Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films.

Exploiting the full potential of layered materials for a broad range of applications requires delamination into functional nanosheets. Delamination via repulsive osmotic swelling is driven by thermodynamics and represents the most gentle route to obtain nematic liquid crystals consisting exclusively of single-layer nanosheets. This mechanism was, however, long limited to very few compounds, including 2:1-type clay minerals, layered titanates, or niobates. Despite the great potential of zeolites and their microporous layered counterparts, nanosheet production is challenging and troublesome, and published procedures implied the use of some shearing forces. Here, we present a scalable, eco-friendly, and utter delamination of the microporous layered silicate ilerite into single-layer nanosheets that extends repulsive delamination to the class of layered zeolites. As the sheet diameter is preserved, nematic suspensions with cofacial nanosheets of ≈9000 aspect ratio are obtained that can be cast into oriented films, e.g., for barrier applications.

Osmotic Delamination: A Forceless Alternative for the Production of Nanosheets Now in Highly Polar and Aprotic Solvents.

Repulsive osmotic delamination is thermodynamically allowed "dissolution" of two-dimensional (2D) materials and therefore represents an attractive alternative to liquid-phase exfoliation to obtain strictly monolayered nanosheets with an appreciable aspect ratio with quantitative yield. However, osmotic delamination was so far restricted to aqueous media, severely limiting the range of accessible 2D materials. Alkali-metal intercalation compounds of MoS2 or graphite are excluded because they cannot tolerate even traces of water. We now succeeded in extending osmotic delamination to polar and aprotic organic solvents. Upon complexation of interlayer cations of synthetic hectorite clay by crown ethers, either 15-crown-5 or 18-crown-6, steric pressure is exerted, which helps in reaching the threshold separation required to trigger osmotic delamination based on translational entropy. This way, complete delamination in water-free solvents like aprotic ethylene and propylene carbonate, N-methylformamide, N-methylacetamide, and glycerol carbonate was achieved.