Boron‐Double‐Ring Sheet,Fullerene, and Nanotubes: Potential Hydrogen Storage Materials

Similar to carbon‐based graphene, fullerenes and carbon nanotubes, boron atoms can form sheets, fullerenes, and nanotubes. Here we investigate several of these novel boron structures all based on the boron double ring within the framework of density functional theory. The boron sheet is found to be metallic and flat in its ground state. The spherical boron cage containing 180 atoms is also stable and has I symmetry. Stable nanotubes are obtained by rolling up the boron sheet, and all are metallic. The hydrogen storage capacity of boron nanostructures is also explored, and it is found that Li‐decorated boron sheets and nanotubes are potential candidates for hydrogen storage. For Li‐decorated boron sheets, each Li atom can adsorb a maximum of 4 H₂ molecules with g_d=7.892 wt %. The hydrogen gravimetric density increases to g_d=12.309 wt % for the Li‐decorated (0,6) boron nanotube.     

Topology, connectivity, and electronic structure of C and B cages and the corresponding nanotubes

After a brief discussion of the structural trends which appear with an increasing number of atoms in B cages, a one-to one correspondence between the connectivity of B cages and C cage structures will be proposed. The electronic level spectra of both systems from Hartree-Fock calculations is given and discussed. The relation of curvature introduced into an originally planar graphitic fragment to pentagonal "defects" such as are present in buckminsterfullerene is also briefly treated. A study of the structure and electronic properties of B nanotubes will then be introduced. We start by presenting a solution of the free-electron network approach for a "model boron" planar lattice with local coordination number 6. In particular the dispersion relation E(k) for the pi-electron bands, together with the corresponding electronic Density Of States (DOS), will be exhibited. This is then used within the zone-folding scheme to obtain information about the electronic DOS of different nanotubes obtained by folding this model boron sheet. To obtain the self-consistent potential in which the valence electrons move in a nanotube, "the March model" in its original form was invoked, and the results are reported for a carbon nanotube. Finally, heterostructures, such as BN cages and fluorinated buckminsterfullerene, will be briefly treated, the new feature here being electronegativity difference.     

Electronic structure of octagonal boron nitride nanotubes

The effect of an octagonal lattice configuration on a boron nitride nanotube is explored using first principle calculations. Calculations show that the formational energy of an octagonal boron nitride nanotube (o‐BNNT) is an exothermic reaction. Boron and nitrogen atoms within an o‐BNNT have an average of 2.88 electrons and 9.09 electrons, respectively, indicating ionic‐like bonding. In addition, the electronic structure of the octagonal boron nitride nanotube shows semiconductive properties, while h‐BNNT is reported to be an insulator. Additional o‐BNNTs with varying diameters are calculated where the results suggest that the diameter has an effect on the binding energy and bandgap of the o‐BNNT. The defect sites of the o‐BNNT are reactive against hydrogen where a boron defect is particularly reactive. Thus, this work suggests that physical and chemical properties of a boron nitride nanotube can be tailored and tuned by controlling the lattice configuration of the nanotube.     

The effect of molecular weight on the separation of semiconducting single‐walled carbon nanotubes using poly(2,7‐carbazole)s

The use of selective interactions between conjugated polymers and single‐walled carbon nanotubes has emerged as a promising method for the separation of nanotubes by electronic type. Although much attention has been devoted to investigating polyfluorenes and their ability to disperse semiconducting carbon nanotubes under specific conditions, other polymer families, such as poly(2,7‐carbazole)s, have been relatively overlooked. Poly(2,7‐carbazole)s have been shown to also preferentially interact with semiconducting carbon nanotubes, however a detailed investigation of polymer parameters, such as molecular weight, has not been performed. We have prepared seven different molecular weights of a poly(2,7‐carbazole), from short chain oligomers to high molecular weight polymers, and have investigated their effectiveness at dispersing semiconducting single‐walled carbon nanotubes. Although all polymer chain lengths were able to efficiently exfoliate carbon nanotube bundles using a mild dispersion protocol, only polymers above a certain threshold molecular weight (M_n ～ 27 kDa) were found to exhibit complete selectivity for semiconducting nanotubes, with no observable signals from metallic species. Additionally, we found the quality of separation to be strongly dependent on the ratio of polymer to carbon nanotube. Contrary to previous reports, we have found that an excess of poly(2,7‐carbazole) leads to incomplete removal of metallic carbon nanotubes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2510–2516     

