Ultrahigh sensitive and selective triethylamine sensor based on h-BN modified MoO3 nanowires

In this work, a novel structure of 1D MoO₃ nanowires wrapped by 2D hexagonal boron nitride (h-BN) was synthesized via a simple solvothermal method with subsequent annealing process for triethylamine (TEA) detection. The samples were characterized by XPS, SEM, HRTEM and N₂ adsorption-desorption. Gas sensing performance test results illuminate that the typical 2 wt% h-BN/MoO₃ sensor possesses an ultrahigh response (8616) toward 500 ppm TEA. The promoted sensing performance of TEA may be caused by the forming of heterojunction between h-BN and MoO₃, the increased specific surface area of h-BN modification, providing a highly active sites for the adsorption of TEA gas, which greatly enhance the response of the sensor. The adsorption energy of a single oxygen molecule on MoO₃ (0 1 0) surface was calculated by DFT, indicating the most stable site is the terminal oxygen position (Top O-1), with an adsorption energy of ?2.075 eV. This work provides an inspiration to design highly efficient TEA gas sensor on basis of h-BN/MoO₃ nanocomposites.     

A Robust n-n Heterojunction: Cu?N and B?N Boosting for Ambient Electrocatalytic Nitrogen Reduction to Ammonia

An n-n type heterojunction comprising with Cu N and B N dual active sites is synthesized via in situ growth of a conductive metal–organic framework (MOF) [Cu₃(HITP)₂] (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) on hexagonal boron nitride (h-BN) nanosheets (hereafter denoted as Cu₃(HITP)₂@h-BN) for the electrocatalytic nitrogen reduction reaction (eNRR). The optimized Cu₃(HITP)₂@h-BN shows the outstanding eNRR performance with the NH₃ production of 146.2 µg h⁻¹ mg_cat⁻¹ and the Faraday efficiency of 42.5% due to high porosity, abundant oxygen vacancies, and Cu N/B N dual active sites. The construction of the n-n heterojunction efficiently modulates the state density of active metal sites toward the Fermi level, facilitating the charge transfer at the interface between the catalyst and reactant intermediates. Additionally, the pathway of NH₃ production catalyzed by the Cu₃(HITP)₂@h-BN heterojunction is illustrated by in situ FT-IR spectroscopy and density functional theory calculation. This work presents an alternative approach to design advanced electrocatalysts based on conductive MOFs.     

Synthesis of the uniform hollow spherical Sr2SiO4:Eu2+ phosphors via an h-BN protective method

The uniform hollow spherical Sr₂SiO₄:Eu²⁺ green emitting phosphors have been successfully synthesized using hollow silica spheres as templates by an h-BN protective method. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results directly confirmed the existence of the hollow spherical structure with a narrow size distribution and a shell thickness of 15–25 nm. The h-BN protective film, observed by high resolution TEM, plays an important role in the formation of the hollow spherical morphology and the improvement of photoluminescence properties. Comparing with the Sr₂SiO₄:Eu²⁺ micron-phosphor prepared by the traditional solid state reaction method, the hollow spherical phosphor with nano-sized grains exhibits stronger green emission under ultraviolet–blue light excitation. This could be attributed to the elimination of surface defects by the h-BN coating. This research gives an economic and convenient way to synthesize uniform spherical phosphors with high quantum efficiency.     

Crystallization Kinetics of Cubic Boron Nitride in the B-N-Mg-H-F System

The kinetics of the h-BN → c-BN transformation in a mixture of composition 78% h-BN + 5% NH₄F + 2% B + 15% Mg are studied at 5 GPa and temperatures from 1670 to 1910 K. The activation energy of c-BN formation, temperature-dependent reaction rate constant, strength of the forming c-BN particles, and density of paramagnetic defects in c-BN are evaluated.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 816–818.Original Russian Text Copyright © 2005 by Shipilo, Ignatenko, Anichenko, Azarko.     

