Activation Energy For Diffusion Research Articles

Crystal plane orientation-dependent surface atom diffusion in sub-10-nm Au nanocrystals.

Surface atom diffusion is a ubiquitous phenomenon in nanostructured metals with ultrahigh surface-to-volume ratios. However, the fundamental atomic mechanism of surface atom diffusion remains elusive. Here, we report in situ atomic-scale observations of surface pressure-driven atom diffusion in gold nanocrystals at room temperature using high-resolution transmission electron microscopy with a high-speed detection camera. The topmost layer of atoms on (001) plane initially diffuse in a column-by-column manner. As diffusion proceeds, the remaining atomic columns collectively inject into adjacent underlayer, accompanied by nucleation of a surface dislocation. In comparison, atoms on (111) plane directly diffuse to the base without collective injection. Quantitative calculations indicate that these crystal plane orientation-dependent atom diffusion behaviors contribute to the larger diffusion coefficient of (111) plane compared to (001) plane in addition to the effect of diffusion activation energy. Our findings provide valuable insights into atomic mechanisms of diffusion-dominant morphology evolution of nanostructured metals and guide the design of nanostructured materials with enhanced structural stability.

Growth of variable aspect ratio ZnO nanorods by hydrothermal technique

Zinc oxide (ZnO) nanorods were successfully prepared by hydrothermal process. The influence of the solution temperature on the ZnO nanorods aspect ratio is investigated in the present work. The x-ray diffraction (XRD) and scanning electron microscopy (SEM) results and analysis reveal the formation of ZnO nanorods owing hexagonal Wurtzite structure with preferential orientation along the c-axis. We found that the solution temperature is a key parameter controlling the aspect ratio of the formed ZnO nanorods. The later increases linearly with the preparation temperature. The rod length is thermally activated with an activation energy of 0.48 eV, which corresponds to the activation energy of the reaction forming ZnO, indicating that the nanorods growth is controlled by the surface reaction rather than by mass transport. While, the rods diameter is reduced with increasing temperature, its activation energy of 0.23 eV is equal to the species diffusion activation energy in the solution and to the crystallite size activation energy suggesting, thereafter that the rod diameter variation is controlled by the nucleation dynamic.

High-throughput investigation of stability and Li diffusion of doped solid electrolytes via neural network potential without configurational knowledge

Solid electrolytes hold substantial promise as vital components of all-solid-state batteries. Enhancing their performance necessitates simultaneous improvements in their stability and lithium conductivity. These properties can be calculated using first-principles simulations, provided that the crystal structure of the material and the diffusion pathway through the material are known. However, solid electrolytes typically incorporate dopants to enhance their properties, necessitating the optimization of the dopant configuration for the simulations. Yet, performing such calculations via the first-principles approach is so costly that existing approaches usually rely on predetermined dopant configurations informed by existing knowledge or are limited to systems doped with only a few atoms. The proposed method enables the optimization of the dopant configuration with the support of neural network potential (NNP). Our approach entails the use of molecular dynamics to analyze the diffusion after the optimization of the dopant configuration. The application of our approach to Li10\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{10}$$\\end{document}MP2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}S12-x\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{12-x}$$\\end{document}Ox\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{x}$$\\end{document} (M = Ge, Si, or Sn) reproduce the experimental results well. Furthermore, analysis of the lithium diffusion pathways suggests that the activation energy of diffusion undergoes a percolation transition. This study demonstrates the effectiveness of NNPs in the systematic exploration of solid electrolytes.

