Green and efficient production of boron nitride nanosheets via oxygen doping-facilitated liquid exfoliation

As the structural analogue of graphene, boron nitride nanosheets (BNNSs) are anticipated to have a wide range of potential applications. BNNSs exhibit good mechanical properties, outstanding thermal conductivity, oxidation and chemical stability and are excellent electrical insulators. While BNNSs have gained recognition as one of the most versatile 2D materials in recent years, their application in research and industry is still hampered by the lack of methods to produce BNNSs in large quantity and a cost-effective way. In this study, we report highly efficient h-BN exfoliation via the oxygen doping-facilitated liquid exfoliation. Oxygen atoms are introduced into the hexagonal boron nitride (h-BN) structure via a facile thermal treatment. The relationship of thermal treatment, structural changes and h-BN exfoliation are studied to elucidate the key factor for advancing the BNNS production. The optimum concentration of hydroxyl groups and weakening of interlayer interactions have synergistically facilitated the delamination of h-BN in water under mild exfoliation conditions, resulting in up to 1255% yield increment and without noticeable new defects in the BNNS structure as compared with the untreated control. An efficient and environmentally friendly exfoliation process of h-BN is a crucial starting point towards the cost-effective and mass production of BNNSs which is needed for the currently identified and myriad future applications of BNNSs.     

Sustainable preparation of graphene-analogue boron nitride by ball-milling for adsorption of organic pollutants

The method of fabricating low-cost adsorbents with high activity and durability via a convenient and eco-friendly procedure is of great importance to wastewater treatment. Herein, a high-efficient mechanical exfoliation strategy was proposed to facilely prepare few-layered graphene-analogue boron nitride (BN) via a one-step non-organic solvent assisted wet ball mill procedure. Ball-milling treatment increased the specific surface area of BN 3.5-fold by reducing the thickness to ~3 layers with 45 min. The exfoliated BN exhibited strikingly improved sorption performance to organic contaminants with around 124% and 116% increased removal efficiency respectively for oxytetracycline (OTC) and Rhodamine B (RhB) as compared to the bulk BN. Batches sorption experiments showed that the sorption processes were thermodynamic endothermic, and well fitted to pseudo-second-order kinetic model and Freundlich isotherm equation. The π-π stacking interaction, hydrophobic effect and electrostatic interaction were proposed as the dominated sorption mechanism. In addition, no significant decline in adsorptive removal ability for the sorbent after 5 times recycling. The results indicate that the ball-milling exfoliation is a fast, green, sustainable and promising strategy for synthesis of highly potent BN based two-dimensional layered adsorbents.     

Mechanical and dielectric properties of functionalized boron nitride nanosheets/silicon nitride composites

Uniformly dispersed boron nitride nanosheets (BNNSs) reinforced silicon nitride (Si₃N₄) composites were prepared by surface modification assisted flocculation combined with SPS sintering. In order to improve the dispersibility of the BNNSs in the composites, the liquid phase stripped BNNSs are surface functionalized by a two-step covalently modification. The amino-modified BNNSs (NH₂-BNNSs) and Si₃N₄ powders have opposite surface potential, mixed evenly by electrostatic interaction during flocculation. The results showed that mechanical properties of Si₃N₄ composites were obviously enhanced by adding NH₂-BNNSs. The fracture toughness and bending strength of Si₃N₄ composites added 0.75 wt% NH₂-BNNSs were increased by 34% and 28%, respectively, compared with monolithic Si₃N₄. Toughening mechanisms are synergistic action of the torn, pull-out or bridging of BNNSs and crack deflection mechanisms with microstructural analyzes. The dielectric properties of the Si₃N₄ ceramics are also improved after the addition of NH₂-BNNSs.     

