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.     

Essential (Mg,Fe, Zn and Cu) and Non-Essential (Cd and Pb) Elements in Predatory Insects (Vespa crabro and Vespa velutina): A Molecular Perspective

The recent introduction of the Asian yellow-legged hornet, Vespa velutina, into Europe has raised concern regarding the threat to honeybees and the competition with the European hornet, Vespa crabro. The aim of this study was to investigated essential (Mg, Fe, Zn, Cu) and non-essential (Cd and Pb) elements in these two species. Element concentrations were determined in the whole body and separately in the head, thorax and abdomen using atomic absorption spectrometry (AAS). The changes in essential element concentration and speciation during metamorphosis were also studied using size exclusion chromatography followed by AAS and proteomic analysis. In both species, the essential elements were more concentrated in the abdomen due to the presence of fat bodies. Magnesium, Fe and Zn concentrations were significantly higher in V. crabro than in V. velutina and could have been related to the higher aerobic energy demand of the former species required to sustain foraging flight. Low concentrations of Cd and Pb were indicative of low environmental exposure. The concentration and speciation of essential elements, particularly Fe, varied among the developmental stages, indicating a modification of ligand preferences during metamorphosis. Overall, the results in the present study provide a better understanding of the hornet metal metabolism and a foundation for additional studies.     

Estimation of gradient size of interfacial strain and its optimization for effective magnetoelectric coupling in (CoFe2O4) – (0.93Na0.5Bi0.5TiO3 – 0.07BaTiO3), 2-2 nano-composites

Strain-mediated coupling between the magnetic and electrically ordered phases plays a significant role in magnetoelectric (ME) nano-composites. This study explores a method to analyse and quantify interfacial strain using a grazing angle scan (α) in a ME composite optimised for a specific microstructure. The details of strain around the interface CoFe₂O₄ (CFO) – 0.93Na_0.5Bi_0.5TiO₃ – 0.07BaTiO₃ (NBT-BT) was determined by performing ‘α’ scan, in order to gather information at various depths of the NBT-BT layer around maximum intensity (110) reflection. The strain around the interface was observed to dominate over a spatial region of ～20–30 nm away from the interface. The Piezoresponse force microscopy (PFM) studies performed near the interface reveal that the strain constrain experienced by the ferroelectric layer operates such that polarisation rotation and domain wall motion are constrained compared to the strain relaxed region of the film. For effective strain transfer, heterostructures grown with optimised thicknesses (～20–30 nm) exhibited a superior inverse piezomagnetic effect.     

The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

Sulfur doped biocarbon obtained from Sargassum spp. for the oxygen reduction reaction

Sulfured doped carbon electrocatalysts is synthesized from the waste biomass Sargassum spp. Two doping procedures are examined to determine which is better for Oxygen Reduction Reaction (ORR); one by doping biocarbon obtained from the pyrolysis of the biomass and the second through a process of in situ doping in autoclave. The electrocatalyst are obtained from pyrolysis of the sample at 700 °C, which is finally characterized as a metal free electrocatalyst for the ORR. The electrocatalyst are characterized by BET surface area analysis, Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and the electrochemical characterization is determined in 0.1 M KOH. The sample SSKPT-1 exhibits a promising electrocatalytic activity with an onset potential of 0.896 V vs RHE and a current density of 5 mA cm^?2 (at 0.2 V vs. RHE) which could be partly attributed to its high BET surface area of 2755 m² g^?1.     

Temperature adaptability of the soluble lead flow battery using different solutions of fluoborate,perchlorate, methanesulfonate and trifluoromethanesulfonate

The evaluation of cell's weatherability is of practical interest. To further improve the soluble lead flow battery's weatherability, physiochemical properties of electrolytes containing fluoborate, perchlorate, methanesulfonate and trifluoromethanesulfonate are investigated from ?60 to 50 °C. Activities of CF₃SO₃H and HClO₄ are poor in trifluoromethanesulfonate and perchlorate solutions due to common anion effect. The solubility of lead salt can be improved by increasing temperature, but worsened by increasing acid's content. With the temperature increasing, the conductivity is enhanced, and the viscosity is lowered for four solutions. The same results have been found by increasing acid's content except for CF₃SO₃H. The high energy efficiency can be achieved for cells over ?40–0 °C using fluoborate and perchlorate solutions, 73.2% at ?40 °C and 78.1% at ?30 °C respectively. Over the temperature range of 20–50 °C, the cells with methanesulfonate and trifluoromethanesulfonate solutions have good performance, 77.4% and 73.7% at 50 °C respectively.     

Resistance reduction effect of potassium bismuth titanate doping in yttrium–manganese co-doped medium Curie temperature barium titanate lead free ceramics through improved synthesis process

Through improved synthesis process, resistance reduction effect of (K_0.5Bi_0.5)TiO₃ (KBT) doping in Y–Mn co-doped BaTiO₃ (BT) lead free ceramics was investigated. By different doping methods (doping K₂O, Bi₂O₃ and TiO₂ or synthesized KBT), medium Curie temperature (around 130 °C) lead free BT ceramics were obtained with ultra-low resistivity (13.84 Ωcm) with a temperature maintaining process at 700 °C. In this contribution, effect of sintering process and doping methods is discussed in detail.     

Activity-Directed Synthesis: A Flexible Approach for Lead Generation

Activity-directed synthesis (ADS) is a structure-blind, functional-driven molecular discovery approach. In this Concept, four case studies highlight the general applicability of ADS and showcase its flexibility to support different medicinal chemistry strategies. ADS deliberately harnesses reactions with multiple possible outcomes, and allows many chemotypes to be evaluated in parallel. Resources are focused on bioactive molecules, which emerge in tandem with associated synthetic routes. Some of the future challenges for ADS are highlighted, including the realisation of an autonomous molecular discovery platform. The prospects for ADS to become a mainstream lead generation approach are discussed.     

Modeling and analysis of passive worm propagation in the P2P file-sharing network

A number of worms, named P2P (peer-to-peer) passive worms, have recently surfaced, which propagate in P2P file-sharing networks and have posed heavy threats to these networks. In contrast to the majority of Internet worms, it is by exploiting users’ legitimate activities instead of vulnerabilities of networks in which P2P passive worms propagate. This feature evidently slows down their propagation, which results in them not attracting an adequate amount of attention in literature. Meanwhile, this feature visibly increases the difficulty of detecting them, which makes it very possible for them to become epidemic. In this paper, we propose an analytical model for P2P passive worm propagation by adopting epidemiological approaches so as to identify their behaviors and predict the tendency of their propagation accurately. Compared with a few existing models, dynamic characteristics of P2P networks are taken into account. Based on this proposed model, the sufficient condition for the global stability of the worm free equilibrium is derived by applying epidemiological theories. Large scale simulation experiments have validated both the proposed model and the condition.