Boron Nitride Materials Research Articles

Reduction of carbon dioxide to methane and ethanol on the surface of graphyne-like boron nitride (BNyen) monolayer: A DFT study

Recently, scientists have created a novel type of boron nitride material known as BNyen. This material is similar in structure to Graphyne and has a higher N:B ratio than traditional boron nitride due to the addition of boron and nitrogen connecting segments within its units. This material has been studied for its potential as a photocatalyst for reduction of CO2 using DFT approaches. Optical and electronic attributes of BNyen suggest that it has a wider visible-light range and a band gap of 5.69 eV. By adding boron to BNyen, patial distributions of LUMO and HOMO indicate that π network has been extended, resulting in significantly greater photocatalytic efficiency. Upon the adsorption of CO2 on BNyen monolayer, the band gap significantly decreases, indicating a strong interaction between the BNyen and CO2. DFT computations were employed to explore the mechanism of CO2 reduction to a single carbon product catalyzed by BNyen. Based on the ΔG values, the optimized pathway for this reduction is from CO2 to CH4. Additionally, the potential formation of di-carbon products was considered, and based on the free energy values, CH3CH2OH is identified as the final di-carbon product. The Gibbs free energies for potential CO2 reaction pathways on BNyen were calculated, revealing that CO2 can be reduced to CH4 with a low limiting potential of −0.37 V and to CH3CH2OH with a low limiting potential of −0.57 V, both processes being powered by solar energy. In CO2RR, the competing hydrogen evolution reaction (HER) must be considered. The free energy of HER (ΔG = 0.96 eV) is significantly higher than the ΔG of the rate-determining steps for the mono-carbon product (0.37 eV) and the di-carbon product (0.57 eV) on BNyen. Therefore, BNyen effectively suppresses HER during the CO2RR process. This research can serve as a valuable guide for developing novel types of BNyen as appropriate photocatalysts for CO2 reduction reactions (CO2RR).

Self-rectifying and forming-free resistive switching with Cu/BN/SiO2/Pt bilayer device

Selector-free 3D vertical crossbar with low power consumption is necessary for developing high-density memory devices. Sneaking current in these devices is the prime factor for their degradation as they lose power, and there are glitches in data retrieval. In this article, we have successfully illustrated a forming free and self-rectifying cell in a chemically synthesized 2D memristive device based on hexagonal Boron Nitride (h-BN) material. The device performs well with a Rectification Ratio (RR) > 102 with SiO2/BN bi-layer structure at ±1.3 V. The device performed over 20000 cycles at a pulse width of 10 μs. Also, the device endurance decays with a different pulse width of 100 μs and 1 ms. Schottky barrier formation and development of conductive filament of oxygen vacancies are the primary causes for the proposed device to show Rectifying Resistive Switching (RRS) and Bipolar Resistive Switching (BRS), respectively. The device also performs good stability with the temperature range from Room Temperature (RT) to 250 °C. The sneak path concern and thermal stability enable potential applications for neuromorphic computing and future memory technology.

Comparison of lattice thermal conductivity using ab-initio DFT, machine learning interatomic potentials, and temperature dependent effective potential: a case study of hexagonal BN and BP bilayer

Discovering high thermal conductivity materials is essential for various practical applications, particularly in electronic cooling. The significance of two-dimensional (2D) materials lies in their unique properties that emerge due to their reduced dimensionality, making them highly promising for a wide range of applications. Hexagonal boron nitride (BN), both monolayer and bilayer forms, has garnered attention for its fascinating properties. In this work, we focus on bilayer boron phosphide (BP), which is isostructural to its BN analogue. The lattice thermal conductivity of both bilayer BN and BP have been calculated using ab-initio density functional theory, machine learning with the moment tensor potential method, and the temperature-dependent effective-potential method (TDEP). The TDEP approach gives more accurate results for both BN and BP materials. The lattice thermal conductivity of bilayer BP is lower than that of bilayer BN at room temperature, attributed to increased phonon anharmonicity. This study highlights the importance of understanding phonon scattering mechanisms in determining the thermal conductivity of 2D materials, contributing to the broader understanding and potential applications of these materials in future technologies.