Tuning and thermal exfoliation graphene-like carbon nitride nanosheets for superior photocatalytic activity

In this work, ultrathin graphene-like carbon nitride nanosheets with rich nanoporous and excellent hydrophilic characteristics were synthesized by a simple and effective thermal exfoliation of bulk g-C₃N₄. In order to fully understand the effect of thermal exfoliation conditions on the texture, surface state, and photocatalytic activity of the resulting g-C₃N₄, a series of exfoliated g-C₃N₄ were prepared by adjusting the thermal exfoliation temperature and time. The detailed characterization and analysis distinctly suggested that increasing exfoliation temperature led to a large number of nitrogen vacancies and increased specific surface area, further prolonging exfoliation time, the thermal exfoliation degree was enhanced, more carbon vacancies and enlarged pore volume formed in the resulting products. Further, the exfoliation degree and photocatalytic ability of the resultant products were enhanced by increasing thermal exfoliation temperature and time. The optimized ultrathin graphene-like carbon nitride nanosheets exhibited a 89.6% degradation efficiency for Rh6G only in 10 min, which was much faster than other such nanosheets reported in previous literature.     

Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets

The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.     

Surface-diffusion mechanism for synthesis of substrate-free and catalyst-free boron nitride nanosheets

This study presents an innovative surface-diffusion mechanism for the growth of substrate-free and catalyst-free boron nitride nanosheets (BNNSs) by annealing an ammonium borate hydroxide hydrate precursor in a NH₃ chemical vapor deposition system. At elevated temperatures, part of NH₄B₅O₈ slowly decomposes and forms B₂O₃, and flowing NH₃ gradually diffuses to the B₂O₃ surface to form vertically aligned BNNSs. The lateral dimension and crystallinity of the BNNSs increase, while their thickness decreases with the continuous surface-diffusion reaction. The residual NH₄B₅O₈ and B₂O₃ absorbs moisture in the air to constitute NH₄B₅O₈·4H₂O and H₃BO₃ substrates. With increasing annealing temperature and soaking time (at 1400 °C for 7 h), all NH₄B₅O₈ decomposes and the surface-diffusion reaction between B₂O₃ and NH₃ completely occurs, forming substrate-free BNNSs with a lateral dimension of 1 μm and a thickness of 10 nm. This reliable approach for synthesizing BNNSs paves the way for future applications in advanced ceramic composites.     

Evaluation of antibacterial and catalytic potential of copper-doped chemically exfoliated boron nitride nanosheets

Boron nitride (BN) nanosheets were prepared by chemical exfoliation method and incorporation of Cu as a dopant was achieved using hydrothermal route. Hexagonal phase of BN (h-BN) was detected using x-ray difractometer (XRD). Functional group analysis with fourier transform infrared spectroscope (FTIR) was employed to identify the chemicals used in the process, which was then further confirmed with energy dispersive x-ray spectroscopy (EDS) coupled with FESEM. Optical analysis undertaken with UV–vis. spectroscopy indicated absorption at UV region. Raman spectroscopy was used to acquire molecular fingerprints of BN molecules. Photoluminescence (PL) spectroscopy was carried out to study the exciton behaviour of samples in order to elucidate the electron migration and transfer rate. Field emission scanning electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM) were employed to examine the morphology and structure of materials. The experimental results indicate that Cu-doped BN nanosheets possess excellent catalytic potential and superior antibacterial activity.     

Characterization of boron nitride nanosheets synthesized by boron-ammonia reaction

Boron nitride nanosheets (BNNS) with thickness 5–11 nm were successfully produced when pure boron powder (1–2 μm) interacted with ammonia gas in chemical vapour deposition set up. Under the optimized parameters, at 1200 °C and for uninterrupted 1 h of reaction duration, 2D BNNS with thickness of ca.11 nm were synthesized. BNNS were characterized by X-ray diffraction (XRD) for crystal structure, scanning electron microscopy for dimensions and morphology, energy dispersive X-ray analysis for chemical composition and Fourier transform infrared spectroscopy for sp² BN bond detection. The thickness of BNNS determined from both XRD data (using Scherrer equation) and atomic force microscopic analysis confirmed the stated product thickness. The BNNS obtained at 1200 °C had high crystallinity, purity and yield.     

Enhancing mechanical properties of fused silica composites by introducing well-dispersed boron nitride nanosheets

Well-dispersed boron nitride nanosheets (BNNSs) reinforced fused silica composites were successfully fabricated by surface modification assisted flocculation method. Surface modification can enhance the performance of flocculation process. BNNSs were homogeneously mixed with fused silica through the electrostatic interaction between hydroxylated BNNSs with negative charge and amino-modified fused silica with positive charge. The BNNSs can act as excellent nanofillers for enhancing the mechanical properties of fused silica composites. Approximately 74% and 48% increases in flexure strength and fracture toughness can be achieved for the 1.5 wt% BNNSs/fused silica composite, respectively. The toughening mechanisms were analyzed by microstructural characterization, especially for pull-out mechanism.     