New strategy in light-weight and ultrastrong Ti40Nb15Mo30(NbC)15 refractory complex concentrated alloy

Traditional refractory high-entropy alloys (RHEAs) generally exhibit a trade-off between high-temperature strength and light weight. In present work, a novel design strategy based on tailoring element distribution is proposed to achieve excellent high-temperature strength at a density lower than 7 g·cm-3. Specifically, a Ti40Nb15Mo30(NbC)15 composite was designed and prepared by powder metallurgy. The composite is found to be composed of two ultrafine-grained (UFG) phases including a body-centered cubic (bcc) solid-solution phase and a face-centered cubic (fcc) ceramic reinforcement phase (Ti, Nb)C. The as-sintered composite shows a uniform and UFG microstructure where two phases are interconnected. Due to this unique microstructure, the Ti40Nb15Mo30(NbC)15 composite displays superb specific yield strengths among surveyed RHEAs, complex concentrated alloys, and metal-matrix composites from 800°C (243 MPa·g-1·cm3) to 1000°C (127 MPa·g-1·cm3). The outstanding high-temperature compressive strength was found to be associated with high resistance to dislocation motion and strong dislocation interactions in both the bcc and fcc phases. The phase interface after hot compression remained semi-coherent, vindicating its high stability. The high-density of stable phase interfaces not only retards the dislocation motion due to the large image force near the phase boundary but also induces a high value of activation energy for diffusion. The high activation energy can further achieve significant microstructure stability even after a long-term annealing (36 h) at 1000°C. This work provides new perspectives for the design and application of light and ultrastrong refractory complex concentrated alloys (RCCAs) by comparison to the insufficient strength of many traditional and light RCCAs.

Drying kinetics and thermodynamic properties of jabuticaba peel

Jabuticaba is a fruit of high nutritional value, and the peel, which is usually discarded, contains nutrients in greater concentration. An alternative for the use of jabuticaba bark is the preparation of flour. The aim of this research was to analyze the drying kinetics of jabuticaba bark by adjusting mathematical models and determining the effective diffusion coefficient, activation energy, and thermodynamic properties at different drying temperatures. The jaboticaba residues were dried in a forced ventilation oven at different temperatures of 45, 55, 65, and 75°C. Among the various models analyzed, Page was employed to streamline the drying phenomenon. The research observed that effective diffusion coefficient decreased with increasing temperature, and the activation energy for the liquid diffusion on drying was 32.63 kJ mol-1. Furthermore, enthalpy and entropy decreased with increasing drying temperature, while Gibbs’ free energy increased with increasing drying temperature.

Investigating the role of network former interactions on charge carrier diffusivity in glasses

Ionic transport is a critical property for the glass industry, since emerging applications such as sensors, batteries, and electric melting are based on the phenomenon. Short-range interactions (anion-charge carrier) have not been able to explain the total activation barrier observed experimentally, and, as such, it is critical to understand the larger role of all ions in a glass, not just the carrier and the ‘site’ ions. This research focuses on the role of network formers and their impact on diffusion in glasses, something that current models lack an explicit explanation of. Atomistic simulations with randomly generated parameters for the cation potentials and classical simulations were used to determine the diffusion coefficients and activation energies for synthetic network formers. Using this database, explainable machine learning algorithms were employed to explore network former interactions and determine which parameters are the most influential for ion diffusion. Results suggest that the bond length of the cations changes the geometry of the structure contributing the greatest to cation-modifier interactions.

An insight into the influence of precipitation phase on the surface quality in diamond turning of an Aluminium alloy

Diamond turning is an effective technology for processing metal mirrors used in photoelectric communications, radar, and other fields. In diamond turning, the precipitated phase is an essential factor that influences the surface quality of the metal mirrors. However, in previous studies, the precipitation phase has typically been handled as a random variable in a surface morphology model to evaluate its influence on the surface roughness, instead of determining the formation mechanism and proposing suppression solutions. In this study, a new phenomenon is observed in the diamond turning of metal mirrors, that is, the micro diamond tool can reduce the protrusion of the precipitated phase under a small feed rate and improve the surface quality. Investigating the turning process using diamond tools with varying tool nose radii at small feed rates (<1 μm/r), the underlying transformation mechanism of the precipitation phase is determined with the advanced material characterization technologies. The growth of the precipitated phase with an increase in the tool nose radius is explained using the energy gradient theory. The results showed that the increased material strain on the machined surface decreased the activation energy of solute diffusion in the material, causing solute accumulation and precipitate phase growth. With a further increase of tool nose radius to around 1000 μm, the β'' phase breaks and rotates. The representative volume element method shows that when undergoing severe plastic deformation, dislocations and grain boundaries quickly aggregate and slide on the precipitated phase, which will lead to the fracture and rotation of β'' phase. These findings provide a theoretical basis for the development of highly smooth mirrors.

