Hexagonal boron nitride (h-BN) is traditionally considered to be insoluble in water. However, here we demonstrate that water is effective to exfoliate the layered h-BN structures with the assistance of bath sonication, forming “clean” aqueous dispersions of h-BN nanosheets without the use of surfactants or organic functionalization. Besides few-layered h-BN nanosheets, there was also evidence on the presence of monolayered nanosheet and nanoribbon species. Most nanosheets were of reduced lateral sizes, which was attributed to the cutting of parent h-BN sheets induced by the sonication-assisted hydrolysis (evidenced by the ammonia test and spectroscopy results). The hydrolysis effect also assisted in the exfoliation of h-BN nanosheets in addition to the solvent polarity effect. The h-BN nanosheets in such “clean” aqueous dispersions were demonstrated to be conveniently processed via solution methods with retained physical properties. The dispersed h-BN nanosheets in water also exhibited strong affinity toward proteins such as ferritin, suggesting that the nanosheet surfaces were available for further bioconjugations. The above findings may pave the way for the applications of these novel 2-dimensional nanomaterials in various fields such as composites, electronics, and biology.

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A pristine hexagonal boron nitride (h-BN) powder sample with layered crystalline sheetlike particles of ∼1−10 μm in lateral sizes and a few hundred nanometers in thicknesses was mechanically treated using a ball-mill to intentionally introduce defect sites. The h-BN was ball-milled for various times and subsequently was functionalized with a long alkyl chain amine via Lewis acid−base interactions between the amino groups and the boron atoms of h-BN to obtain soluble amine-attached nanosheet samples as the products. The functionalized h-BN nanosheet samples were characterized via various microscopic and spectroscopic techniques. The results strongly support a direct correlation between increasing defect site concentrations of the h-BN nanosheet samples and improved reaction efficiency with the amine. This suggests the enhanced reactivity of defect boron atoms in comparison to conjugated ones on an unperturbed h-BN plane. NMR investigations provided the strongest evidence supporting the hypothesis that the amino groups reacted with the h-BN at specific defect sites induced by ball-milling. The mechanistic implications are discussed.