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Liquid phase exfoliation (LPE) is a method that can be used to produce bulk quantities of two-dimensional (2D) nanosheets from layered van der Waals (vdW) materials. In recent years, LPE has been applied to several non-vdW materials with anisotropic bonding to produce nanosheets and platelets, but it has not been demonstrated for materials with strong isotropic bonding. In this paper, we demonstrate the exfoliation of boron carbide (B 4 C), the third hardest known material, into ultrathin nanosheets. B 4 C has a structure consisting of strongly bonded boron icosahedra and carbon chains, but does not have anisotropic cleavage energies to suggest that it can be readily cleaved into nanosheets. B 4 C has been widely studied for its very high melting point, high mechanical strength, and chemical stability, as well as its zero- and one-dimensional nanostructured forms. Herein, ultrathin nanosheets are successfully prepared by sonication of B 4 C powder in organic solvents and are characterized by microscopy and spectroscopy. Density functional theory (DFT) simulations reveal that B 4 C can be cleaved along several different crystallographic planes with similar energetic favourability, facilititated by an unexpected mechanism of breaking boron icosahedra and forming new boron-rich cage structures at the surface. Atomic force microscopy (AFM) shows that the nanosheets produced by LPE are as thin as 5 nm, with an average thickness of 31.4 nm and average area of 16 000 nm 2 . Raman spectroscopy shows that many of the nanosheets exhibit additional carbon-rich peaks that change with laser irradiation, which are attributed to atomic rearrangements and amorphization at the nanosheet surfaces, consistent with the diverse cleavage planes. High-resolution transmission electron microscopy (HRTEM) demonstrates that many different cleavage planes exist among the exfoliated nanosheets, in agreement with DFT simulations. This work elucidates the exfoliation mechanism of 2D B 4 C and suggests that LPE can be applied to generate nanosheets from a variety of non-layered and non-vdW materials. 

The removal of heavy metal contaminants from water is important for public health, and recently many two-dimensional (2D) materials with high specific surface areas are being studied as promising new active components in water purification. In particular, 2D MoS₂nanosheets have been used for the removal of various heavy metals, but usually in either in complex geometries and composites, or in the chemically exfoliated metallic 1T-MoS₂phase. However, the interaction of heavy metals dissolved in water with unmodified semiconducting 2H-MoS₂is not well studied. In this paper, we report a detailed fundamental investigation of how Pb²⁺ions interact with 2H-MoS₂. We observe small solid clusters that form on the MoS₂surfaces after exposing them to Pb(NO₃)₂aqueous solutions as shown by atomic force microscopy and transmission electron microscopy, and for liquid phase exfoliated MoS₂we observe the nanosheets precipitating out of dispersion along with insoluble solid granules. We use a combination of x-ray photoelectron spectroscopy and x-ray diffraction to identify these solid clusters and granules as primarily PbSO₄with some PbMoO₄. We put forth an interaction mechanism that involves MoS₂defects acting as initiation sites for the partial dissolution in aqueous oxygenated conditions which produces MoO₄²⁻and SO₄²⁻ions to form the solids with Pb²⁺. These results are an important contribution to our fundamental understanding of how MoS₂interacts with metal ions and will influence further efforts to exploit MoS₂for water remediation applications.