Unleashing the Potential of Boron Nitride Spheres for High‐Performance Thermal Management

AbstractHighly integrated and miniaturized electronic devices require advanced thermal management techniques to improve reliability and performance. Thanks to their high thermal conductivity and electrical insulation, boron nitride nanosheets (BNNSs) are commomly used as fillers to construct thermally conductive polymer composites for heat dissipation. However, the BNNS reinforced composites exhibit anisotropic thermal conductivity due to the anisotropic structure of BNNSs. Micro‐sized boron nitride spheres (BNSs) with isotropic thermal conductivity are considered one of the best solutions. Nevertheless, precisely measuring the thermal conductivity of BNSs remains a challenge, limiting the understanding of the thermal transport mechanism. Herein, we have successfully estimated the thermal conductivity of BNSs using the laser flash method. Factors influencing BNSs’ thermal conductivity, including precursor, polymer binder and sintering temperature, are also investigated. Under optimized conditions, BNSs exhibit high, isotropic thermal conductivity of 37.2±2.5 W/(m ⋅ K), and the BNS pellet outperforms its h‐BN counterpart in heat dissipation for an LED light. This superiority is attributed to outstanding heat transfer performance in the cross‐plane direction, in addition to high in‐plane thermal conductivity. This study provides a feasible method to estimate the thermal conductivity of spherical materials and highlights promising boron nitride materials with isotropic thermal conductivity for heat dissipation in advanced electronics.

The Stability Prediction and Epitaxial Growth of Boron Nitride Nanodots on Different Substrates.

Boron nitride (BN) is a wide-bandgap material for various applications in modern nanotechnologies. In the technology of material science, computational calculations are prerequisites for experimental works, enabling precise property prediction and guidance. First-principles methods such as density functional theory (DFT) are capable of capturing the accurate physical properties of materials. However, they are limited to very small nanoparticle sizes (<2 nm in diameter) due to their computational costs. In this study, we present, for the first time, an important computational approach to DFT calculations for BN materials deposited on different substrates. In particular, we predict the total energy and cohesive energy of a variety of face-centered cubic (FCC) and hexagonal close-packed (HCP) boron nitrides on different substrates (Ni, MoS2, and Al2O3). Hexagonal boron nitride (h-BN) is the most stable phase according to our DFT calculation of cohesive energy. Moreover, an experimental validation equipped with a molecular beam epitaxy system for the epitaxial growth of h-BN nanodots on Ni and MoS2 substrates is proposed to confirm the results of the DFT calculations in this report.

A First-Principle Study of Two-Dimensional Boron Nitride Polymorph with Tunable Magnetism

Using the first-principles calculation, two doping two-dimensional (2D) BN (boron nitride) polymorphs are constructed in this work. The two doping 2D BN polymorphs B5N6Al and B5N6C sheets are thermally stable under 500 K. All the B6N6, B5N6Al, and B5N6C sheets are semiconductor materials with indirect band gaps on the basis of a hybrid functional. The anisotropic calculation results indicate that Young’s modulus (E) and Poisson’s ratio (v) of the B6N6, B5N6Al, and B5N6C sheets are anisotropic in the xy plane. In addition, the magnetic properties of the B6N6, B5N6Al, and B5N6C sheets have also been investigated. According to the calculation of the magnetic properties, B6N6 sheet does not exhibit magnetism, while it shows weak magnetism after doping carbon atom to the BN sheet. This paper explores the influence mechanism of doping different atoms on the basic physical properties of two-dimensional BN sheets. It not only constructs a relationship between structure and performance but also provides theoretical support for the performance regulation of BN materials.

Optimizing the electronic configuration of h-BN for boosting the photocatalytic transformation of acid gases under visible light

The incorporation of heteroatomic carbon optimizes the electronic configuration of boron nitride (BN) to enhance its performance in photocatalytic elimination of acidic gases.

Low-dimensional lateral heterojunctions made of hexagonal boron nitride and carbon materials as efficient electrocatalysts for the chlorine evolution reaction: a study of DFT and machine learning

The reduction of the catalyst's dimension is conducive to facilitating the CER. The increase of Cl− concentration is helpful for accelerating the CER. The oxygen evolution reaction promotes the selectivity of Cl2 generation.

