New insights into synthesis of nanocrystalline hexagonal BN

Uncovering the mechanism behind nanocrystalline hexagonal boron nitride (h-BN) formation at relatively low temperatures is of great scientific and practical interest. Herein, the sequence of phase transformations occurring during the interaction of boric acid with ammonia in a temperature range of 25-1000 °C has been studied in detail by means of thermo-gravimetric analysis, X-ray diffraction, infrared spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicate that at room temperature boric acid reacts with ammonia to form an ammonium borate hydrate (NH4)2B4O7x4H2O. Its interaction with ammonia upon further heating at 550 °C for 1 h leads to the formation of turbostratic BN. Nanocrystalline h-BN is obtained either during heating in ammonia at 550 °C for 24 h or at 1000 °C for 1 h. This result is important for the development of novel cost-effective and scalable syntheses of h-BN nanostructures, such as nanosheets, nanoparticles, nanofibers, and nanofilms, as well as for sintering h-BN ceramic materials

(Ni,Cu)/hexagonal BN nanohybrids - new efficient catalysts for methanol steam reforming and carbon monoxide oxidation

This work is aimed at the development of bimetallic (Ni0.2Cu0.8) catalysts with hexagonal boron nitride (h-BN) nanosheet (BNNS) supports and elucidating their catalytic activity in the methanol steam reforming and CO oxidation reactions. The hybrid Ni0.2Cu0.8/BN catalysts consist of curved h-BN nanosheets, up to 10–20 nm in lateral size, decorated with metallic nanoparticles, 3.0–8.2 nm in dimensions. The methanol conversion starts at ~20 °C and is nearly completed at 320 °C. The (Ni0.2Cu0.8)/BN nanohybrids exhibit high catalytic stability and high selectivity for CO2 over the whole temperature range. No carbon monoxide is detected during full methanol conversion. The possible mechanism of CO utilization during methanol reforming is proposed using ab initio calculations. The onset temperature of catalytic CO oxidation is 100 °C and full conversion is completed at 200 °C. These results indicate high catalytic efficiency of (Ni0.2Cu0.8)/BN nanohybrids in methanol steam reforming and CO oxidation reactions.</p

Elevated-temperature high-strength h-BN-doped Al2014 and Al7075 composites: experimental and theoretical insights

High-strength Al2014 (Al2) and Al7075 (Al7) series composites with and without addition of hexagonal BN (h-BN) flakes (1, 3, and 5 wt%) were fabricated from the powder mixtures of individual elements using a combination of high-energy ball milling (HEBM) and spark plasma sintering (SPS). Phase compositions of Al2 and Al7 composites were different from standard alloys obtained via casting and subsequent heat treatment. Thorough structural study revealed the presence of the following phases: Al(Mg,Si,Mn,Fe,Cu), AlCux, MgOx, and Al5Cu6Mg2 [Al2], Al(Mg,Si,Mn,Fe,Cu), AlCux, Al5Cu6Mg2, Al6CuMg4, MgO2, AlB2, and SiNx [Al2-BN], Al(Cu,Zn,Mg), Fe(Al,Cu), AlCu3, Al2Cu/Fe3Al, Al5Cu6Mg2, Al4Cu9, MgO2 [Al7], and Al(Cu,Zn,Mg), AlCux, MgOx, MgNxOy, MgB2, Mg3(BO3)2, BN, and BNO [Al7-BN]. The important role of h-BN additives in the microstructure formation during HEBM and SPS was demonstrated. Classical molecular dynamics simulations were carried out to estimate critical shear stress between Al nanoparticles with and without intermediate h-BN layers. The obtained results indicated that the h-BN nanosheets had provided solid lubrication, prevented nanoparticle agglomeration during HEBM, led to a reduced porosity and more homogeneous reinforcing phase distributions in the powder mixtures and resultant composites. Structural analysis showed, that during SPS, one part of BN additives had reacted with Al, Si, and Mg to form AlB2, SiNx, and MgB2/Mg3(BO3)2 inclusions, while the other part remained unreacted and contributed to the material strength. Doping with 3 wt% of BN led to an increase in hardness from 76 HV10 to 123 HV10 (Al2 series), and from 97 HV10 to 130 HV10 (Al7 series). The maximum room-temperature tensile strength of 310 MPa (Al7-BN) and 235 MPa (Al2-BN) was observed for the samples with 3 wt% of BN, which corresponds to an increase in strength by approximately 74% and 16%, respectively. At elevated temperatures, the tensile strength values were 227 MPa (350 °C) and 221 MPa (500 °C) for Al2–3%BN, and 276 MPa (350 °C) and 187 MPa (500 °C) for Al7–3%BN. The superior mechanical properties were attributed to the combination of high thermal stability of the reinforcing phases, solid solution hardening, and Orowan (precipitation) strengthening.</p

