Hydrothermal hot-pressing induced phase transition in hexagonal boron nitride

The phase transition of hBN nanocrystals induced by hydrothermal hot-pressing process has been investigated by XRD, FTIR, TEM and HRTEM. It was found that a phase transition of hBN → tBN → aBN occurred with increasing hot-pressing temperature, i.e., hBN transformed into tBN at above 270 °C, and followed by another transformation from tBN to aBN at 310 °C. In addition, FTIR spectra and HRTEM images indicate that a small amount of cBN formed directly from the amorphous BN matrix at 75 MPa and 310 °C. This phenomenon is similar to what happened in conventional high temperature and high pressure method, which is believed to promote the phase transition from hBN to cBN.     

Transverse pressure induced phase transitions in boron nitride nanotube bundles and the lightest boron nitride crystal

We simulate the phase transition processes of aligned crystalline boron nitride (BN) nanotube bundles under transverse pressure, and investigate the phase transition mechanism and transition conditions. The antiparallel polar bonds rule, associated with the interaction between the tubes, is demonstrated to be crucial to such phase transitions. And the curvature of the tubes can greatly affect the phase transition behavior. We discover a unique sp(2)-sp(3)-sp(2) transition and a series of new BN crystal phases including a novel porous sheet-stacking-up form with the lightest density (2.01 g/cm(3)), which could be used in highly efficient energy storage.     

Ambient carbon dioxide capture by boron-rich boron nitride nanotube

Carbon dioxides (CO(2)) emitted from large-scale coal-fired power stations or industrial manufacturing plants have to be properly captured to minimize environmental side effects. From results of ab initio calculations using plane waves [PAW-PBE] and localized atomic orbitals [ONIOM(wB97X-D/6-31G*:AM1)], we report strong CO(2) adsorption on boron antisite (B(N)) in boron-rich boron nitride nanotube (BNNT). We have identified two adsorption states: (1) A linear CO(2) molecule is physically adsorbed on the B(N), showing electron donation from the CO(2) lone-pair states to the B(N) double-acceptor state, and (2) the physisorbed CO(2) undergoes a carboxylate-like structural distortion and C═O π-bond breaking due to electron back-donation from B(N) to CO(2). The CO(2) chemisorption energy on B(N) is almost independent of tube diameter and, more importantly, higher than the standard free energy of gaseous CO(2) at room temperature. This implies that boron-rich BNNT could capture CO(2) effectively at ambient conditions.     

Hydrogen adsorption on carbon-doped boron nitride nanotube

The adsorption of atomic and molecular hydrogen on carbon-doped boron nitride nanotubes is investigated within the ab initio density functional theory. The binding energy of adsorbed hydrogen on carbon-doped boron nitride nanotube is substantially increased when compared with hydrogen on nondoped nanotube. These results are in agreement with experimental results for boron nitride nanotubes (BNNT) where dangling bonds are present. The atomic hydrogen makes a chemical covalent bond with carbon substitution, while a physisorption occurs for the molecular hydrogen. For the H(2) molecule adsorbed on the top of a carbon atom in a boron site (BNNT + C(B)-H(2)), a donor defect level is present, while for the H(2) molecule adsorbed on the top of a carbon atom in a nitrogen site (BNNT + C(N)-H(2)), an acceptor defect level is present. The binding energies of H(2) molecules absorbed on carbon-doped boron nitride nanotubes are in the optimal range to work as a hydrogen storage medium.     

Synthesis of boron nitride nanotube films with a nanoparticle catalyst

Boron nitride nanotube (BNNT) films were synthesized by combining ball milling and thermal chemical vapor deposition (CVD) using nano-Fe₃O₄ as a catalyst. The as-produced BNNTs have a bamboo-like structure and have a diameter in the range of 50~200 nm with an average length of more than 40 mm. Moreover, BNNT nanojunction structures were synthesized. The structure and morphology of the BNNTs were characterized by XRD, SEM, TEM and HRTEM. The possible growth mechanism of BNNTs and BNNT nanojunction structures were proposed. Though the BNNT films were observed, out of our expectation, BNNTs with thin tube wall and small average diameter have not been achieved, and this could be mainly ascribed to the aggregation of the nanoparticle catalyst, resulting in greater catalyst particles during the process of BNNT growth. This result will provide a promising approach to obtain the desired shape of BNNTs and produce branched junctions of BNNTs.     