Spectroscopic Characteristics of Differently Produced Single‐Walled Carbon Nanotubes

Single‐walled carbon nanotubes (SWNTs) synthesized with different methods are investigated by using multiple characterization techniques, including Raman scattering, optical absorption, and X‐ray absorption near edge structure, along with X‐ray photoemission by following the total valence bands and C 1s core‐level spectra. Four different SWNT materials (produced by arc discharge, HiPco, laser ablation, and CoMoCat methods) contain nanotubes with diameters ranging from 0.7 to 2.8 nm. The diameter distribution and the composition of metallic and semiconducting tubes of the SWNT materials are strongly affected by the synthesis method. Similar sp² hybridization of carbon in the oxygenated SWNT structure can be found, but different surface functionalities are introduced while the tubes are processed. All the SWNTs demonstrate stronger plasmon resonance excitations and lower electron binding energy than graphite and multiwalled carbon nanotubes. These SWNT materials also exhibit different valence‐band X‐ray photoemission features, which are considerably affected by the nanotube diameter distribution and metallic/semiconducting composition.     

UV-light mediated decomposition of a polyester for enrichment and release of semiconducting carbon nanotubes

Purification of single-walled carbon nanotubes using conjugated polymers to selectively disperse either semiconducting or metallic nanotubes is effective and has received significant attention. However, the interaction between the conjugated polymer and the nanotube surface is very strong, making it difficult to remove the adsorbed polymer. Here, we report a poly(carbazole-co-terephthalate) polymer that is not only selective for semiconducting carbon nanotubes but can also be largely removed from the nanotube surface via irradiation with UV light. Irradiation of the polymer-nanotube dispersion causes degradation of ester linkages in the polymer backbone, effectively cutting the polymer into fragments that no longer bind strongly to the nanotube surface. Characterization of the electronic nature of the samples was carried out via the combination of absorption, Raman, and fluorescence spectroscopy. In addition, thermogravimetric analysis allowed determination of the amount of polymer left on the nanotube surface after irradiation and indicated that a large proportion of the polymer is removed. The reported methodology opens new possibilities for purification of semiconducting single-walled carbon nanotubes and their isolation from the polymeric dispersant.     

Effect of impurity on electronic properties of carbon nanotubes

We have studied the effect of impurity on electronic properties of single-walled carbon nanotubes using Density Functional Theory. Electronic band structures and density of states of (4, 4) and (7, 0) carbon nanotubes in the presence of different amount of B and N impurities were calculated. It was found that these impurities have significant effect on the conductivity of carbon nanotubes. The metallic (4, 4) nanotube remains to be metallic after doping with B and N. The electronic properties of small gap semiconducting (7, 0) tube can extensively change in the presence of impurity. Our results indicate that B-doped and N-doped (7, 0) carbon nanotubes can be p-type and n-type semiconductors, respectively.     

NMR parameters of SiC-doped (6,0) zigzag single-walled boron phosphide nanotubes: a density functional study

Abstract  

Nuclear magnetic resonance (NMR) parameters including isotropic and anisotropic chemical shielding parameters and electronic structures were calculated using density functional theory (DFT) for silicon–carbide-doped boron phosphide nanotubes. Geometry optimizations were carried out at the B3LYP/6-31G* level of theory using the Gaussian 03 program suite. The isotropic and anisotropic chemical shielding parameters were calculated for the sites of various ¹³C, ²⁹Si, ¹¹B, and also ³¹P atoms in pristine and SiC-doped (6,0) zigzag boron phosphide nanotube models. The calculations indicated that doping of ¹¹B and ³¹P atoms by C and Si atoms had a more significant influence on the calculated shielding tensors than did doping of the B and P atoms by Si and C atoms. In comparison with the pristine model, Si- and C-doping of P and B sites of the zigzag nanotubes reduces the energy gaps of the nanotubes and increases their electrical conductance.     

Nanocomposites based on functionalized nanotubes in polyaniline matrix by plasma polymerization

A co-spraying method of binary mixture aniline–single-walled nanotubes (SWNTs) in a plasma stream is proposed as an alternative to design new composites and nanotube functionalizing. The electrical characterizations, Fourier transform-infrared spectroscopy (FT-IR) and Raman spectra show a chemical bonding to the nanotube surface. I–V characteristics show a combined effect of the conduction mechanisms imposed by space charged limited currents (SLCS) and the metallic/semimetallic character of the nanotubes.     