Single Photon Emitters in Hexagonal Boron Nitride Fabricated by Focused Helium Ion Beam

AbstractThe 2D layered hexagonal boron nitride (hBN) material is a promising platform for making single photon emitters (SPEs). Integrate SPEs with photonic cavities or waveguides, requires the deterministic positioning of these emitters as accurately as possible. Among all of the alternative techniques, He+ focused ion beam (FIB) theoretically has sub‐nanometer precision, but its practical positioning accuracy in processing SPEs is limited by the inevitable detrimental byproduct defects. So far, it remains challenging to achieve an accuracy below 100 nm for the positioning of SPEs in hBN. Here, we present a two‐step method for creating SPEs at the predetermined positions in hBN that combines the He+ FIB irradiation and thermal annealing under an oxygen atmosphere. With this method, we have realized the positioning accuracy of less than 50 nm, which, to the best of our knowledge, stands as the highest among the currently available hBN SPEs preparation methods. Moreover, the SPE conversion yield was over 35% and the emission brightness of individual SPE achieved up to 3 × 105 counts/s at room temperature. These SPEs fabricated precisely with nanoscale accuracy in hBN are expected to be good candidates for making large‐scale integrated SPEs in photonic circuits.

Novel thermal conductivity and anti-corrosion coating with hydrophobic properties for heat exchanger applications

Industrial heat exchangers commonly encounter the issue of metal corrosion. Conventional anti-corrosion coatings typically exhibit poor heat conduction, leading to diminished heat exchange efficiency. This study presents a novel coating that combines high thermal conductivity with enduring anti-corrosion performance. The interfacial compatibility between the boron nitride (BN) / silicon carbide (SiC) and fluorosilicone resin (FSR) is effectively enhanced through fluorosilane modification. This improvement, in conjunction with the superior thermal conductivity of the BN/SiC composite filler and the multi-barrier effects of the two-dimensional BN material, results in the composite coating with a high thermal conductivity of 1.65 W/(m·K). After 60 days of immersion in 3.5 wt% NaCl solution, the coating maintains a low-frequency impedance exceeding 1011 Ω·cm2. Good hydrophobicity can promote the long-term anti-corrosion performance of the coating. Thanks to the inherent hydrophobicity of FSR and the reduced surface energy of the filler due to fluorosilane modification, the coating also exhibits hydrophobic characteristics, evidenced by a water contact angle of 109.69°. The development of this novel multifunctional coating holds significant implications for heat exchangers and other applications requiring a balance between thermal conductivity and anti-corrosion performance.

Composites and Materials Prepared from Boron Cluster Anions and Carboranes.

Here, we present composites and materials that can be prepared starting with boron hydride cluster compounds (decaborane, decahydro-closo-decaborate and dodecahydro-closo-dodecaborate anions and carboranes). Recent examples of their utilization as boron protective coatings including using them to synthesize boron carbide, boron nitride, metal borides, metal-containing composites, and neutron shielding materials are discussed. The data are generalized demonstrate the versatile application of materials based on boron cluster anions and carboranes in various fields.

Study on the Experimental Conditions of Adsorption of Lanthanum (III) on Boron Nitride Nanosheets

This paper investigated the adsorption properties of boron nitride materials for La(III), and the possible action mechanism was put forward based on experiments. Then the boron nitride materials were characterized by SEM, TEM, XRD, and FT-IR before and after adsorption. In addition, the effects of pH, the amount of adsorbent, the concentration of La(III) solution, and adsorption time on the adsorption efficiency were also investigated. It is found that under a certain amount of adsorbent when the pH is 7.0 and the concentration of La(III) is 40 mg.L-1, the adsorption ability of La(III) is the best. The maximum adsorption capacity is 201.45 mg.g-1. The adsorption kinetic data are in good agreement with the pseudo-second-order and intra-particle diffusion models. These results show that boron nitride has a good application prospect for removing and recovering La(III) in water and has a certain practical application value.

Transition metal embedded in two‐dimensional bi‐BN as high activity single atom electrocatalyst for oxygen reduction reactions

AbstractSearching for stable, highly effective and cost‐efficient catalysts for the oxygen reduction reaction (ORR) is important to addressing the energy crisis and environmental issues. A single atom embedded in two‐dimensional boron nitride materials is a viable candidate for the ORR to replace Pt‐based catalysts. Herein, by making use of density functional theory (DFT) simulations, we systematically study a novel two‐dimensional boron nitride materials (bi‐BN) embedded by 23 kinds of transition metal (TM) atoms ranging from Ti to Au as high activity single atom electrocatalyst for the ORR. According to the initial screening criteria (−4.92 eV &lt; ΔGO* &lt; 0 eV), 13 kinds of TM‐bi‐BN (TM = Ti, V, Cr, Mn, Fe, Co, Ni, Ru, Rh, Pd, Ag, Pt, Au) meet the criteria and are selected to study their ORR performance in this work. Our calculations indicate that Au‐bi‐BN has the most superior ORR performance with the lowest overpotential (0.43 V), which was lower than that of Pt (0.45 V) as ORR catalyst. The origin of the catalytic activity of the ORR is studied by the linear correlation between these oxygen‐containing intermediates, the volcanic curve, the d‐band center and the crystal orbital Hamilton populations. Ab Initio Molecular Dynamics simulation suggests that Au‐bi‐BN is thermodynamically stable at 300 K. Our results not only offer valuable insights into the utility of boron‐nitride materials as catalysts for ORR, but also facilitate the development of novel catalysts for ORR through improved comprehension of the material properties.