Z-BN: a novel superhard boron nitride phase

A superhard boron nitride phase dubbed as Z-BN is proposed as a possible intermediate phase between h-BN and zinc blende BN (c-BN), and investigated using first-principles calculations within the framework of density functional theory. Although the structure of Z-BN is similar to that of bct-BN containing four-eight BN rings, it is more energetically favorable than bct-BN. Our study reveals that Z-BN, with a considerable structural stability and high density comparable to c-BN, is a transparent insulator with an indirect band gap of about 5.27 eV. Amazingly, its Vickers hardness is 55.88 GPa which is comparable to that of c-BN. This new BN phase may be produced in experiments through cold compressing AB stacking h-BN due to its low transition pressure point of 3.3 GPa.     

Adsorption of transition-metal atoms on boron nitride nanotube: a density-functional study

Adsorption of transition atoms on a (8,0) zigzag single-walled boron nitride (BN) nanotube has been investigated using density-functional theory methods. Main focuses have been placed on configurations corresponding to the located minima of the adsorbates, the corresponding binding energies, and the modified electronic properties of the BN nanotubes due to the adsorbates. We have systemically studied a series of metal adsorbates including all 3d transition-metal elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) and two group-VIIIA transition-metal elements (Pd and Pt). We found that many transition-metal atoms can be chemically adsorbed on the outer surface of the BN nanotubes and that the adsorption process is typically exothermic. Upon adsorption, the binding energies of the Sc, Ti, Ni, Pd, and Pt atoms are relatively high (>1.0 eV), while those of V, Fe, and Co atoms are modest, ranging from 0.62 to 0.92 eV. Mn atom forms a weak bond with the BN nanotube, while Zn atom cannot be chemically adsorbed on the BN nanotube. In most cases, the adsorption of transition-metal atoms can induce certain impurity states within the band gap of the pristine BN nanotube, thereby reducing the band gap. Most metal-adsorbed BN nanotubes exhibit nonzero magnetic moments, contributed largely by the transition-metal atoms.     

A computational study of water adsorption on boron nitride nanotube

The effect of water molecule adsorption on the surface of (5,0) zigzag boron nitride nanotube was studied by density functional theory calculations. Geometrical optimizations were carried out at the B3LYP/6-31+G* level of theory. Six different configurations of water molecule(s) adsorption process including monomer (1WB and 1WN), dimer (2WB, 2WNN, and 2WBN), and trimer (3WB) clusters were obtained. The strengths of interactions were analyzed by the equilibrium geometries, binding energies, and charge transfer. The natural bonding analysis was also performed to investigate electronic properties. The results reveal that the adsorption of water is more favorable as the water cluster size increases.     

A computational study of oxygen-termination of a (6,0) boron nitride nanotube

Abstract  

We performed density functional theory (DFT) calculations to investigate the properties of electronic structures of representative armchair and zigzag silicon carbide nanotubes (SiCNTs). The model structures were optimized and the NMR parameters were calculated at the sites of silicon-29 and carbon-13 atoms in these structures. Our results indicated that different electronic environments could be detected by using the atoms of nanotubes in which the atoms of tips, especially for zigzag SiCNT, exhibit distinctive properties among other atoms.     

Structural characterizations and electronic properties of boron nitride nanotube crystalline bundles

The structural characterizations and electronic properties of aligned armchair single-walled boron nitride nanotube (BNNT) bundles are theoretically investigated. In the spontaneous bundling process, the cylindrical shapes of bundled BNNTs are preserved all along, whereas their diameters expand, then shrink, and return back to the initial dimensions. Owing to the nonuniform distribution of positive and negative charges among BNNTs, the multipole interaction in bundles is completely dependent upon the chirality of each BNNT and the arrangement of bundled BNNTs. The effect of intertube coupling on the dispersions of BNNT bundles is demonstrated. Our systematical simulations might be helpful for the understanding of potential applications of BNNT bundles in the nanometer manufacturing techniques such as doping, adsorption, and derivative synthesis.     