Revealing the Unusual Rigid Boron Chain Substructure in Hard and Superconductive Tantalum Monoboride

Poor electrical conductivity severely limits the diverse applications of high hardness materials in situations where electrical conductivities are highly desired. A “covalent metal” TaB with metallic electrical conductivity and high hardness has been fabricated by a high pressure and high temperature method. The bulk modulus, 302.0(4.9) GPa, and Vickers hardness, 21.3 GPa, approaches and even exceeds that of traditional insulating hard materials. Meanwhile, temperature-dependent electrical resistivity measurements show that TaB possesses metallic conductivity that rivals some widely-used conductors, and it will transform into a superconductor at T_c=7.8 K. Contrary to common understanding, the hardness of TaB is higher than that of TaB₂, which indicates that low boron concentration borides could be mechanically better than the higher boron concentration counterparts. Compression behavior and first principles calculations denote that the high hardness is associated with the ultra-rigid covalent boron chain substructure. The hardness of TaB with different topologies of boron substructure shows that besides incorporating higher boron content, manipulating light element backbone configurations is also critical for higher hardness amongst transition metal borides with identical boron content.     

Ab initio simulations of doped single-walled carbon nanotube sensors

The interactions between oxygen and nitrogen atoms with single-walled carbon nanotubes were investigated for nanotubes with two different geometrical configurations using first-principle calculations within the framework of the density functional theory. We introduced a new type of toxic gas sensor that can detect the presence of H₂, Cl₂, CO, and NO molecules. We also demonstrated that the sensitivity of this device can be controlled by the concentration of the dopants on the surface of the nanotube. In addition, the transport properties of the doped nanotube were studied for different concentrations of oxygen or nitrogen atoms that were randomly distributed on the surface of the single-walled carbon nanotube. We observed that small amounts of dopants can modify the electronic and transport properties of the nanotube and can lend metallic properties to the nanotube. Band-gap narrowing occurs when the nanotube is doped with either oxygen or nitrogen atoms.     

Oxygen adsorption characteristics on hybrid carbon and boron‐nitride nanotubes

In this work, first‐principles density functional theory (DFT) is used to predict oxygen adsorption on two types of hybrid carbon and boron‐nitride nanotubes (CBNNTs), zigzag (8,0), and armchair (6,6). Although the chemisorption of O₂ on CBNNT(6,6) is calculated to be a thermodynamically unfavorable process, the binding of O₂ on CBNNT(8,0) is found to be an exothermic process and can form both chemisorbed and physisorbed complexes. The CBNNT(8,0) has very different O₂ adsorption properties compared with pristine carbon nanotubes (CNTs) and boron‐nitride nanotube (BNNTs). For example, O₂ chemisorption is significantly enhanced on CBNNTs, and O₂ physisorption complexes also show stronger binding, as compared to pristine CNTs or BNNTs. Furthermore, it is found that the O₂ adsorption is able to increase the conductivity of CBNNTs. Overall, these properties suggest that the CBNNT hybrid nanotubes may be useful as a gas sensor or as a catalyst for the oxygen reduction reaction. © 2014 Wiley Periodicals, Inc.     

A first principles study of NO2 chemisorption on silicon carbide nanotubes

Using methods based on first principles, we find that an NO₂ molecules can be chemisorbed on silicon carbide nanotubes (SiCNTs) with an appreciable binding energy (∼−1.0 eV), and that this is not the case for either carbon nanotubes (CNTs) or boron nitride nanotubes (BNNTs). A detailed analysis of the energetics, geometry, and electronic structure of various isomers of the complexes was performed. The SiCNT–NO₂ complex can be metallic or nonmetallic depending on the type of adsorption site and the chirality of the tube. However, our analysis of the electronic structure predicts that a strong p-type effect of the adsorption turns semiconducting systems into metallic ones at room temperature, irrespective of the chirality of the tube.     

碳化硼纳米线的制备和结构

以碳纳米管为模板，通过加热碳纳米管与硼粉的混合物，获得了笔直的硼碳纳米线.对纳米线的结构和成分进行研究，结果表明纳米线主要为B4C纳米线.在部分B4C纳米线的端部存在Ni颗粒，这些端部具有Ni颗粒的纳米线构成了纳米磁针.讨论了B4C纳米线的生长机制，B4C纳米线的生长主要为硼原子在碳纳米管中扩散并发生化学反应，使得碳纳米管晶格结构发生重组，形成B4C纳米线.反应后，硼原子部分取代了碳纳米管中碳原子，修补了碳纳米管中的晶格缺陷，获得了形态笔直的B4C纳米线.     

