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.

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Boron Nitride Nanotubes and Nanosheets

π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements

Functionalization is an important way to breed new properties and applications for a material. This review presents an overview of the progresses in functionalized hexagonal boron nitride (h-BN) nanomaterials. It begins with an introduction of h-BN structural features, physical and chemical properties, followed by an emphasis on the developments of BN functionalization strategies and its emerging properties/applications, and ends with the research perspectives. Different functionalization methods, including physical and chemical routes, are comprehensively described toward fabrication of various BN derivatives, hetero- and porous structures, etc. Novel properties of functionalized BN materials, such as high water solubility, excellent biocompatibility, tunable surface affinities, good processibility, adjustable band gaps, etc., have guaranteed wide applications in biomedical, electronic, composite, environmental and "green" energy-related fields.

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Functionalized hexagonal boron nitride nanomaterials: emerging properties and applications.

The recent surge in graphene research has stimulated interest in the investigation of various 2-dimensional (2D) nanomaterials. Among these materials, the 2D boron nitride (BN) nanostructures are in a unique position. This is because they are the isoelectric analogs to graphene structures and share very similar structural characteristics and many physical properties except for the large band gap. The main forms of the 2D BN nanostructures include nanosheets (BNNSs), nanoribbons (BNNRs), and nanomeshes (BNNMs). BNNRs are essentially BNNSs with narrow widths in which the edge effects become significant; BNNMs are also variations of BNNSs, which are supported on certain metal substrates where strong interactions and the lattice mismatch between the substrate and the nanosheet result in periodic shallow regions on the nanosheet surface. Recently, the hybrids of 2D BN nanostructures with graphene, in the form of either in-plane hybrids or inter-plane heterolayers, have also drawn much attention. In particular, the BNNS–graphene heterolayer architectures are finding important electronic applications as BNNSs may serve as excellent dielectric substrates or separation layers for graphene electronic devices. In this article, we first discuss the structural basics, spectroscopic signatures, and physical properties of the 2D BN nanostructures. Then, various top-down and bottom-up preparation methodologies are reviewed in detail. Several sections are dedicated to the preparation of BNNRs, BNNMs, and BNNS–graphene hybrids, respectively. Following some more discussions on the applications of these unique materials, the article is concluded with a summary and perspectives of this exciting new field.

Advances in 2D boron nitride nanostructures: nanosheets, nanoribbons, nanomeshes, and hybrids with graphene

Noncarbon support materials for polymer electrolyte membrane fuel cell electrocatalysts.

Synthetic routes to boron nitride

Recent Advances in Phosphinoborane Chemistry

Uranium(VI) alkoxide complexes are prepared via metathesis reactions of [UO2Cl2(THF)2]2 with potassium alkoxides in nonaqueous media. The dark red compound U[OCH2C(CH3)3]6, 1, results from redistributive exchange of oxo and neopentoxide ligands between more than one uranium species. Single-crystal X-ray diffraction analysis of 1 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by six neopentoxide ligands. Imposition of steric congestion at the metal center prevents oxo-alkoxide ligand exchange in the reactions using more sterically demanding alkoxides. Simple metathesis between uranyl chloride and alkoxide ligands occurs in the synthesis of golden yellow-orange UO2(OCHPh2)2(THF)2, 2, and yellow UO2[OCH(tBu)Ph]2(THF)2, 3. Single-crystal X-ray diffraction analysis of 2 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by two apical oxo ligands, two diphenylmethoxide ligands occupying trans positions, and two tetrahydrofuran ligands. Coordination of diisopropylmethoxide allows for synthesis of a more complex binary alkoxide system. Single-crystal X-ray diffraction analysis of watermelon red [UO2(OCH(iPr)2)2]4, 4, reveals a tetramer in which each uranium is coordinated in a pseudooctahedral fashion by two apical oxo ligands, one terminal alkoxide, two bridging alkoxide ligands, and one bridging oxo ligand from a neighboring uranyl group. These compounds are characterized by elemental analysis, 1H NMR, infrared spectroscopy, and, for 1, 2, and 4, single-crystal X-ray diffraction analysis. Luminescence spectroscopy is employed to evaluate the extent of aggregation of compounds 2-4 in various solvents. Vibrational spectroscopic measurements of 2-4 imply that, in contrast to the case of uranyl complexes prepared in aqueous environments, coordination of relatively strongly donating alkoxide ligands allows for enhancement of electron density on the uranyl groups such that the uranyl U=O bonds are weakened. Crystal data are as follows. 1: monoclinic space group C2/m, a = 10.6192(8) A, b = 18.36(1) A, c = 10.6151(8) A, beta = 109.637(1) degrees, V = 1949.1(3) A3, Z = 2, dcalc = 1.297 g cm-3. Refinement of 2065 reflections gave R1 = 0.045. 2: monoclinic space group P2(1)/c, a = 6.1796(4) A, b = 15.669(1) A, c = 16.169(1) A, beta = 95.380(1) degrees, V = 1558.7(2) A3, Z = 2, dcalc = 1.664 g cm-3. Refinement of 3048 reflections gave R1 = 0.036. 4: tetragonal space group I4, a = 17.8570(6) A, b = 17.8570(6) A, c = 11.4489(6) A, V = 3650.7(3) A3, Z = 2, dcalc = 1.821 g cm-3. Refinement of 1981 reflections gave R1 = 0.020.

Basicity of uranyl oxo ligands upon coordination of alkoxides.

Synthetic Routes to Boron Nitride

A series of eight porous boron nitride materials with nitrogen/BET surface areas of 437-712 m[sup 2]/g have been produced using polymeric precursors varied by systematic synthesis modifications. All samples exhibit type I isotherms indicating that a majority of the porosity occurs in pores with radius less than 1.0 nm. Carbon dioxide adsorption at 273 K was analyzed using the Dubinin-Radushkevich (D-R) and Dubinin-Astakov (D-A) equations. Significant differences between BET/N[sub 2] and D-R/CO[sub 2] surface areas are observed. Adsorption of carbon dioxide and methane is measured at 273 K over the pressure range of 0-800 Torr, and significant differences in adsorption selectivity are observed. Although all eight samples have similar BET surface areas, the carbon dioxide uptake at 273 K and 800 Torr varies from 9.5 to 125 cm[sup 3]/g. Differences in the chemical and physical structure of the samples are probed with Fourier transform IR, X-ray diffraction, and small angle X-ray scattering measurements. CH[sub 4]/CO[sub 2] selectivity correlates with both the radius of gyration obtained from SAXS and the D-A coefficient from CO[sub 2] adsorption. 16 refs., 9 figs., 1 tab.

R. T. Paine

Papers

Synthetic routes to boron nitride

Recent Advances in Phosphinoborane Chemistry

Basicity of uranyl oxo ligands upon coordination of alkoxides.

Synthetic Routes to Boron Nitride

Boron nitride as a selective gas adsorbent