Search Results (15)

Ammonia borane is a promising hydrogen storage material due to its high hydrogen content, but its use as hydrogen carrier under thermal stimuli involves the production of several byproducts, such as borazine, reducing hydrogen purity and the overall efficiency. This work is focused on the use of high-boiling-point amines to modulate ammonia borane decomposition, aiming to enhance hydrogen release and suppress volatile N_xB_y species. Kissinger’s equation kinetics revealed that amines significantly influence the decomposition mechanism, and TGA-IR investigation showed a maximum of 2.4 wt.% of pure hydrogen release in the presence of triphenyl amine. Furthermore, the experimental data herein discussed, together with a computational study of activation energies, allowed us to derive a detailed mechanism that leads to a foundation for further advancement in the exploitation of ammonia borane as a hydrogen carrier, suggesting that the formation of linear species is anchored to amine over the release of borazine and production of poly borazine-like species. Full article

Ammonia borane (AB), with a theoretical hydrogen content of 19.6 wt%, is constrained by its low crystalline density (0.758 g/cm³) and poor thermal stability (decomposing at 100 °C). In this study, AB/ammonium perchlorate (AP) composites were synthesized via freeze-drying at a 1:1 molar ratio. The integration of AP introduced intermolecular interactions that suppressed AB decomposition, increasing the onset temperature by 80 °C. Subsequent vacuum calcination at 100 °C for 2 h formed oxygen/fuel-integrated ammonium perchlorate borane (APB), which achieved decomposition temperatures exceeding 350 °C. The proposed mechanism involved AB decomposing into borazine and BN polymers at 100 °C, which then NH₃BH₂⁺/ClO₄⁻ combined to form APB. At 350 °C, APB underwent the following redox reactions: 4NH₃BH₂ClO₄ → N₂↑ + 4HCl↑ + 2B₂O₃ + N₂O↑ + O₂↑ + 7H₂O↑ + H₂↑, while residual AP decomposed. The composite exhibited improved density (1.66 g/cm³) and generated H₂, N₂, O_2, and HCl, demonstrating potential for hydrogen storage. Additionally, safety was enhanced by the suppression of AB’s exothermic decomposition (100–200 °C). APB, with its high energy density and thermal stability, was identified as a promising high-energy additive for high-burning-rate propellants. Full article

Imidazo-fused diazaborines, which serve as intermediary structures somewhat alongside benzene and borazine, had been of particular interest to Dewar and Snyder more than 60 years ago. To this end, Dewar utilised his ‘$\pi$-complex theory’so as to represent ‘borazaros’as a ‘quadrivalent’ species; however, sadly, modern representations have deviated and leapt into ‘trivalent’ counterparts. Bonding in boron species has never been straightforward, to such an extent that the orthodox ‘ethane’ like diborane, i.e., H₃B–BH₃, which conformed to the paradigmatic rules of molecular structure, in particular, hybridisation and electronegativity, was later evolved to a more realistic ‘3-centre 2-electron’ bonding so as to give the lie to the purported diborane structures of X-ray diffractors. Herein ¹¹B NMR together with IR spectroscopy sheds light on the nature of bonding in borazaros, and ‘caged’ cyclic oxazaborons so as to reinforce, and reinvigorate the old literature, which could be of interest to both the synthetic, and medicinal chemist alike. Full article