Scalable production of boron nitride nanosheets in ionic liquids by shear-assisted thermal treatment

Due to their intriguing properties, boron nitride nanosheets (BNNSs) with large lateral size and high crystallinity have great promise for many applications. However, the quantitative exfoliation of hexagonal boron nitride (h-BN) into good quality BNNSs still remains a key challenge. Herein, we report a scalable method to exfoliate BNNSs in ionic liquids (ILs) via shear-assisted thermal treatment. Few-layer BNNSs with well-preserved structural integrity are successfully prepared by this method. The synergistic effects of strong physical adsorption and intercalation of IL molecules, chemical interactions between hydrogen fluoride (HF) and h-BN, activation energy provided by heat treatment, and shear forces generated by repetitive stirring effect contribute to the exfoliation of BNNSs.     

Few-layer boron nitride nanosheets: Preparation,characterization and application in epoxy resin

Large-scale exfoliated boron nitride nanosheets were achieved via a liquid exfoliation sonication method by using sodium fluoride and ammonium hydroxide as Lewis base compounds. The crystal structure, surface functional groups, morphology and thickness of the as-prepared samples were characterized by X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and atomic force microscopy, respectively. The as-prepared samples were introduced into epoxy resin to fabricate the polymer-based composites. Experimental results showed that the layer thickness of the as-prepared nanosheets was in the range of 1 to 3 layers. Moreover, it could improve the tensile properties of the matrix. When the loading of the as-prepared nanoparticles was 0.4 wt%, the tensile strength and elongation at break of the composites reached to their maximum values 65.6 MPa and 25.9%, which were increased by 118% and 192% more than that of pure resin. In addition, the as-prepared boron nitride samples could improve the thermostability and promote the curing of the matrix.     

Construction of CaTiO3 nanosheets with boron nitride quantum dots as effective photogenerated hole extractor for boosting photocatalytic performance under simulated sunlight

Herein, titanate-based perovskite CaTiO₃ nanosheets were successfully designed via boron nitride quantum dots (BNQDs) to fabricate CaTiO₃/BNQDs catalyst. The as-fabricated composite catalysts were analysed by transmission electron microscope (TEM), scanning electron microscopy coupled with energy dispersive spectrometry (SEM-EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), X-ray diffraction (XRD), UV–vis spectroscopy (UV-DRS), photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) techniques. SEM-Mapping analysis showed that the boron and nitrogen elements dispersed well over the CaTiO₃ surface which was useful for building electronic channels for rapid transport of photo-induced charge pairs. TEM images verified the attachment of BNQDs around the surface of host CaTiO₃ forming intimate interface while the distribution of chemical states was observed by XPS analysis demonstrating strong coupling effect between BNQDs and CaTiO₃ through Ti–O–N and Ti–O–B bonds. Moreover, PL and light absorption properties enhanced with the quantum confinement effect of BNQDs. As expected, the photocatalytic degradation rate of CaTiO₃/BNQDs was increased to k_app = 0.015 min^{? 1} with optimum BNQDs loading, which was 2.31 times folder than that of bare CaTiO₃ (0.006 min^{? 1}). The enhanced photocatalytic efficiency was observed for CaTiO₃/BNQDs than pristine perovskite on account of formation of electron tapping sites, decreased band gap energy and hindered recombination rate. On the other hand, in the presence of H₂O₂, the degradation percentage increased from 88.5% to 92.1% at the end of 120 min of irradiation while 96.8% of TC was quickly degraded within 60 min after activating with peroxymonosulfate which created strong sulphate radicals. Radical trapping tests indicated that the photo-generated holes were the primary active species in the photocatalytic mechanism. Moreover, CaTiO₃/BNQDs catalyst showed excellent stability in recycling tests. Besides, the possible degradation mechanism was proposed. This study shed light on the significance of BNQDs in the enhancement of the photocatalytic activities of titanate-based perovskite for effective degradation of tetracycline antibiotic in contaminated water.     

