Formation processes, size changes, and properties of nanosheets derived from exfoliation of soft layered inorganic–organic composites

Exfoliation is a general route to obtain two-dimensional (2D) nanomaterials. A variety of methods have been developed for controlled exfoliation of layered materials based on stacking via van der Waals interaction, such as graphite and transition-metal dichalcogenides. On the other hand, rigid layered materials consisting of inorganic layers and interlayer metal ions stacked via electrostatic interaction, such as transition-metal oxides and clays, have a limited number of exfoliation methods. Here we studied a new exfoliation route through formation of soft layered composites. Intercalation of guest organic molecules changed rigid inorganic layered compounds into soft layered composites with stacking via van der Waals interaction. The soft layered inorganic–organic composites were exfoliated into surface-modified nanosheets in organic media. The layered composites showed swelling with dispersion in organic media. The time-course analyses suggest that the layered composites were simultaneously exfoliated in the vertical direction and fractured in the lateral direction. Thinner and smaller nanosheets were obtained with an increase in the exfoliation time. Although the resultant nanosheets gradually aggregated in the colloidal liquid, the original dispersion state was recovered with sonication for 5 min at room temperature. This exfoliation route using soft layered composites can be used in the synthesis and application of a variety of 2D nanomaterials.