Electronic structure of sulfur terminated zigzag boron nitride nanotube: A computational study

Density functional theory (DFT) calculations have been performed to investigate the electronic and structural properties of sulfur (S) terminated models of zigzag boron nitride (BN) nanotube. Four models including pristine, boron (B) tip terminated by S, nitrogen (N) tip terminated by S, and both of B and N tips terminated by S have been considered for optimizations and chemical shielding (CS) parameters calculations. The results indicate that the B–N bond lengths do not detect any changes due to the S-termination but the band gaps and dipole moments detect notable changes especially for the model of the N-tip terminated by the S atoms. The CS parameters also indicate that the atoms of the models are divided into layers with similar parameters in each layer. In the model of the B-tip terminated by the S atoms, the CS parameters indicate strong chemical bonding of N- and S-layers; however, only some attractions between the B- and S-layers of the model of the N-tip terminated by the S atoms have been detected. In the model of B and N tips terminated by the S atoms, the most significant changes among the models are detected.     

Determination of boron and nitrogen in boron nitride

Improved techniques are described for the determination of boron and nitrogen in pure boron nitride. Controlled fusion of boron nitride with sodium carbonate in a muffle furnace is followed by a potentiometric titration of the boric acid. A special quartz vessel is described for the determination of nitrogen. The boron nitride is fused with sodium hydroxide and the resulting ammonia is swept into a receiver and titrated with standard hydrochloric acid. Boron and nitrogen values with their standard deviation are given for a typical pure boron nitride.     

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B¹¹N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =−1, 0, +1 sequences of the triplet system (transition A³Π–X³Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B¹⁰N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B¹¹N constants. Nevertheless, the presence of the lower abundant isotopic radical B¹⁰N was not proved due the noise level which masked the low emission intensity of the B¹⁰N band heads.     

Ni adsorption on Stone-Wales defect sites in single-wall carbon nanotubes

Ni adsorption on Stone-Wales defect sites in (10,0) zigzag and (5,5) armchair single-wall carbon nanotubes was studied using the density functional theory. The stable adsorption sites and their binding energies on different Stone-Wales defect types were analyzed and compared to those on perfect side walls. It was determined that the sites formed via fusions of 7-7 and 6-7 rings are the most exothermic in the cases of (10,0) and (5,5) defective tubes. In addition C-C bonds associated with Stone-Wales defects are more reactive than the case for a perfect hexagon, thus enhancing the stability of the Ni adsorption. Moreover, the Ni adsorption was found to show a noticeable relationship to the orientation of the Stone-Wales defects with respect to the tube axis. The nature of the Ni adsorption on Stone-Wales defects that have the similar orientation is identical, in spite of the different chiralities.     

Specifics of the thermal transformations of the wurtzite phase of boron nitride

The kinetics of the transformation of the BN wurtzite phase to the graphite modification was studied at normal pressure and 600–970°C. At these temperatures and certain thermal treatment durations, along with the formation of the graphite phase, the reverse transition from g-BN to w-BN occurs, a behavior indicative of a higher thermodynamics stability of the wurtzite phase.     

Prediction of formation of cubic boron nitride by construction of temperature-pressure phase diagram at the nanoscale

The size-dependent phase diagram of BN was developed on the basis of the nanothermodynamic theory. Our studied results suggest that cubic BN (c-BN) is more stable than hexagonal BN (h-BN) in the deep nanometer scale and the triple point of c-BN, h-BN and liquid shifts toward the lower temperature and pressure with decreasing the crystal size. Moreover, surface stress, which is determined by the experimental conditions, is the main reason to influence the formation of c-BN nuclei. The developed phase diagram of BN could help us to exploit new techniques for the fabrication of c-BN nanomaterials.