The current study investigates the influence of several R substituents (e.g., Me, SiH₃, F, Cl, Br, OH, NH₂, etc.) on the aromaticity of borazine, also known as the “inorganic benzene”. By performing hybrid DFT methods, blended with several computational techniques, e.g., Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM), Gauge-Including Magnetically Induced Current (GIMIC), Nucleus-Independent Chemical Shift (NICS), and following a simultaneous evaluation of four different aromaticity indices (para-delocalization index (PDI), multi-centre bond order (MCBO), ring current strength (RCS), and NICS parameters), it is emphasized that the aromatic character of B-substituted (B₃R₃N₃H₃) and N-substituted (B₃H₃N₃R₃) borazine derivatives can be tailored by modulating the electronic effects of R groups. It is also highlighted that the position of R substituents on the ring structure is crucial in tuning the aromaticity. Systematic comparisons of calculated aromaticity index values (i.e., via regression analyses and correlation matrices) ensure that the reported trends in aromaticity variation are accurately described, while the influence of different R groups on electron delocalization and related aromaticity phenomena is quantitatively assessed based on NBO analyses. The most relevant interactions impacting the aromatic character of investigated systems are (i) the electron conjugations occurring between the p lone pair electrons (LP) on the F, Cl, Br, O or N atoms, of R groups, and the π*(B=N) orbitals on the borazine ring (i.e., LP(R)→π*(B=N) donations), and (ii) the steric-exchange (Pauli) interactions between the same LP and the π(B=N) bonds (i.e., LP(R)↔π(B=N) repulsions), while inductive/field effects influence the aromaticity of the investigated trisubstituted borazine systems to a much lesser extent. This work highlights that although the aromatic character of borazine can be enhanced by grafting electron-donor substituents (F, OH, NH₂, O⁻, NH⁻) on the N atoms, the stabilization due to aromaticity has only a moderate impact on these systems. By replacing the H substituents on the B atoms with similar R groups, the aromatic character of borazine is decreased due to strong exocyclic LP(R)→π*(B=N) donations affecting the delocalization of π-electrons on the borazine ring. Full article

Boron-doped organic compounds display unique properties as a result of the presence of an empty p orbital on boron and the ability to switch between a trigonal planar and a tetrahedral geometry. In recent years, they have found several applications not only as synthetic reagents, e.g., in the Suzuki–Miyaura reaction, but also as pharmaceuticals and as specialized materials due to their optical and electronic properties. Some boron compounds may exist as atropisomers, and these rotamers may have different properties according to their sense of rotation. Synthetic strategies to separate them and, more recently, to obtain them in an asymmetric manner are becoming popular. In this review, we survey the literature on this emerging field of research. Full article

The ability of 2D hybrid structures formed by boron, nitrogen and carbon atoms (h-BNCs) to act as potential substrates for the surface-enhanced Raman spectroscopy (SERS) detection of dioxin-like pollutants is theoretically analyzed. The strong confinement and high tunability of the electromagnetic response of the carbon nanostructures embedded within the h-BNC sheets point out that these hybrid structures could be promising for applications in optical spectroscopies, such as SERS. In this work, two model dioxin-like pollutants, TCDD and TCDF, and a model h-BNC surface composed of a carbon nanodisk of ninety-six atoms surrounded by a string of borazine rings, BNC96, are used to simulate the adsorption complexes and the static and pre-resonance Raman spectra of the adsorbed molecules. A high affinity of BNC96 for these pollutants is reflected by the large interaction energies obtained for the most stable stacking complexes, with dispersion being the most important contribution to their stability. The strong vibrational coupling of some active modes of TCDF and, specially, of TCDD causes the static Raman spectra to show a ”pure” chemical enhancement of one order of magnitude. On the other hand, due to the strong electromagnetic response of BNC96, confined within the carbon nanodisk, the pre-resonance Raman spectra obtained for TCDD and TCDF display large enhancement factors of 10⁸ and 10⁷, respectively. Promisingly, laser excitation wavelengths commonly used in SERS experiments also induce significant Raman enhancements of around 10⁴ for the TCDD and TCDF signals. Both the strong confinement of the electromagnetic response within the carbon domains and the high modulation of the resonance wavelengths in the visible and/or UV region in h-BNCs should lead to a higher sensitivity than that of graphene and white graphene parent structures, thus overcoming one of the main disadvantages of using 2D substrates for SERS applications. Full article

The growth of hexagonal boron nitride (hBN) on epitaxial Ge(001)/Si substrates via high-vacuum chemical vapor deposition from borazine is investigated for the first time in a systematic manner. The influences of the process pressure and growth temperature in the range of 10⁻⁷–10⁻³ mbar and 900–980 °C, respectively, are evaluated with respect to morphology, growth rate, and crystalline quality of the hBN films. At 900 °C, nanocrystalline hBN films with a lateral crystallite size of ~2–3 nm are obtained and confirmed by high-resolution transmission electron microscopy images. X-ray photoelectron spectroscopy confirms an atomic N:B ratio of 1 ± 0.1. A three-dimensional growth mode is observed by atomic force microscopy. Increasing the process pressure in the reactor mainly affects the growth rate, with only slight effects on crystalline quality and none on the principle growth mode. Growth of hBN at 980 °C increases the average crystallite size and leads to the formation of 3–10 well-oriented, vertically stacked layers of hBN on the Ge surface. Exploratory ab initio density functional theory simulations indicate that hBN edges are saturated by hydrogen, and it is proposed that partial de-saturation by H radicals produced on hot parts of the set-up is responsible for the growth. Full article

