Interfacial structure and interaction of kaolinite intercalated with N-methylformamide insight from molecular dynamics modeling

The evolution of basal spacing and interfacial structure of kaolinite-N-methylformamide (NMF) complexes during the intercalation process were difficult to obtain using experimental methods. In present study, a series of kaolinite-NMF complex models with various numbers of NMF molecules in the interlayer space were constructed to mimic the progressive stage of the intercalation process of kaolinite intercalated by NMF. The MD simulations were performed on these models to explore the evolution of basal spacing and interfacial structure of kaolinite-NMF complexes during the intercalation process. It was found that the basal spacing of complex was stabilized at 11 Å during the intercalation process, where the molecular plane of NMF oriented at small angles with respect to the interlayer surface with the CO groups and NH bonds pointing toward the octahedral and tetrahedral surfaces, respectively, due to the hydrogen bonding interactions. The basal spacing can be enlarged to larger values with the prerequisite of overcoming the energy barrier. With the increase of basal spacing during the intercalation process, the NMF were rearranged as a pillar with the molecular planes orienting at higher angles with respect to the interlayer surface, and then developed to disordered bilayer structure. For the interfacial interaction of kaolinite-NMF complex, both the octahedral surface and tetrahedral surface showed binding affinity to the NMF, which is the driving force for the intercalation of NMF in kaolinite. The octahedral surface displays stronger binding affinity to the NMF in terms of the the H-bonds and energetics compared to the tetrahedral surface partially due to the highly active surface hydroxyl groups. The present study provides insight into the basal spacing evolution, and interfacial structure and interaction of kaolinite-NMF complexes, which can enhance the understanding of kaolinite intercalated by small molecules.