fine-tuned if a comprehensive understanding of the microscopic structure in the interlamellar space is achieved, especially with respect to the reorganization under water uptake (swelling). In this work, we combined experiments and simulations to rationalize the behavior of LDHs intercalating three carboxylates, the general structure of which can be given as [Mg4Al2(OH)12]A2-·XH2O (with A2- = succinate, aspartate, or glutamate and X representing increasing water content). Following this strategy, we were able to provide an interpretation of the different shapes observed for the experimental water adsorption isotherms and for the evolution of the infrared carboxylate band of the anions. Apart from small differences, due to the different reorganization of the conformational space under confinement, the behavior of the two amino acids is very similar. However, such behavior is quite different in the case of succinate. We were able to describe the different response of the anions, which has a significant impact on the isotherm and on the size of the interlamellar region, in terms of a different interaction mechanism with the inorganic layer.