Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

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.     

Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Effect of temperature on raw whole milk density and its potential impact on milk payment in the dairy industry

The objective of this study was to determine the effect of temperature on whole milk density measured at four different temperatures: 5, 10, 15, and 20 °C. A total of ninety-three individual milk samples were collected from morning milking of thirty-two Holstein Friesian dairy cows, of national average genetic merit, once every two weeks over a period of 4 weeks and were assessed by Fourier transform infrared spectroscopy for milk composition analysis. Density of the milk was evaluated using two different analytical methods: a portable density meter DMA35 and a standard desktop model DMA4500M (Anton Paar GmbH, UK). Milk density was analysed with a linear mixed model with the fixed effects of sampling period, temperature and analysis method; triple interaction of sampling period x analysis method x temperature; and the random effect of cow to account for repeated measures. The effect of temperature on milk density (ρ) was also evaluated including temperature (t) as covariate with linear and quadratic effects within each analytic method. The regression equation describing the curvature and density–temperature relationship for the DMA35 instrument was ρ = 1.0338−0.00017T−0.0000122T² (R² = 0.64), while it was ρ = 1.0334 + 0.000057T−0.00001T² (R² = 0.61) for DMA4500 instrument. The mean density determined with DMA4500 at 5 °C was 1.0334 g cm⁻³, with corresponding figures of 1.0330, 1.0320 and 1.0305 g cm⁻³ at 10, 15 and 20 °C, respectively. The milk density values obtained in this study at specific temperatures will help to address any bias in weight–volume calculations and thus may also improve the financial and operational control for the dairy processors in Ireland and internationally.     

Mechanical damage characterization of glass fiber-reinforced polymer laminates by ultrasonic maps

A method for simultaneous measurement of the thickness and density for Glass Fiber-Reinforced Polymer (GFRP) laminate plates with ultrasonic waves in C-Scan mode is presented in the form of maps. The method uses three different signals in immersion pulse-echo C-Scan mode. The maps obtained based on the density show the heterogeneity of the material at high resolution at the pixel level (1 × 1 mm²) and therefore they represent an efficient tool to assess and evaluate the damage of the composite structures after manufacturing and after an applied mechanical loading.     

The effect of charge on the dihydrogen storage capacity of Sc2–C6H6

The effect of charge on the dihydrogen storage capacity of Sc₂–C₆H₆ has been investigated at B3LYP-D3/6-311G(d,p) level. The neutral system Sc₂–C₆H₆ can store 8H₂ with gravimetric density of 8.76 wt %, and one H₂ dissociates and bonds atomically on the scandium atom. The adsorption of 8H₂ on Sc₂–C₆H₆ is energetically favorable below 155 K. The atom-centered density matrix propagation (ADMP) molecular dynamics simulations show that Sc₂–C₆H₆ can adsorb 3H₂ within 1000 fs at 300K. Compared with Sc₂–C₆H₆, the charged systems can adsorb more hydrogen molecules with higher gravimetric density, and all the H₂ are adsorbed in the molecular form. The gravimetric densities of Sc₂–C₆H₆⁺ and Sc₂–C₆H₆²⁺ are 9.75 and 10.71 wt%. Moreover, the maximum adsorption of charged systems are favorable in wider temperature range. Most importantly, the ADMP-MD simulations indicate that Sc₂–C₆H₆²⁺ can adsorb 6 hydrogen molecules within 1000 fs at 300K. It can be found that the gravimetric density (6.72 wt%) of Sc₂–C₆H₆²⁺ still exceeds the target of US Department of Energy (DOE) under ambient conditions.     

Densities and Viscosities of Oleic Acid at Atmospheric Pressure

The densities of oleic acid were measured over the temperature range from (293 to 459) K at atmospheric pressure using a densimeter based on the modified hydrostatic weighing method. The dynamic viscosities of the same oleic acid sample were measured using a capillary viscometer (VPZ-2 m) in the range from (293 to 363) K at atmospheric pressure. The combined expanded uncertainty of the density, atmospheric pressure, viscosity, and temperature measurements at the 95% confidence level with a coverage factor of k = 2 is estimated to be 0.15%, 1.0%, 3.5%, and 15 mK, respectively. The values of uncertainty for density and viscosity include the effects of purity and calibration (total expanded uncertainty). These experimental data were used to develop wide-range correlations for the density and viscosity based on theoretically confirmed Arrhenius–Andrade and Vogel-Tamman-Fulcher (VTF) models. The value of the glass temperature ( T _g= 179.78 K.) for the oleic acid was estimated using the VTF parameters derived from the present viscosity measurements. To additionally validate the reliability of the measured density data, the same oleic acid samples were measured using the pycnometric method. The present study showed that the densities measured using the modified hydrostatic weighing densimeter (HWD) agree with the values obtained using the pycnometric method within 0.09% for Sample 1 and 0.25% for Sample 2.     

Fluoride-mediately solvothermal synthesis and tunable photocatalytic selectivity of urchin-like ZrO2 hollow microspheres

Photocatalysts often show excellent performances on the basis of their surface state of exposed faces with high reactivity, but unfortunately surfaces of this type are usually concealed into the interior of crystals for their high surface energy. We report here a possibility that for fluorine-terminated surfaces of monoclinic ZrO₂, these higher-energy surfaces could be retained and exposed. Urchin-like ZrO₂ hollow microspheres (UZHS) composed of nanoribbons with exposed (010) facets are obtained through a fluoride mediately solvothermal method. We prove the stabilization effect of fluorine adsorption on (010) facets by density functional theory calculations. More interestingly, UZHS exhibit tunable photocatalytic selectivity in dye degradation. The fluorinated UZHS exhibit good performances both on decomposing Congo red (CR) and methylene blue, while the surface-modified UZHS by calcination only favor decomposition of CR.     

In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.