Boron nitride (BN) ceramic fibers containing amounts of silicon nitride (Si₃N₄) were prepared using hybrid precursors of poly(tri(methylamino)borazine) (PBN) and polycarbosilane (PCS) via melt-spinning, curing, decarburization under NH₃ to 1000 °C and pyrolysis up to 1600 °C under N₂. The effect of Si₃N₄ contents on the microstructure of the BN/Si₃N₄ composite ceramics was investigated. Series of the BN/Si₃N₄ composite fibers containing various amounts of Si₃N₄ from 5 wt% to 25 wt% were fabricated. It was found that the crystallization of Si₃N₄ could be totally restrained when its content was below 25 wt% in the BN/Si₃N₄ composite ceramics at 1600 °C, and the amorphous BN/Si₃N₄ composite ceramic could be obtained with a certain ratio. The mean tensile strength and Young’s modulus of the composite fibers correlated positively with the Si₃N₄ mass content, while an obvious BN (shell)/Si₃N₄ (core) was formed only when the Si₃N₄ content reached 25 wt%. Full article

We present the research findings of the DOE-funded Hydrogen Storage Engineering Center of Excellence (HSECoE) related to liquid-phase and slurry-phase chemical hydrogen storage media and their potential as future hydrogen storage media for automotive applications. Chemical hydrogen storage media other than neat liquid compositions will prove difficult to meet the DOE system level targets. Solid- and slurry-phase chemical hydrogen storage media requiring off-board regeneration are impractical and highly unlikely to be implemented for automotive applications because of the formidable task of developing solid- or slurry-phase transport systems that are commercially reliable and economical throughout the entire life cycle of the fuel. Additionally, the regeneration cost and efficiency of chemical hydrogen storage media is currently the single most prohibitive barrier to implementing chemical hydrogen storage media. Ideally, neat liquid-phase chemical hydrogen storage media with net-usable gravimetric hydrogen capacities of greater than 7.8 wt% are projected to meet the 2017 DOE system level gravimetric and volumetric targets. The research presented herein is a collection of research findings that do not in and of themselves warrant a dedicated manuscript. However, the collection of results do, in fact, highlight the engineering challenges and short-comings in scaling up and demonstrating fluid-phase ammonia borane and alane compositions that all future materials researchers working in hydrogen storage should be aware of. Full article

We found that oxidized Cu nanoparticles can catalyze the growth of boron nitride nanotubes from borazine via plasma-assisted chemical vapor deposition. The Raman spectra suggest that the formation of thin-walled nanotubes show a radial breathing mode vibration. The presence of oxygen in the plasma environment was necessary for the growth of the nanotubes, and a part of the nanotubes had a core shell structure with a cupper species inside it. In atomic resolution transmission electron microscope (TEM) images, Cu₂O was found at the interface between the Cu-core and turbostratic BN-shell. The growth mechanism seemed different from that of carbon nanotube core-shell structures. Therefore, we pointed out the important role of the dynamic morphological change in the Cu₂O-Cu system. Full article

Hexagonal boron nitrite (hBN) is an attractive material for many applications such as in electronics as a complement to graphene, in anti-oxidation coatings, light emitters, etc. However, the synthesis of high-quality hBN at cost-effective conditions is still a great challenge. Thus, this work reports on the synthesis of large-area and crystalline hBN nanosheets via the modified polymer derived ceramics (PDCs) process. The addition of both the BaF₂ and Li₃N, as melting-point reduction and crystallization agents, respectively, led to the production of hBN powders with excellent physicochemical properties at relatively low temperatures and atmospheric pressure conditions. For instance, XRD, Raman, and XPS data revealed improved crystallinity and quality at a decreased formation temperature of 1200 °C upon the addition of 5 wt% of BaF₂. Moreover, morphological determination illustrated the formation of multi-layered nanocrystalline and well-defined shaped hBN powders with crystal sizes of 2.74–8.41 ± 0.71 µm in diameter. Despite the compromised thermal stability, as shown by the ease of oxidation at high temperatures, this work paves way for the production of large-scale and high-quality hBN crystals at a relatively low temperature and atmospheric pressure conditions. Full article

