Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Wear and corrosion properties of wollastonite and boron nitride doped,hydroxyapatite-based HAp-Wo-BN composite coatings prepared by pulsed laser deposition

In this study, hydroxyapatite-based hydroxyapatite-wollastonite-boron nitride (HAp-Wo-BN) composite film was formed on the surface of Ti6Al4V by pulsed laser deposition (PLD). Based on a survey in scientific literature, it is presumed that this is the first time such a process is being undertaken. The wear and corrosion resistance of this film were analyzed comparatively in simulated body fluid (SBF) to simulate the human body environment. In the coating, HAp was used to form a bone-like layer, wollastonite was to enhance bone-tissue regeneration and BN was used for its bone-tissue healing and anti-bacterial properties. The results showed that the wear as well as the corrosion resistance of all samples after PLD treatment increased. Relatively the best wear resistance was achieved from boron nitride and wollastonite doped hydroxyapatite layers, where the best corrosion resistance was from the ones that consisted of only hydroxyapatite.     

Epitaxial Growth of 2D Materials on High-Index Substrate Surfaces

Recently, the successful synthesis of wafer-scale single-crystal graphene, hexagonal boron nitride (hBN), and MoS₂ on transition metal surfaces with step edges boosted the research interests in synthesizing wafer-scale 2D single crystals on high-index substrate surfaces. Here, using hBN growth on high-index Cu surfaces as an example, a systematic theoretical study to understand the epitaxial growth of 2D materials on various high-index surfaces is performed. It is revealed that hBN orientation on a high-index surface is highly dependent on the alignment of the step edges of the surface as well as the surface roughness. On an ideal high-index surface, well-aligned hBN islands can be easily achieved, whereas curved step edges on a rough surface can lead to the alignment of hBN along with different directions. This study shows that high-index surfaces with a large step density are robust for templating the epitaxial growth of 2D single crystals due to their large tolerance for surface roughness and provides a general guideline for the epitaxial growth of various 2D single crystals.     

Investigation on thermal conductivity and mechanical properties of Si3N4 ceramics via one-step sintering

High thermal conductivity Si₃N₄ ceramics were fabricated using a one-step method consisting of reaction-bonded Si₃N₄ (RBSN) and post-sintering. The influence of Si content on nitridation rate, β/(α+β) phase rate, thermal conductivity and mechanical properties was investigated in this work. It is of special interest to note that the thermal conductivity showed a tendency to increase first and then decrease with increasing Si content. This experimental result shows that the optimal thermal conductivity and fracture toughness were obtained to be 66 W (m K)^-1 and 12.0 MPa m^1/2, respectively. As a comparison, the nitridation rate and β/(α+β) phase rate in a static pressure nitriding system, i.e., 97% (MS10), 97% (MS15), 97% (MS20) and 8.3% (MS10), 8.3% (MS15), 8.9% (MS20), respectively, have obvious advantages over those in a flowing nitriding system, i.e., 91% (MS10), 91% (MS15), 93% (MS20) and 3.1% (MS10), 3.3% (MS15), 3.3% (MS20), respectively. Moreover, high lattice integrity of the β-Si₃N₄ phase was observed, which can effectively confine O atoms into the β-Si₃N₄ lattice using MgO as a sintering additive. This result indicates that one-step sintering can provide a new route to prepare Si₃N₄ ceramics with a good combination of thermal conductivity and mechanical properties.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

Platinum nanoparticles decorated on graphitic carbon nitride-ZIF-67 composite support: An electrocatalyst for the oxidation of butanol in fuel cell applications

In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C₃N₄) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C₃N₄ was prepared through thermal polymerization method. Later, ZIF-67 and g-C₃N₄ were hybridized through sonication to get homogeneous g–C₃N₄–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C₃N₄–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C₃N₄–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C₃N₄–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C₃N₄–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells.     

