Gigantic swelling of inorganic layered materials: a bridge to molecularly thin two-dimensional nanosheets

J Am Chem Soc. 2014 Apr 9;136(14):5491-500. doi: 10.1021/ja501587y. Epub 2014 Mar 31.


Platy microcrystals of a typical layered material, protonated titanate, have been shown to undergo an enormous degree of swelling in aqueous solutions of various amines, including tertiary amines, quaternary ammonium hydroxides, and primary amines. Introducing these solutions expanded the crystal gallery height by up to ~100-fold. Through systematic analysis, we determined that ammonium ion intercalation is predominantly affected by the acid-base equilibrium and that the degree of swelling or inflow of H2O is controlled by the osmotic pressure balance between the gallery and the solution environment, both of which are relatively independent of electrolyte identity but substantially dependent on molarity. In solutions of tertiary amines and quaternary ammonium hydroxides, the uptake of ammonium ions increases nearly linearly with increasing external concentration before reaching a saturation plateau, i.e., ~40% relative to the cation-exchange capacity of the crystals used. The only exception is tetrabutylammonium ions, which yield a lower saturation value, ~30%, owing to steric effects. The swelling behaviors in some primary amine solutions differ as a result of the effect of attractive forces between amine solute molecules on the solution osmotic pressure. Although the swelling is essentially colligative in nature, the stability of the resultant swollen structure is heavily dependent on the chemical nature of the guest ions. Intercalated ions of higher polarity and smaller size help stabilize the swollen structure, whereas ions of lower polarity and larger size lead readily to exfoliation. The insight gained from this study sheds new light on both the incorporation of guest molecules into a gallery of layered structures in general and the exfoliation of materials into elementary single-layer nanosheets.