Synthesis and Characterization of Folate Conjugated Boron Nitride Nanocarriers for Targeted Drug Delivery

International audienceWe have developed advanced folate bonded to boron nitride (BN) nanocarriers with a high potential for targeted drug delivery. The folic acid (FA) molecules were successfully conjugated to BN nanoparticles (BNNPs) in three consecutive stages (i) FA preactivation by N,N'-dicyclohexylcarbodiimide (DCC), (ii) BNNP modification by AgNPs and their further NH2-functionalization with L-cysteine, and (iii) final conjugation of activated FA to modified BNNPs. To shed light on the FA-BNNPs binding mechanism, detailed energetic analysis of the atomic structure and stability of the FA-BNNPs system using density functional theory (DFT) calculations was carried out. The results indicated that the FA was successfully bonded with the BNNPs by a condensation reaction between amino groups of Cyst-Ag/BNNPs and carboxyl groups of FA using DCC. Theoretical analysis also demonstrated that the grafting of FA to the surface of BNNP does not affect FA targeting properties

Amorphous MoSxOy/h-BNxOy Nanohybrids: Synthesis and Dye Photodegradation

Molybdenum sulfide is a very promising catalyst for the photodegradation of organic pollutants in water. Its photocatalytic activity arises from unsaturated sulfur bonds, and it increases with the introduction of structural defects and/or oxygen substitutions. Amorphous molybdenum sulfide (a-MoSxOy) with oxygen substitutions has many active sites, which create favorable conditions for enhanced catalytic activity. Here we present a new approach to the synthesis of a-MoSxOy and demonstrate its high activity in the photodegradation of the dye methylene blue (MB). The MoSxOy was deposited on hexagonal boron oxynitride (h-BNO) nanoflakes by reacting h-BNO, MoCl5, and H2S in dimethylformamide (DMF) at 250 &deg;C. Both X-ray diffraction analysis and high-resolution TEM show the absence of crystalline order in a-MoSxOy. Based on the results of Raman and X-ray photoelectron spectroscopy, as well as analysis by the density functional theory (DFT) method, a chain structure of a-MoSxOy was proposed, consisting of MoS3 clusters with partial substitution of sulfur by oxygen. When a third of the sulfur atoms are replaced with oxygen, the band gap of a-MoSxOy is approximately 1.36 eV, and the valence and conduction bands are 0.74 eV and &minus;0.62 eV, respectively (relative to a standard hydrogen electrode), which satisfies the conditions of photoinduced splitting of water. When illuminated with a mercury lamp, a-MoSxOy/h-BNxOy nanohybrids have a specific mass activity in MB photodegradation of approximately 5.51 mmol g&minus;1 h&minus;1, which is at least four times higher than so far reported values for nonmetal catalysts. The photocatalyst has been shown to be very stable and can be reused

Extended UV detection bandwidth: h-BN/Al powder nanocomposites photodetectors sensitive in a middle UV region due to localized surface plasmon resonance effect

The development of high-effective photodetectors operating in a wide spectral range is an important technological task. In this work we have demonstrated that the detection bandwidth of h-BN photodetectors in the UV range can be extended due to the surface plasmon resonance (SPR) effect. Theoretical calculations showed that, among Al, Au, Ag, and Cu, Al is the most suitable metal for the h-BN UV sensible detectors due to the SPR effect in the middle UV range. Based on the theoretical predictions, a simple and highly efficient method for obtaining h-BN/Al nanocomposites for localized SPR-based UV detectors was developed. It was demonstrated that the h-BN/Al material is sensitive to UV radiation with a wavelength of 266 nm that is far away of the detection limit of 240 nm inherent for pure h-BN

Polyol Synthesis of Ag/BN Nanohybrids and their Catalytic Stability in CO Oxidation Reaction