Large scale fabrication of porous boron nitride microrods with tunable pore size for superior copper (II) ion adsorption

Herein, large scale fabrication of porous boron nitride (BN) microrods has been achieved via a facile process, which involves the synthesis of melamine diborate precursors and subsequent thermal treatment process. The fabrication can be scaled up to ultra-large scale which is limited by the furnace. The characterization results show that the as-obtained products are porous BN microrods with diameters in the range of ten to tens of micrometers and length of a few millimeters, respectively. The specific surface area and porosity of these porous BN microrods are tunable by adjusting the synthesis processes of precursors. A highest specific surface area of 653.66?m²/g is obtained for the sample of BN-4, corresponding to the differential pore volume of 0.289?cm³/(g?nm) and pore size of about 1.928?nm. Further measurement shows that the as-obtained porous BN microrods possess excellent copper ion adsorption property with a highest adsorption capacity of 365.4?mg/g. This adsorption capacity is superior to those of most copper ion adsorbents reported in recent literature. The high copper ion adsorption capacity combining with the unique properties of hexagonal BN makes them promising candidates for copper ions adsorption in practical wastewater treatment.     

Hexagonal boron nitride nanosheets exfoliated by sodium hypochlorite ball mill and their potential application in catalysis

The unique physicochemical properties of two-dimensional (2D) h-BN and its promising applications in future optoelectronics have motivated an extensive study of its properties. However, a major limiting factor is its high quality and scalable preparation of few-layer h-BN. Herein, a facile, low cost, and high yield process is developed by using a sodium hypochlorite aqueous solution-assisted ball milling exfoliation process. The facile process results in scalable production of few-layer (2–4 sheets) h-BN from commercial BN powders, with little damage of its in-plane structure and high yield amounting to 21%. Furthermore, few-layer h-BN has been demonstrated to be good carrier to support and disperse Ag nanoparticles with high catalytic activity for the reduction of p-nitrophenol to p-aminophenol with NaBH₄. The pseudo-first-order reaction rate constant of the pre-prepared catalyst was calculated to be 7.13×10⁻³ s⁻¹, larger than that of pristine BN supported Ag nanoparticles. The results indicate that stable exfoliation process could open the way to a range of important applications of h-BN based materials.     

Atomically thin hydroxylation boron nitride nanosheets for excellent water-based lubricant additives

Hexagonal Boron nitride (BN) can be used as a lubricant additive, which can dramatically reduce friction energy. However, due to the accumulation of BN in the water-based lubricants and the difficulty of entering the friction contact area, the tribological performance of BN becomes worse. To address this issue, the atomically thin hydroxylated boron nitride nanosheets (HO-BNNS) were successfully prepared. The thickness of HO-BNNS is only 0.6-0.8 nm. Meanwhile, the HO-BNNS has excellent dispersion stability in water-based lubricants because of the hydroxyl group on the surface of HO-BNNS. The as-prepared HO-BNNS exhibits unique friction properties as a water-based dispersible lubricant additive. Additionally, the average wear scar diameter, average friction coefficient, and mean wear volume of HO-BNNS/water-based (0.05 wt%) drop by about 64.7%, 60%, and 95.73%. Finally, the introduction of HO-BNNS can well control the temperature of water-based lubricant.     

Silicon nitride/boron nitride ceramic composites fabricated by reactive pressureless sintering

Using Si and BN powders as raw materials, silicon nitride/hexagonal boron nitride (Si₃N₄/BN) ceramic composites were fabricated at a relatively low temperature of 1450 °C by using the reaction bonding technology. The density and the nitridation rate, as well as the dimensional changes of the specimens before and after nitridation were discussed based on weight and dimension measurements. Phase analysis by X-ray diffraction (XRD) indicated that BN could promote the nitridation process of silicon powder. Morphologies of the fracture surfaces observed by scanning electron microscopy (SEM) revealed the fracture mode for Si₃N₄/BN ceramic composites to be intergranular. The flexural strength and Young's modulus decreased with the increasing BN content. The reaction-bonded Si₃N₄/BN ceramic composites showed better machinability compared with RBSN ceramics without BN addition.     