Heat propagation in thermally conductive polymers of PA6 and hexagonal boron nitride

Thermally conductive polymers offer new possibilities for the heat dissipation in electric and electronic components, for example, by a three‐dimensional shaping of the heat sinks. To face safety regulations, improved fire performance of those components is required. In contrast to unfilled polymers, those materials exhibit an entirely different thermal behavior. To investigate the flammability, a phosphorus flame retardant was incorporated into thermally conductive composites of polyamide 6 and hexagonal boron nitride. The flame retardant decreased the thermal conductivity only slightly. However, the burning behavior changed significantly, due to a different heat propagation, which was investigated using a thermographic camera. An optimum content of hexagonal boron nitride for a sufficient thermal conductivity and fire performance was found between 20 and 30 vol%. The improvement of the fire performance was due to a faster heat release out of the pyrolysis zone and an earlier decomposition of the flame retardant. For higher contents of hexagonal boron nitride, the heat was spread faster within the part, promoting an earlier ignition and increasing the decomposition rate of the flame retardant.     

Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites

The enhancement of the thermal conductivity, keeping the electrical insulation, of epoxy thermosets through the addition of pristine and oxidized carbon nanotubes (CNTs) and microplatelets of boron nitride (BN) was studied. Two different epoxy resins were selected: a cycloaliphatic (ECC) epoxy resin and a glycidylic (DGEBA) epoxy resin. The characteristics of the composites prepared were evaluated and compared in terms of thermal, thermomechanical, rheological and electrical properties. Two different dispersion methods were used in the addition of pristine and oxidized CNTs depending on the type of epoxy resin used. Slight changes in the kinetics of the curing reaction were observed in the presence of the fillers. The addition of pristine CNTs led to a greater enhancement of the mechanical properties of the ECC composite whereas the oxidized CNTs presented a greater effect in the DGEBA matrix. The addition of CNTs alone led to a marked decrease of the electrical resistivity of the composites. Nevertheless, in the presence of BN, which is an electrically insulating material, it was possible to increase the proportion of pristine CNTs to 0.25 wt% in the formulation without deterioration of the electrical resistivity. A small but significant synergic effect was determined when both fillers were added together. Improvements of about 750% and 400% in thermal conductivity were obtained in comparison to the neat epoxy matrix for the ECC and DGEBA composites, respectively. © 2019 Society of Chemical Industry     

Combating Biofilm Associated Infection In Vivo: Integration of Quorum Sensing Inhibition and Photodynamic Treatment based on Multidrug Delivered Hollow Carbon Nitride Sphere

Recently, quorum sensing (QS) inhibitors (QSIs) have been combined with antibiotics to enhance antibiofilm efficacy in vitro and in vivo. However, targeting QS signals alone is not enough to prevent bacterial infections. Drug resistance and recurrence of biofilms makes it difficult to eradicate. Herein, photodynamic therapy (PDT) is selected to unite QSIs and antibiotics. A synergistically antibiofilm system, which combines QSIs, antibiotics, and PDT based on hollow carbon nitride spheres (HCNSs) is envisaged. First, HCNS provides the multidrug delivering ability, enabling QSIs and antibiotics to be released in sequence. Subsequently, multistage releases sensitize bacteria effectively, potentiating the chemotherapeutic effects of the antibiotics. Finally, the integration of QSIs and PDT not only minimizes the possibility of drug resistance, but also overcomes the problem of limited mass and extension of PDT. Even after 48 h of incubation, the bacterial biofilm is obviously inhibited. And its biofilm disperse efficiency exceeds 48% (compared with QSI‐potentiated chemotherapy group) and 40% (compared with PDT group). Besides, the inhibition of the QS system influences phenotypes related to virulence factor production and surface hydrophobicity, which weaken biofilm invasion and formation. Eventually, this system is applied to disperse bacterial biofilm in vivo. Overall, PDT and QS modulation are devoted to eradicate drug resistance and recurrence of the biofilm.