Application of localized reactivity index in combination with periodic DFT calculation to rationalize the swelling mechanism of clay type inorganic material

摘要

Clays are layered alumino-silicates. Clays swell and expand in aqueous solution. This property governs the usage of these materials in synthesis of nano-composites and is a source of many of its catalytic applications. We used both localized and periodic calculations within the realm of density functional theory (DFT) on a series of monovalent (Li~+, Na~+, K~+, Rb~+, Cs~+), and divalent (Mg~(2+), Ca~(2+), Sr~(2+), Ba~(2+)) cations, to monitor their effect on the swelling of clays. The activity order obtained for the exchangeable cations among all the monovalent and divalent series studied is: Mg~(2+) > Ca~(2+) > Sr~(2+) > Ba~(2+) > Cs~+ > Rb~+ > Na~+ > Li~+ > K~+. We have studied two types of clays, montmorillonite and beidellite, with different surface structures and with/without water using periodic calculations. We have calculated the layer spacing at the first, second and third hydration shells of exchangeable cation, to compare with the experimental d-spacing values to correlate with humidity. A novel quantitative scale is proposed in terms of the intermolecular relative nucleophilicity of the active cation sites in their hydrated state through Fukui functions using hard-soft acid base (HSAB) principle. Finally, a swelling mechanism is proposed. This is a unique study where a combination of periodic and localized calculations has been performed to validate the capability of reactivity index calculations in material designing.