Development of NiO-based thin film structures as efficient H2 gas sensors operating at room temperatures

P-type NiO thin films have been developed on high resistivity Si and SiO₂ substrates by a pulsed laser deposition technique using an ArF^? 193 nm excimer laser at deposition temperature of 300 °C and in 40 Pa partial oxygen pressure. Structures based on such NiO films as host material in the form of Au-NiO Schottky diodes have been subsequently developed under vacuum. In a different procedure, an n-SnO₂ layer has been deposited by a CVD technique on a NiO film to produce a p/n heterojunction. The sensing properties of all above structures have been tested upon exposure to a H₂ flow in air ambient gas at various operating temperature ranging from 30 to 180 °C. For the NiO films, the optimum temperature was about 150 °C exhibiting a sensitivity of 94%. After surface sensitization of NiO by Au the NiO films showed an H₂ response at operating temperature of 30 °C. The sensitivity of p-NiO/n-SnO₂ heterojunction devices was extracted from I-V measurements in air and under H₂ flow mixed in air. In this case a dramatic increase of the sensitivity was achieved at operating temperature of 30 °C for a forward bias of 0,2 V.     

p-n异质结NiO/TiO2纳米复合材料的构建及应用研究进展

TiO_2和NiO分别作为n型和p型半导体材料,通过复合构建p-n异质结NiO/TiO_2纳米复合材料可以促进光生电子-空穴对的分离,从而提高光电性能。综述了不同形貌的p-n异质结NiO/TiO_2纳米复合材料的构建,如纳米球、纳米棒和纳米带等,以及其在光催化、锂离子电池、染料敏化太阳能电池和传感器等领域中的最新研究进展。     

Preparation of calcium-doped boron nitride by pulsed laser deposition

Calcium-doped BN thin films Ca_xBN_y (x = 0.05–0.1, y = 0.7–0.9) were grown on α-Al₂O₃(0 0 1) substrates by pulsed laser deposition (PLD) using h-BN and Ca₃N₂ disks as the targets under nitrogen radical irradiation. Infrared ATR spectra demonstrated the formation of short range ordered structure of BN hexagonal sheets, while X-ray diffraction gave no peak indicating the absence of long-range order structure in the films. It was notable that Ca-doped film had 5.45–5.55 eV of optical band gap, while the band gap of Ca-free films was 5.80–5.85 eV. This change in the band gap is ascribed to interaction of Ca with the BN sheets; first principle calculations on h-BN structure indicated that variation of inter-plane distance between the BN layers did not affect the band gap. This study highlights that PLD could prepare BN having short-range structure of h-BN sheets and being doped with electropositive cation which varies the optical band gap of the films.     

MOF-Derived In2O3/CuO p-n Heterojunction Photoanode Incorporating Graphene Nanoribbons for Solar Hydrogen Generation

Solar-driven photoelectrochemical (PEC) water splitting is a promising approach toward sustainable hydrogen (H₂) generation. However, the design and synthesis of efficient semiconductor photocatalysts via a facile method remains a significant challenge, especially p-n heterojunctions based on composite metal oxides. Herein, a MOF-on-MOF (metal-organic framework) template is employed as the precursor to synthesize In₂O₃/CuO p-n heterojunction composite. After incorporation of small amounts of graphene nanoribbons (GNRs), the optimized PEC devices exhibited a maximum current density of 1.51 mA cm⁻² (at 1.6 V vs RHE) under one sun illumination (AM 1.5G, 100 mW cm⁻²), which is approximately four times higher than that of the reference device based on only In₂O₃ photoanodes. The improvement in the performance of these hybrid anodes is attributed to the presence of a p-n heterojunction that enhances the separation efficiency of photogenerated electron-hole pairs and suppresses charge recombination, as well as the presence of GNRs that can increase the conductivity by offering better path for electron transport, thus reducing the charge transfer resistance. The proposed MOF-derived In₂O₃/CuO p-n heterojunction composite is used to demonstrate a high-performance PEC device for hydrogen generation.     

Large scale synthesis of single-crystal and polycrystalline boron nitride nanosheets

Boron nitride nanosheets (BNNSs) have an identical crystal structure and similar lattice parameter to those of graphene sheets. However, growing quality BNNSs consisting of only several atomic layers remains a challenge. Here, we report on the synthesis of BNNSs at a temperature of 350 °C using a CO₂ pulsed laser plasma deposition (CO₂-PLD) technique by irradiating a pyrolytic hexagonal boron nitride (h-BN) target. The deposition was performed either in vacuum at a pressure of 0.2 Pa, for which we obtained polycrystalline BN, or in hydrogen (H₂) atmosphere at a pressure of 26 Pa for which we obtained single-crystal BNNSs. The presence of H₂ seems to minimize the side effects of sputtering and the material shows higher purity and better crystallinity. High resolution transmission electron microscopy (HRTEM) showed the sheets to be mostly defect-free and to have the characteristic honeycomb structure of six-membered B₃-N₃ hexagon. HRTEM, electron diffraction, X-ray diffraction, Raman scattering, and Fourier transform infrared spectroscopy clearly identified h-BN.     