Preparation and properties of boron nitride nanosheets/cellulose nanofiber shear-oriented films with high thermal conductivity

A highly thermally conductive boron nitride nanosheets/cellulose nanofiber (BNNS/CNF) oriented film was prepared by doctor blading method via mechanical shear-induced orientation. The SEM images for cross-sectional parts showed that BNNS were well aligned within the film, forming a good layered structure. The XRD results further confirmed the high orientation effect of BNNS. Due to the excellent thermal stability of BNNS and its good physical barrier effect on the matrix after the orientation treatment, the thermal stability of shear-oriented films was largely improved. Resulting from the shear-induced orientation, BNNS were closely contacted with each other, forming a good thermally conductive pathway within the CNF matrix. Thus the influence of the interfacial thermal resistance was dramatically reduced, and the thermal conductivity of shear-oriented films increased in proportion to filler loading. With 50 wt% BNNS, the thermal conductivity of the shear-oriented film reached 24.66 W/(m·K), which exhibited 1106% enhancement compared to the pure CNF.     

Fabrication and mechanical properties of boron nitride nanotube reinforced silicon nitride ceramics

In this study, silicon nitride (Si₃N₄) ceramics added with and without boron nitride nanotubes (BNNTs) were fabricated by hot-pressing method. The influence of sintering temperature and BNNTs content on the microstructures and mechanical properties of Si₃N₄ ceramics were investigated. It was found that both flexural strength and fracture toughness of Si₃N₄ were improved when sintering temperature increases. Moreover, α-Si₃N₄ phase could transform into β-Si₃N₄ phase completely when sintering temperature rises to 1800 °C and above. BNNTs can enhance the fracture toughness of Si₃N₄ dramatically, which increases from 7.2 MPa m^1/2 (no BNNTs) to 10.4 MPa m^1/2 (0.8 wt% BNNTs). However, excessive addition of BNNTs would reduce the fracture toughness of Si₃N₄. Meanwhile, the flexural strength and relative density of Si₃N₄ decreased slightly when BNNTs were added. The related toughening mechanism was also discussed.     

Influence of hexagonal boron nitride nanosheets on phase transformation,microstructure evolution and mechanical properties of Si3N4 ceramics

Fully dense Si₃N₄ materials with 1 wt.% (～ 1.5 vol.%) and 2 wt.% (～ 3.0 vol.%) h-BN nanosheets were prepared by spark plasma sintering at 1750 °C with the dwell of 7 min under a pressure of 50 MPa in a vacuum. BN nanosheets with different dimensions were prepared by ultrasound-assisted liquid phase exfoliation of h-BN powder, followed by centrifugation at different speeds (1000 rpm and 3000 rpm). The addition of BN nanosheets hindered the particle rearrangement stage of sintering, which resulted in the delayed α→β phase transformation of Si₃N₄. To study a direct effect of BN nanosheets on the mechanical properties of Si₃N₄, the results were compared to the monolithic Si₃N₄ with similar grain size and α/β-Si₃N₄ ratio. The addition of 2 wt.% h-BN nanosheets (1000 rpm) increased both the fracture toughness (～ 26 %) and the strength (～ 45 %) of Si₃N₄, when compared to the monolithic Si₃N₄ with similar microstructure.     

Effect of boron nitride nanosheets addition on the mechanical and dielectric properties of magnesium oxide ceramics

Boron nitride nanosheets (BNNSs)/magnesium oxide (MgO) composites were prepared via hot pressing. Mechanical properties of MgO ceramics were improved obviously in virtue of adding BNNSs. The bending strength of the 1 wt% BNNSs/MgO composite increased by about 85% than that of the monolithic MgO. The fracture toughness increased by 34% with the addition of 1.5 wt% BNNSs. Microstructural analyzes have shown that the toughening mechanisms are combinations of the pull-out and bridging of BNNSs, crack deflection, and crack bypassing mechanisms. The addition of a small amount of BNNSs don't destroy the excellent dielectric properties of composites. The dielectric constant of the sample doped with 1 wt% BNNSs was about 9.5 in the whole X-band and the vast majority of P-band, and the loss tangent was less than 5 × 10⁻³ in 10–15.8 GHz.