Polyol method provides variety of options for microstructure control of a synthesized material. The present study aims to demonstrate that in case of Ag/h‐BN nanohybrid fabrication the synthesis time requires precise tuning. Nonlinear correlation between synthesis time and Ag nanoparticles (AgNPs) formation and deposition is found and discussed. Catalytic stability of the studied system toward carbon monoxide oxidation is investigated for the first time. Two stages of catalytic activity decrease are found and associated with the sintering of AgNPs of the certain size. Correlations between Ag content, particle size distribution and temperature of complete CO conversion allow us to conclude that AgNPs, which size is below the critical value (3 nm), have a decisive role in Ag/BN nanohybrid catalytic performance. Density functional theory (DFT) calculations uncover the mechanism behind the increased catalytic activity of smaller AgNPs and highlight an importance of the Ag/BN interfacial regions

Microstructure and catalytic properties of Fe3O4/BN, Fe3O4(Pt)/BN, and FePt/BN heterogeneous nanomaterials in CO2 hydrogenation reaction: Experimental and theoretical insights

Hexagonal boron nitride (h-BN) nanosheets are a promising material for various applications including catalysis. Herein, h-BN-supported Fe-based catalysts are characterised with respect to CO2 hydrogenation reaction. Heterogeneous Fe3O4/BN, Fe3O4(Pt)/BN, and FePt/BN nanostructures are obtained via polyol synthesis in ethylene glycol. The sizes of Fe3O4 nanoparticles and their distributions over h-BN surfaces depend on the amount of H2PtCl6 added to the synthesis media. Bimetallic FePt nanoparticles are formed when Pt content is high enough. In situ TEM analysis shows the formation of core–shell h-BN@FePt nanoparticles during heating that prevents FePt NPs from further sintering during the catalytic process. The mechanism of Fe and Pt interaction is elucidated based on the molecular dynamic simulations. The FePt/BN nanomaterials show significantly higher CO2 conversion rate compared to the Fe3O4/BN and Fe3O4(Pt)/BN heterogeneous nanomaterials and exhibit almost 100% selectivity to carbon monoxide. The Fe3O4/BN and Fe3O4(Pt)/BN nanomaterials show better selectivity to hydrocarbons. The possible reaction pathways are discussed based on the calculated sorption energies of all reactants, intermediate compounds, and reaction products. The study highlights pronounced catalytic properties of the developed system and reveals a unique interaction mechanism between its components increasing their stability.</p

Hexagonal BN- and BNO-supported Au and Pt nanocatalysts in carbon monoxide oxidation and carbon dioxide hydrogenation reactions

Environmental protection requires solving the problem of utilization and reduction of CO and CO2 emissions. Herein, Au/h-BN(O) and Pt/h-BN(O) nanohybrids are thoroughly analyzed in CO oxidation and CO2 hydrogenation reactions. The nanohybrids differ in catalytic particle size and particle distribution. The particles are smaller (1-6 nm) and display a narrower size distribution in the case of Pt-based nanomaterials. The Pt/h-BN(O) nanohybrids exhibit high catalytic activity in CO conversion and carbon dioxide hydrogenation reactions. For both systems, the oxidative state of BN support affects the catalytic activity. The possible catalytic reaction mechanisms are proposed based on DFT calculations. A charge density distribution at the Pt/h-BN interface increases oxygen absorption, thereby accelerating oxygen-associated chemical reactions

BN/Ag hybrid nanomaterials with petal-like surfaces as catalysts and antibacterial agents

BN/Ag hybrid nanomaterials (HNMs) and their possible applications as novel active catalysts and antibacterial agents are investigated. BN/Ag nanoparticle (NP) hybrids were fabricated using two methods: (i) chemical vapour deposition (CVD) of BN NPs in the presence of Ag vapours, and (ii) ultraviolet (UV) decomposition of AgNO3 in a suspension of BN NPs. The hybrid microstructures were studied by high-resolution transmission electron microscopy (HRTEM), high-angular dark field scanning TEM imaging paired with energy dispersion X-ray (EDX) mapping, X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (FTIR). They were also characterized in terms of thermal stability, Ag+ ion release, catalytic and antibacterial activities. The materials synthesized via UV decomposition of AgNO3 demonstrated a much better catalytic activity in comparison to those prepared using the CVD method. The best catalytic characteristics (100% methanol conversion at 350 °C) were achieved using the UV BN/Ag HNMs without preliminary annealing at 600 °C in an oxidizing atmosphere. Both types of the BN/Ag HNMs possess a profound antibacterial effect against Escherichia coli K-261 bacteria