Reversible phase transformation in boron nitride under pulsed mechanical action

It is established that hexagonal boron nitride (h-BN) exhibits transformation to high-pressure diamondlike phases (w-, c-BN) under conditions of treatment in a planetary ball mill. After a 12-h processing, the yield of these phases (?20%) no longer grows with further increasing the process duration, which is evidence for a reversible character of the transformation. This conclusion is confirmed by the w-BN → h-BN transformation observed under the same process conditions. In addition to h-, w-, and c-BN, we have also found several new modifications of boron nitride.     

Thin film growth of boron nitride on α-Al2O3 (0 0 1) substrates by reactive sputtering

Boron nitride thin films were grown on α-Al₂O₃ (0 0 1) substrates by reactive magnetron sputtering. Infrared attenuated total reflection (ATR) spectra of the films gave an intense signal associated with in-plane B-N stretching TO mode of short range ordered structure of BN hexagonal sheets. X-ray diffraction for the film prepared at a low working pressure (ca. 1 × 10⁻³ Torr) gave a diffraction peak at slightly lower angle than that corresponding to crystal plane h-BN (0 0 2). It is notable that crystal thickness calculated from X-ray peak linewidth (45 nm) was close to film thickness (53 nm), revealing well developed sheet stacking along the direction perpendicular to the substrate surface. When the substrates of MgO (0 0 1) and Si (0 0 1) were used, the short-range ordered structure of h-BN sheet was formed but the films gave no X-ray diffraction. The film showed optical band gap of 5.9 eV, being close to that for bulk crystalline h-BN.     

Elastic properties of hybrid graphene/boron nitride monolayer

Recently, hybridized monolayers consisting of hexagonal boron nitride (h-BN) phases inside a graphene layer have been synthesized and shown to be an effective way of opening band gap in graphene monolayers (Ci et?al. in Nat Mater 9(5):430–435, 2010). In this paper, we report a first-principles density functional theory study of the h-BN domain size effect on the elastic properties of graphene/boron nitride hybrid monolayers (h-BNC). We found that both in-plane stiffness and longitudinal sound velocity of h-BNC linearly decrease with h-BN concentration. Our results could be used for the design of future graphene-based nanodevices of surface acoustic wave sensors and waveguides.     

Bio-inspired structured boron carbide-boron nitride composite by reactive spark plasma sintering

Nature creates composite materials with complex hierarchical structures that possess impressive mechanical properties enhancement capabilities. An approach to improve mechanical properties of conventional composites is to mimic the biological material structured ‘hard’ core and ‘soft’ matrix system. This would allow the efficient transfer of load stress, dissipation of energy and resistance to cracking in the composite. In the current study, reactive spark plasma sintering (SPS) of boron carbide B₄C was carried out in a nitrogen N₂ gas environment. The process created a unique core-shell structured material with the potential to form a high impact-resistant composite. Transmission electron microscopy observation of nitrided-B₄C revealed the encapsulation of B₄C grains by nano-layers of hexagonal-boron nitride (h-BN). The effect of the h-BN contents on hardness were measured using micro- and nano-indentation. Commercially available h-BN was also mechanically mixed and sintered with B₄C to compare the effectiveness of nitrided B₄C. Results have shown that nitrided B₄C has a higher hardness value and the optimum content of h-BN from nitridation was 0.4%wt with the highest nano-indentation hardness of 56.7 GPa. The high hardness was attributed to the h-BN matrix situated between the B₄C grain boundaries which provided a transitional region for effective redistribution of the stress in the material.     