Entropy Drives Accelerated Ion Diffusion upon Carbon Dioxide Expansion of Electrolytes.

Carbon dioxide-expanded liquids, organic solvents with high concentrations of soluble carbon dioxide (CO2) at mild pressures, have gained attention as green catalytic media due to their improved properties over traditional solvents. More recently, carbon dioxide-expanded electrolytes (CXEs) have demonstrated improved reaction rates in the electrochemical reduction of CO2, by increasing the rate of delivery of CO2 to the electrode while maintaining facile charge transport. However, recent studies indicate that the limiting behavior of CXEs at higher CO2 pressures is a decline in solution conductivity due to reduced polarity, leading to poorer charge screening and greater ion pairing. In this article, we employ molecular dynamics simulations to investigate the energetic driving forces behind the diffusive properties of an acetonitrile and tetrapropylammonium hexafluorophosphate (TPrAPF6) CXE with increasing CO2 concentration. Our results indicate that entropy drives solvent and electrolyte diffusion with increasing CO2 pressure. The activation energy of ion diffusion increases with higher concentrations of CO2, indicating that increasing the temperature may improve solution conductivity in these systems. This trend in the activation energies is traced to stronger cation-anion Coulombic interactions due to weaker solvent screening at high CO2 concentrations, suggesting that the choice of ion may provide a route to diminish this effect.

Experimental study on moisture diffusivity, activation energy, and mathematical modeling of drying kohlrabi under different solar drying methods

AbstractThe assessment and enhancement of any drying system for optimal drying processes relies on critical parameters, namely moisture diffusivity and activation energy. In this study, medicinally beneficial kohlrabi of 40‐mm diameter and 6‐mm thickness samples were dried under three different drying methods, namely open sun drying (OSD), natural air‐circulation mode (NACM) single slope direct solar dryer (SSDSD), and forced air‐circulation mode (FACM) SSDSD. The experimental results showed that the drying chamber operating temperature and air velocity played significant roles in the moisture diffusion process and activation energy required to dry the kohlrabi sample. The FACM exhibited the highest average moisture diffusivity values at 7.29 × 10−10 m2/s, surpassing both NACM (5.65 × 10−10 m2/s) and OSD (3.28 × 10−10 m2/s). The activation energy needed for the drying process was the lowest in FACM at 27.44 kJ/mol, followed by NACM at 31.37 kJ/mol and OSD at 35.29 kJ/mol. This is due to the uniform temperature distribution and high airflow rate in the case of FACM. Additionally, 10 thin‐layer models were tested for all three experimental conditions. The statistical analysis showed that for OSD and NACM, the Midilli et al. model, and for FACM, the Page model was best suited for representing drying kinetics with lowest χ2 and root mean square error and highest R2 values. Furthermore, the energy and exergy assessment guaranteed an evaluation of the solar drying system's efficiency.Practical applicationsThis research provides valuable insights into optimizing solar drying methods for kohlrabi preservation. Understanding how temperature and air velocity influence moisture diffusivity and activation energy allows practitioners to enhance drying efficiency. Forced air‐circulation mode (FACM) single slope direct solar dryer (SSDSD) emerges superior, with higher moisture diffusivity and lower activation energy. The study also identifies appropriate drying kinetics models for each method, aiding the accurate prediction of drying behavior. Emphasizing efficiency, the research highlights FACM's superior thermal efficiency and natural air‐circulation mode's higher exergetic efficiency. These insights empower practitioners to make informed decisions, potentially improving agricultural product preservation, reducing energy consumption, and promoting sustainability. Moreover, the research's findings hold significant implications for industrial food processing and preservation applications, suggesting the direct implementation of optimized solar drying techniques in large‐scale settings for kohlrabi and similar agricultural products.

