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.     

Polyaniline encapsulated Ti-MOF/CoS for efficient photocatalytic hydrogen evolution

We report the study of conductive polyaniline (PANI) chain embedded Ti-MOF functionalized with CoS as a cocatalyst for hydrogen evolution reaction (HER) application. The post synthetically modified hybrid photocatalyst PANI/Ti-MOF/CoS greatly influences the redox and e^? ? h⁺ separation process and exhibits an impressive rate of HER (～1322 μmol h^?1g^?1), suppressing the pristine Ti-MOF (～62 μmol h^?1g^?1) with apparent quantum yield (AQY) of ～3.2 and transient current response of ～46.4 μA cm^?2. In this system, Ti-MOF provides the circulation of Ti³⁺ and Ti⁴⁺ to the reaction of photocatalytic H₂ generation, where the additional PANI and CoS amended the performance of H₂ production through electron enrichment and thereby improving the stability and integrity of Ti-MOF. The Electrochemical studies demonstrated increased photocurrent by interweaving Ti-MOF crystal with PANI through cation-π interaction thereby enhancing interface connection and then promoting electron transfers. The charge dynamics revealed the initial charge transfer from photoexcited PANI to encapsulated MOF framework to boost the photocatalytic performance of the system. Further, the electron movement at the Ti-MOF/CoS interface is investigated through work function and electrochemical potential of electrons (Fermi level). DFT results demonstrate the importance of CoS in improving the photocatalytic performance of hybrid Ti-MOF catalyst, which leads to superior catalytic behaviour. These results establish that the encapsulation of catalytic active sites inside MOFs with desirable energy band gaps would be an ideal choice for the production of solar fuels.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Effect of cooking temperature on texture and flavour binding of braised sauce porcine skin

To investigate the effect of cooking temperature (55, 65, 75, 85 and 95 °C) on texture and flavour binding of braised sauce porcine skin (BSPS), sensory acceptance, microstructure and flavour-binding capacity were investigated during the processing of BSPS. Samples cooked at 85 and 95 °C showed better texture and aroma scores. Hardness and chewiness of BSPS were obviously improved at 85 and 95 °C than control group. Collagen structure was significantly destroyed over 85 °C. The porcine skin collagen heated at 85 and 95 °C showed relatively higher flavour-binding capacity than other samples. The improvement of texture of BSPS was mainly attributed to the degradation of collagen. Higher aroma scores of BSPS were related to intense binding abilities with aroma compounds at 85 and 95 °C. Cooking at 85 or 95 °C could be an optimal cooking temperature for BSPS.     

Prediction of Chameleonic Efficiency

Chameleonic properties, i. e., the capacity of a molecule to hide polarity in non-polar environments and expose it in water, help achieving sufficient permeability and solubility for drug molecules with high MW. We present models of experimental measures of polarity for a set of 24 FDA approved drugs (MW 405-1113) and one PROTAC (MW 1034). Conformational ensembles in aqueous and non-polar environments were generated using molecular dynamics. A linear regression model that predicts chromatographic apparent polarity (EPSA) with a mean unsigned error of 10 Ų was derived based on separate terms for donor, acceptor, and total molecular SASA. A good correlation (R²=0.92) with an experimental measure of hydrogen bond donor potential, Δlog P_oct-tol, was found for the mean hydrogen bond donor SASA of the conformational ensemble scaled with Abraham's A hydrogen bond acidity. Two quantitative measures of chameleonic behaviour, the chameleonic efficiency indices, are introduced. We envision that the methods presented herein will be useful to triage designed molecules and prioritize those with the best chance of achieving acceptable permeability and solubility.     

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.     

Salt-assisted solution combustion synthesis of NiFe2O4: Effect of salt type

The effects of three types of salt including NaF, KCl, and NaCl on the properties of NiFe₂O₄ nanoparticles using salt-assisted solution combustion synthesis (SSCS) have been investigated. The synthesized powders were evaluated by SEM, TEM, FTIR, XRD, and VSM analysis. Also, the specific surface area (SSA), as well as size distribution and volume of the porosities of NiFe₂O₄ powders were determined by the BET apparatus. The visual observations showed that the intensity and time of combustion synthesis of nanoparticles have been severely influenced by the type of salt. The highest crystallinity was observed in the synthesized powder using NaCl. The SSA has also been correlated completely to the type of salt. The quantities of SSA was achieved about 91.62, 64.88, and 47.22 m²g^-1 for the powders synthesized by KCl, NaCl, and NaF respectively. Although the magnetic hysteresis loops showed the soft ferromagnetic behavior of the NiFe₂O₄ nanoparticles in all conditions, KCl salt could produce the particles with the least coercivity and remanent magnetization. Based on the present study, the salt type is a key parameter in the SSCS process for the preparation of spinel ferrites. Thermodynamic evaluation also showed that the melting point and heat capacity are important parameters for the proper selection of the salt.     

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.