Mn atomic layers under inert covers of graphene and hexagonal boron nitride prepared on Rh(111)

Intercalation of metal atoms into the interface of graphene and its supporting substrate has become an intriguing topic for the sake of weakening the interface coupling and constructing metal atomic layers under inert covers. However, this novel behavior has rarely been reported on the analogous hexagonal boron nitride (h-BN) synthesized on metal substrates. Here, we describe a comparative study of Mn intercalation into the interfaces of graphene/Rh(111) and h-BN/Rh(111), by using atomically-resolved scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The intercalation was performed by annealing as-deposited Mn clusters, and the starting temperature of Mn intercalation into h-BN/Rh(111) was found to be ～80 °C higher than that for graphene/Rh(111). Moreover, the intercalated islands of h-BN/Mn/Rh(111) usually possess more irregular shapes than those of graphene/Mn/Rh(111), as illustrated by temperature-dependent STM observations. All these experimental facts suggest a stronger interaction of Mn with h-BN/Rh(111) than that with graphene/Rh(111).      

First-principles modeling of lattice defects: advancing our insight into the structure-properties relationship of ice

We discuss a number of examples that demonstrate the value of computational modeling as a complementary approach in the physics and chemistry of ice I _h , where real-life experiments often do not give direct access to the desired information or whose interpretation typically requires uncontrollable assumptions. Specifically, we discuss two cases in which, guided by experimental insight, density-functional-theory-based first-principles methods are applied to study the properties of lattice defects and their relationship to ice I _h s macroscopic behavior. First, we address a question involving molecular point defects, examining the energetics of formation of the molecular vacancy and a number of different molecular interstitial configurations. The results indicate that, as suggested by earlier experiments, a configuration involving bonding to the surrounding hydrogen-bond network is the preferred interstitial structure in ice I _h . The second example involves the application of modeling to elucidate on the microscopic origin of the experimental observation that a specific type of ice defect is effectively immobile while others are not. Inspired by previous suggestions that this defect type may be held trapped at other defect sites and our finding that the bound configuration is the preferred interstitial configuration in ice I _h , we use first-principles modeling to examine the binding energetics of the specific ice defect to the molecular vacancy and interstitial. The results suggest a preferential binding of the immobile defect to the molecular interstitial, possibly explaining its experimentally observed inactivity.     

Effect of Different Nanosized NiO Addition on Ag-Sheathed (Bi1.6Pb0.4)Sr2Ca2Cu3O10 Superconductor Tapes

(Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀–(NiO) _x superconductor with x=0, 0.01, 0.02, 0.03, 0.04, and 0.05 wt.% was prepared using the coprecipitation technique. The average size of NiO used was 8 nm and 16 nm. The highest value of the transport critical current density, J _c in the bulk form was observed in the x=0.01 wt.% samples for both sizes. Based on this result, Ag sheathed superconductor tapes with starting composition (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀–(NiO)_0.01 (with NiO particle size 8 and 16 nm) were fabricated using the powder-in-tube method. The effect of these nanoparticles addition on the microstructure, phase formation, and transport critical current density were studied. The J _c of the tape at 77 K in zero fields with NiO (8 nm) addition (4500 A/cm²) was slightly higher than that of NiO (16 nm) added tape (4120 A/cm²). The nonadded tape showed a lower J _c (1080 A/cm² at 77 K). These results indicated that magnetic nanoparticles such as NiO could act as an effective flux pinning centers leading to the enhancement of J _c in the bulk and tape form. Moreover, NiO with size closer to the coherence length, ξ was more effective in enhancing J _c.     

In situ fabrication of α-Fe2O3/CaFe2O4 p-n heterojunction with enhanced VOCs photodegradation activity

α-Fe₂O₃/CaFe₂O₄ p-n heterojunctions were prepared via a simple in-situ hydrolysis process as highly efficient VOCs degradation photocatalyst, wherein no additional conditions such as high pressure, high temperature and surfactants were required. The structures and morphologies of the as-prepared samples were analyzed by XRD, SEM and TEM. The results revealed that α-Fe₂O₃/CaFe₂O₄ p-n heterojunctions exhibited superior photocatalytic activity of VOCs degradation compared to pure CaFe₂O₄ and α-Fe₂O₃ in both steady model and flow bed model. It can degrade more than 82% of acetaldehyde within 180?min in steady mode and 65% in flow mode under visible light irradiation. The prominent VOCs remove property could be attributed to the strong interfacial contact caused by the in-situ fabrication process and the promoted charge carrier separation efficiency due to the constructing of α-Fe₂O₃/CaFe₂O₄ p-n heterojunction. It provides some new insights into the design and fabrication of advanced photocatalytic materials with p-n heterojunction for high efficiency in VOCs photodegradation.     

