Molecular Dynamics Simulation of Basal Spacing, Energetics, and Structure Evolution of a Kaolinite-Formamide Intercalation Complex and Their Interfacial Interaction

S Zhang and QF Liu and F Gao and BJ Teppen, JOURNAL OF PHYSICAL CHEMISTRY C, 122, 3341-3349 (2018).

DOI: 10.1021/acs.jpcc.7b10234

Molecular dynamics simulations were performed on kaolinite formamide complex models with various numbers of formamide molecules loaded in the kaolinite interlayer to explore the basal spacing, energetics, and structure evolution of the kaolinite formamide complex during the intercalation process. Additionally, the interfacial interactions of formamide with kaolinite interlayer surfaces were calculated. The calculation revealed that the basal spacing of kaolinite was enlarged to 9.6 angstrom at the beginning of intercalation. Formamide was arranged as a monolayer structure in the kaolinite interlayer with the molecular plane oriented at small angles with respect to the interlayer surface. With continuous intercalation, the basal spacing readily reached a stable stage at 10.6 angstrom, where formamide rearranged its structure by rotating the molecule plane along the C N bond that was parallel to the interlayer surface, which resulted in the molecular plane orienting at higher angles with respect to the interlayer surface. During this process, the C=O groups oriented toward the hydroxyl groups on the interlayer octahedral surface, and one of N H bonds progressively pointed toward the basal oxygens on the opposing interlayer tetrahedral surface. Continuous intercalation can enlarge the basal spacing to more than 14 angstrom with the prerequisite of overcoming the energy barrier, and then formamide evolved to a disordered bilayer structure in the kaolinite interlayer. The affinity of kaolinite interlayer surfaces for formamide motivated the intercalation process. The octahedral surface displayed a relatively larger affinity toward formamide compared to the tetrahedral surface partially due to the presence of hydroxyl groups that are more active in the intermolecular interactions with formamide.

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