Hexagonal boron nitride (h-BN) is a layered material with a graphite-like structure in which planar networks of BN hexagons are regularly stacked. As the structural analogue of a carbon nanotube (CNT), a BN nanotube (BNNT) was first predicted in 1994; since then, it has become one of the most intriguing non-carbon nanotubes. Compared with metallic or semiconducting CNTs, a BNNT is an electrical insulator with a band gap of ca. 5 eV, basically independent of tube geometry. In addition, BNNTs possess a high chemical stability, excellent mechanical properties, and high thermal conductivity. The same advantages are likely applicable to a graphene analogue-a monatomic layer of a hexagonal BN. Such unique properties make BN nanotubes and nanosheets a promising nanomaterial in a variety of potential fields such as optoelectronic nanodevices, functional composites, hydrogen accumulators, electrically insulating substrates perfectly matching the CNT, and graphene lattices. This review gives an introduction to the rich BN nanotube/nanosheet field, including the latest achievements in the synthesis, structural analyses, and property evaluations, and presents the purpose and significance of this direction in the light of the general nanotube/nanosheet developments.

Fluorination of BN nanotubes has been performed using a catalytic growth method, which leads to the appearance of markedly curved fluorine-doped BN sheets and converts originally insulating BN nanotubes to semiconductors, as confirmed by the comparative electron transport four-probe measurements on doped and undoped individual BN nanotubes.

A new concept is proposed to explain the formation of spherical boron nitride (BN) nanoparticles synthesized by the chemical vapor deposition (CVD) reaction of trimethoxyborane (B(OMe)3) with ammonia. The intermediate phases formed during the CVD under different reaction conditions are analyzed by X‐ray diffraction, electron microscopy, thermogravimetry, and spectroscopy techniques. The transition mechanism from an intermediate B(OMe)3–xH3–xN (x < 2) phase having single BN bonds to the BN nanoparticles is elucidated. This particularly emphasizes the CVD temperature effect governing the conversion of the NH···OB hydrogen bonds in (OMe)3B · NH3 into the NB bonds in B(OMe)3–xH3–xN. The spherical morphology strongly depends on the remnant impurity oxygen formed upon Me2O group elimination in the intermediate. Two types of spherical BN nanoparticles primarily attractive for immediate commercialization (with C and H impurities at a level less than 1 wt %) are synthesized by the adjustment of experimental parameters: high oxygen‐containing (∼6.3 wt %) BN spheres with a diameter of ∼90 nm and a specific surface area of 26.8 m2 g−1; and low oxygen‐containing (<1 wt %) BN spheres with a diameter of ∼30 nm and a surface area of 52.7 m2 g−1. Finally, the regarded synthetic techniques are fully optimized in the present work.