Functionalized Graphene Quantum Dot Modification of Yolk–Shell NiO Microspheres for Superior Lithium Storage

Yolk–shell NiO microspheres are modified by two types of functionalized graphene quantum dots (denoted as NiO/GQDs) via a facile solvothermal treatment. The modification of GQDs on the surface of NiO greatly boosts the stability of the NiO/GQD electrode during long‐term cycling. Specifically, the NiO with carboxyl‐functionalized GQDs (NiO/GQDs? COOH) exhibits better performances than NiO with amino‐functionalized GQDs (NiO/GQDs? NH₂). It delivers a capacity of ≈1081 mAh g^?1 (NiO contribution: ≈1182 mAh g^?1) after 250 cycles at 0.1 A g^?1. In comparison, NiO/GQDs? NH₂ electrode holds ≈834 mAh g^?1 of capacity, while the bald NiO exhibits an obvious decline in capacity with ≈396 mAh g^?1 retained after cycling. Except for the yolk–shell and mesoporous merits, the superior performances of the NiO/GQD electrode are mainly ascribed to the assistance of GQDs. The GQD modification can support as a buffer alleviating the volume change, improve the electronic conductivity, and act as a reservoir for electrolytes to facilitate the transportation of Li⁺. Moreover, the enrichment of carboxyl/amino groups on GQDs can further donate more active sites for the diffusion of Li⁺ and facilitate the electrochemical redox kinetics of the electrode, thus together leading to the superior lithium storage performance.     

Facile synthesis and microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere and multi-shelled NiO hollow sphere

We reported the preparation of C@Ni–NiO core–shell hybrid solid spheres or multi-shelled NiO hollow spheres by combining a facile hydrothermal route with a calcination process in H₂ or air atmosphere, respectively. The synthesized C@Ni–NiO core–shell solid spheres with diameters of approximately 2–6 μm were in fact built from dense NiO nanoparticles coated by random two-dimensional metal Ni nanosheets without any visible pores. The multi-shelled NiO hollow spheres were built from particle-like ligaments and there are a lot of pores with size of several nanometers on the surface. Combined Raman spectra with X-ray photoelectron spectra (XPS), it suggested that the defects in the samples play a limited role in the dielectric loss. Compared with the other samples, the permeability of the samples calcined in H₂ and air was increased slightly and the natural resonance frequency shifted to higher frequency (7, 11 and 14 GHz, respectively), leading to an enhancement of microwave absorption property. For the sample calcined in H₂, an optimal reflection loss less than − 10 was obtained at 7 GHz with a matching thickness of 5.0 mm. Our study demonstrated the potential application of C@Ni–NiO core–shell hybrid solid sphere or multi-shelled NiO hollow sphere as a more efficient electromagnetic (EM) wave absorber.     

Construction of CoTiO3/BiOI p-n heterojunction with nanosheets-on microrods structure for enhanced photocatalytic degradation of organic pollutions

Herein, a novel CoTiO₃/BiOI (CTOB) p-n heterojunction with nanosheets-on microrods structure were prepared via a simple coprecipitation method for the first time. The catalysts were carefully characterized by various instruments. The CTOB heterostructures display improved photocatalytic performance towards RhB degradation. Among CTOB composites, CTOB-15 exhibits the optimal photocatalytic performance. Moreover, CTOB-15 also shows enhanced photocatalytic activity for MO and TC degradation compared to bare catalysts. The degradation rate constants for RhB and MO by CTOB-15 heterostructure are ca 1.6 and 1.4-fold higher than bare BiOI. The improved photocatalytic performance could be on account of the efficient separation of photoinduced carriers as well as enhanced light absorbance. Trapping experiments indicates that holes (h⁺) and superoxide anion radical (O₂^–) play a significant role in the removal of RhB by CTOB composites. The excellent photocatalytic activity and stability make it a promising photocatalyst in environmental remediation.