First-principles study of the electronic structures of α-rhombohedral boron codoped with lithium and oxygen

α-Rhombohedral (α-rh) boron, which is the most stable of boron's polymorphs at low temperatures, has p-type semiconductive properties. There have been some attempts to dope the interstitial sites with alkali atoms to create metallic or n-type semiconductive α-rh boron, but this has yet to be achieved. In a previous work, we proposed the codoping of α-rh boron with Li and P or As, and revealed from first principles calculations that B₁₂PLi and B₁₂AsLi could be synthesized and become narrow-gap semiconductors. The band structure suggested that the mobility of electrons might be greater than that of holes. In this paper, based on these prospective results, we selected a new combination of dopants, Li and O, and theoretically studied such compounds as B₁₂OLi and B₁₂O₂Li. The results showed that both of these materials are metallic, while the reaction energies of the Li insertion into B₁₂O and B₁₂O₂ are lower (more unstable) than with B₁₂PLi and B₁₂AsLi. It was proved that the differences in the electronic structures are caused by the dangling bonds of the dopant atoms, O, P and As.     

First-principles study of the crystal and electronic structures of α-tetragonal boron

The crystal and electronic structures of α-tetragonal (α-t) boron were investigated by first-principles calculation. Application of a simple model assuming 50 atoms in the unit cell indicated that α-t boron had a metallic density of state, thus contradicting the experimental fact that it is a p-type semiconductor. The presence of an additional two interstitial boron atoms at the 4c site made α-t boron semiconductive and the most stable. The cohesive energy per atom was as high as those of α- and β-rhombohedral boron, suggesting that α-t boron is produced more easily than was previously thought. The experimentally obtained α-t boron in nanobelt form had about two interstitial atoms at the 8i sites. We consider that the shallow potential at 8i sites generates low-energy phonon modes, which increase the entropy and consequently decrease the free energy at high temperatures. Calculation of the electronic band structure showed that the highest valence band had a larger dispersion from Γ to Z than from Γ to X; this indicated a strong anisotropy in hole conduction.     

Adsorption of the nitrosamine and thionitrosamine molecules as carcinogen compounds on the BN and B3Al N nanotubes: A DFT study

DFT calculations were performed to investigation of the influence of doping three atoms of aluminum on the electronic properties of the (4,0) zigzag boron nitride nanotube (BNNT). Also, adsorption properties of nitrosamine (NA) and thionitrosamine (TNA) molecules as carcinogen agents onto BN and B_Al3N nanotubes were studied. The results show that the B_3AlN nanotube is the most energetically favorable candidates for adsorption of these molecules. Also, B(B_3Al)NNT/TNA complexes are more stable than B(B_3Al)NNT/NA complexes. The HOMO–LUMO gap, electronic chemical potential (μ), hardness (?), softness (S), the maximum amount of electronic charge (ΔN_max) and electrophilicity index (ω) for monomers and complexes in the gas and polar solvent phases were calculated. The results show that the conductivity and reactivity of BNNT increase by doping Al atoms instead of B atoms. Also, the interaction of NA and TNA molecules with BN and B_Al3N nanotubes results in significant changes in the electronic properties of nanotubes. Based on the natural bond orbital (NBO) analysis, in all complexes charge transfer occurs from NA and TNA molecules to nanotubes. Theory of atoms in molecules (AIM) was applied to characterize the nature of interactions in nanotubes. It is predicted that, BN and B_3AlN nanotubes can be used to as sensor for detection of NA and TNA molecules.     

Ultrastable Crystalline Semiconducting Hydrogenated Borophene

Borophene sheets have been synthesized in recent experiments, but the metallic nature and structural instability of the sheets seriously prevent emerging applications. Hydrogenated borophene has been predicted as an ideal material for nanoelectronic applications due to its high stability as well as excellent electronic and mechanical properties. However, the fabrication of hydrogenated borophene is still a great challenge. Here, we demonstrate that hydrogenated borophenes in large quantities can be prepared without any metal substrates by a stepwise in‐situ thermal decomposition of sodium borohydride under hydrogen as the carrier gas. The borophenes with good crystallinity exhibit superior stability in strong acid or base solvents. The structure of the grown borophene is in good agreement with the predicted semiconducting α‐boron sheet. A fabricated borophene‐based memory device shows a high ON/OFF‐current ratio of 3×10³ and a low operating voltage of less than 0.35 V as well as good stability.