Composite ceramic fibers comprising about 80 wt% boron nitride (h-BN) and 20 wt% Si₃N₄ were fabricated through melt-spinning, electron-beam curing, and pyrolysis up to 1600 °C in atmospheres of NH₃ and N₂, using a mixture of poly[tri(methylamino)borazine] (PBN) and polysilazane (PSZ). By analyzing the microstructure and composition of the pyrolyzed ceramic fibers, we found the formation of binary phases including crystalline h-BN and amorphous Si₃N₄. Further investigations confirmed that this heterogeneous microstructure can only be formed when the introduced ratio of Si₃N₄ is below 30% in mass. The mean modulus and tensile strength of the fabricated composite fibers were about 90 GPa and 1040 MPa, twice the average of the pure h-BN fiber. The dielectric constant and dielectric loss tangent of the composite fibers is 3.06 and 2.94 × 10⁻³. Full article

A preceramic polymer of B,B′,B′′-(dimethyl)ethyl-acrylate-silyloxyethyl-borazine was synthesized by three steps from a molecular single-source precursor and characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectrometry. Six-member borazine rings and acrylate groups were effectively introduced into the preceramic polymer to activate UV photo-induced polymerization. Photo-Differential Scanning Calorimetry (Photo-DSC) and real-time FTIR techniques were adapted to investigate the photo-polymerization process. The results revealed that the borazine derivative exhibited dramatic activity by UV polymerization, the double-bond conversion of which reached a maximum in 40 s. Furthermore, the properties of the pyrogenetic products were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which proved the ceramic annealed at 1100 °C retained the amorphous phase. Full article

Boron nitride (BN) is a III-V compound which is the focus of important research since its discovery in the early 19th century. BN is electronic to carbon and thus, in the same way that carbon exists as graphite, BN exists in the hexagonal phase. The latter offers an unusual combination of properties that cannot be found in any other ceramics. However, these properties closely depend on the synthesis processes. This review states the recent developments in the preparation of BN through the chemistry, shaping and ceramic conversion of borazine derivatives. This concept denoted as Polymer-Derived Ceramics (PDCs) route allows tailoring the chemistry of precursors to elaborate complex BN shapes which cannot be obtained by conventional process. The effect of the chemistry of the molecular precursors, i.e., borazine and trichloroborazine, and their polymeric derivatives i.e., polyborazylene and poly[tri(methylamino)borazine], in which the specific functional groups and structural motifs determine the shaping potential by conventional liquid-phase process and plastic-forming techniques is discussed. Nanotubes, nano-fibers, coatings, monoliths and fiber-reinforced matrix composites are especially described. This leads to materials which are of significant engineering interest. Full article

The spray-pyrolysis of borazine at 1400 °C under nitrogen generates boron nitride (BN) nanoparticles (NPs). The as-prepared samples form elementary blocks containing slightly agglomerated NPs with sizes ranging from 55 to 120 nm, a Brunauer-Emmett-Teller (BET)-specific surface area of 34.6 m² g⁻¹ and a helium density of 1.95 g cm⁻³. They are relatively stable in air below 850 °C in which only oxidation of the NP surface proceeds, whereas under nitrogen, their lower size affects their high temperature thermal behavior in the temperature range of 1450–2000 °C. Nitrogen heat-treated nanostructures have been carefully analyzed using X-ray diffraction, electron microscopy and energy-dispersive X-ray spectroscopy. The high temperature treatment (2000 °C) gives hollow-cored BN-NPs that are strongly facetted, and after ball-milling, hollow core-mesoporous shell NPs displaying a BET-specific surface area of 200.5 m²·g⁻¹ and a total pore volume of 0.287 cm³·g⁻¹ were produced. They have been used as host material to confine, then destabilize ammonia borane (AB), thus improving its dehydrogenation properties. The as-formed AB@BN nanocomposites liberated H₂ at 40 °C, and H₂ is pure in the temperature range 40–80 °C, leading to a safe and practical hydrogen storage composite material. Full article