Boron nitride and ZIF-67 composite material to improve the long term corrosion resistance of epoxy resin coating

During the solidification, the solvent in the organic epoxy resin coating evaporates, causing micropores and cracks inside the coating, resulting in poor corrosion resistance. To solve the problem, perfluorooctane trethoxy silane (PFTS) was used to modify the cobalt-based organic framework (ZIF-67) loaded with the corrosion inhibitor 2-mercaptobenzothiazole (MBT) to synthesise PHBN-ZIF@MBT composite nanomaterial. Afterwards, this nanomaterial was mixed with epoxy resin to form PHBN-ZIF@MBT composite coating. The PHBN-ZIF@MBT composite has good barrier properties and corrosion inhibitor-releasing ability. The contact angle of the coating increased from 78.35°to 116.8°after soaking, and the adhesion increased by 82.6 %. The electrochemical impedance spectroscopy showed that the PHBN-ZIF@MBT composite coating still had a high impedance of 1.90×108 Ω cm2 at low frequency after 28 days of immersion. It is proved in this work that the excellent corrosion resistance of the coating is attributed to (1) the barrier property of PHBN-ZIF@MBT composite; (2) the controllable release of MBT disregarding the change of pH; (3) ZIF-67 increasing the cross-linking density through its catalytic activity of curing epoxy resin.

Adsorption properties of boron nitride: A promising material for depollution applications

The interest in boron nitride (BN) materials has progressively increased due to their special properties such as high chemical stability and non-toxicity. The synthesis of the BN-based materials, starting from boric acid, urea (BN-u) and boric acid and melamine (BN-m) was presented. The obtained materials were characterized by BET, IR Spectroscopy, DR UV-Vis analysis, and Scanning Electron Microscopy (SEM). The synthesized BNs have a high surface area (538.0 m2/g for BN-u and 994 m2/g for BN-m) and large pore volume. However, even the material obtained starting from melamine presents a large pore volume, the pore size is higher from BN obtained from urea making it suitable for dye adsorption from wastewater. For this purpose, its performances in adsorption of Brilliant Blue FCF dye, as a model for dye molecules, were studied. The maximum adsorbed quantity of 24.8 mg/g was calculated based on Sips isotherm. The materials were also tested for CO2 adsorption, with promising results.

Boron Nitride-Based Nanomaterials: Synthesis and Application in Rechargeable Batteries

Conventional boron nitride material is a resistant refractory compound of boron and nitrogen with various crystalline forms. The hexagonal form, which corresponds to graphite, is used as a lubricant and an additive to cosmetic products because of its higher stability and softness. Recently, various nanostructured boron nitride materials, including nanosheets, nanotubes, nanoparticles, and nanocomposites with diverse new properties, have been achieved through the development of advanced synthesis techniques as well as a deeper understanding of the properties and related applications. As nanostructured boron nitride materials exhibit high chemical, thermal and mechanical stability, the incorporation of nanostructured boron nitride materials into the key components (electrolytes, separators, and electrodes) of electrochemical systems can alleviate various inherent problems. This review article systematically summarizes the integration of nanostructured boron nitride into electrolytes, separators, and electrodes of lithium-ion, sodium-ion, and lithium-sulfur batteries. Various structures, synthesis methods, properties, and electrochemical performance of nanostructured boron nitride incorporated electrolytes, separators, and electrodes in rechargeable batteries are discussed. The challenges and possibilities for future application of boron nitride-based nanomaterials in electrochemical energy storage systems are also highlighted.

Improving the composition and multifunctional properties of amorphous boron nitride films prepared by post-annealing assisted femtosecond pulsed laser deposition method

Amorphous boron nitride (aBN) materials have similar density to crystalline phases and retain many unique electronic properties, valuable chemical inertness and high thermal stability characteristics. However, the current research on aBN materials has mainly focused on the synthesis and electrical properties of ultrathin aBN films. In this study, we developed a post-annealing assisted femtosecond laser deposition route towards stoichiometric, continuous, and multifunctional aBN films with thickness values of ∼1 μm. A series of boron nitride films were deposited on silicon wafers using a 1030 nm, 300 fs laser with a pulse energy of ∼1 mJ and a high repetition rate of 2 kHz to ablate a hexagonal boron nitride target. The deposited films were then annealed at 900 °C in a nitrogen atmosphere. The structures and chemical compositions of these obtained films were analysed by X-ray diffraction and X-ray photoelectron spectroscopy. Fourier transform infrared and nano-scratch tests were performed to measure the infrared optical and frictional properties of the adhered films. An infrared thermal imager was used to investigate the heat-dissipation performance of these films. The results indicate the components of the aBN film are further purified, the number of large heterogeneous particles is effectively reduced, and the surface becomes smooth after post-annealing treatment. This improvement promotes the transfer of heat flux and increases the transmittance in the mid-infrared light band. The significant effect mechanisms of the post-annealing treatment on the enhancement of the composition and multifunctional properties of aBN films prepared by the femtosecond pulsed laser were provided. The uniform coverage of the aBN films on the substrates, as well as the mid-infrared optical transparency and the protective performance are highly valuable and practical for infrared window protection applications.

Investigation of Adsorption of Nd(III) on Boron Nitride Nanosheets in Water

In this paper, boron nitride materials were prepared by a two-step synthesis method, and this material’s adsorption property for neodymium ions was explored. The experimental results show that the adsorption capacity of boron nitride is closely related to pH. When the pH is 6.0, the adsorption performance of the material is the best; the kinetic data show that the adsorption equilibrium can be reached in about 150 min, and the adsorption capacity at equilibrium is 207.3 mg.g-1. In addition, the Freundlich and Langmuir models were used to fitting the thermodynamic results. It was found that the adsorption process of boron nitride on Nd(III) involved both monolayer adsorption and multi-layer adsorption. These data indicate that boron nitride has a good adsorption effect on Nd(III) in water and is a promising material for environmental remediation.

Boron nitride nanolayers in optical spectroscopic materials

Subject of study. This paper discusses nanostructures such as protective windows, plane-parallel sheets, and model plane-parallel sheets used in the development of modern fixed and mobile optical emission spectrometers and composition analyzers for rapid elemental analysis and determination of metal grades. These instruments are capable of determining the elemental compositions of pure metals and multi-component alloys within a few seconds. This paper also discusses a model depositional nanostructure: boron nitride nanotubes deposited in a single layer on an MgF2 optical-crystal substrate being used as a prototype spark-protective window in an optical emission spectrometer. Aim of study. We aim to determine whether a boron nitride nanotube nanostructure deposited on the high-wear parts of protective windows in an optical emission spectrometer can be used to stabilize instrument operations in the ultraviolet spectral region. Methods. This paper uses a density functional theory with atomic basis sets (Hartree-Fock HF/STO-3G SP). Main results. In this paper, we discuss the use of boron nitride nanotubes deposited in a single layer as a special protective coating for spectrometers. Note that deposition of boron nitride nanolayers on spectrometer components such as protective windows has practical benefits in spectroscopy because the boron nitride material used in the fabrication of washers to hold wires and rods in analyzer instruments is resistant to high temperatures. Practical significance. The solutions proposed herein are specifically relevant to optical emission spectrometers used in metal analysis and can be used to generate requirements for upgrades to improve the service life and measurement stability and provide wear-resistant protective windows for such instruments.

Pyrolyzed synthesis of boron nitride for photocatalytic degradation of indigo carmine studies

A non-metal type photocatalytic layered boron nitride (BN) material was synthesized by precursor conversion hydrothermal process followed by adequate temperature pyrolysis. The characterization of BN was performed through various analytical instrumental techniques. The results show that a hexagonal crystal structure BN with a strong BN bond was formed. The photocatalytic decolorization of indigo carmine (IC) dye was examined using synthesized BN with influencing factors like time, pH, catalyst, and dye concentration under ultra-violet light (UV) illumination. The decolorization efficiency was found to be 88%. The optimization of operating parameters was investigated and also found a model equation of decolorization efficiency through response surface methodology (RSM) based box - behnken design (BBD). The photocatalytic decolorization mechanism was suggested based on the experiments performed.