Mechanical properties: Lifespan and retention forecast for jute fiber woven fabric reinforced epoxy matrix composite

AbstractPolymer composites bonded with natural fibers are extensively used for a range of engineering purposes. Preserving their mechanical strength and estimating their maximum service life are thus essential for efficient usage. The primary goals of this effort are to analyze and forecast the longest possible life span of composites. To do this, Fick's law and the Arrhenius principle are employed to analyze the diffusion coefficient and activation energy. Compression molding technology and a manual technique for layup were employed to make the composites reinforced with epoxy laminate and woven mats of jute fiber (JRC). Three layering patterns were used to prepare the laminated composite: 45° angle‐ply laminate [0°/+45°/0°/−45°/0°], 0° balanced laminate [0°/0°/0°/0°/0°/0°], and 30° angle‐ply laminate [0°/+30°/0°/−30°/0°]. In order to examine how aging affected the composites' mechanical properties, the materials were immersed in water for 10, 20, 30, and 40 days throughout the study. The study's conclusions showed that the composite samples' weight rose with age. It was possible to make precise predictions about strength retention by comparing the mechanical characteristics of aged (wet) and unaged composites. It was discovered that the strongest composites were those with a 45‐degree stacking pattern. The activation energy of composites with a 45° angle‐ply laminate layering pattern is maximum, according to the Arrhenius principle. Additionally, using an electron microscope with scanning capabilities (SEM), it was possible to determine the fiber matrix and the tensile cracked surface contact connection.Highlights The widespread usage of polymer composites with natural fibers in engineering applications. Preservation of mechanical strength and predicting the maximum service life of these composites show how important these materials are for engineering efficiency. Fick's rule and the Arrhenius principle are used to analyze diffusion coefficient and activation energy. Laminated composites are made using 45° angle‐ply, 0° balanced laminate, and 30° angle‐ply layering patterns. The impact of simulated aging on composite mechanical characteristics by water immersion for varied periods.

Feeling the strain: Enhancing the thermodynamics characteristics of magnesium nickel hydride Mg2NiH4 for hydrogen storage applications through strain engineering

This work is based on density functional theory (DFT) and studies the structural, electronic, thermodynamic properties and dehydrogenation kinetics of the hydride Mg2NiH4 under different uniaxial and biaxial strain applied to Mg2Ni or Mg2NiH4. structural properties are first studied based on generalized gradient (GGA) and local density (LDA). Thermodynamic and electronic properties and dehydrogenation kinetics are then studied using the GGA method based on the Perdew-Burke-Ernzerhor (PPE) approximation. The results obtained show that uniaxial/biaxial tensile and compressive strains are capable of inducing structural deformation by increasing the value of the strain step on both Mg2Ni and Mg2NiH4, and that these strains applied to Mg2NiH4 are capable of reducing the stability of the system more than strains applied to Mg2Ni, due to the contribution of strain energy. More specifically, it lowers the enthalpy of formation to −40 kJ/mol.H2 under compressive strain ε = −7.5% or biaxial tensile strain ε = +7.8%, which corresponds exactly to the ideal value suggested by the US Department of Energy (DOE) for materials suitable for hydrogen storage. And the decomposition temperature fell within the fuel cell operating range (PEM) of 289–393 K. On the other hand, under uniaxial and biaxial strains, the activation energy of hydrogen atom diffusion in Mg2NiH4 varied between 0.40 eV and 0.22 eV, resulting in a remarkable improvement in dehydrogenation properties. Analysis of the total (TDOS) and partial (PDOS) density curves shows that the Mg2NiH4 system has a metallic characteristic, and that this characteristic is maintained by increasing the strain pitch, with a variation in the energy width of the valence band.

Towards a low-emission resource circulation of valuable metals from municipal solid waste incineration fly ash

The incineration fly ash (IFA) resulting from municipal solid waste combustion is laden with heavy metals, necessitating proper treatment not only for environmental management but also to reclaim the metal values. The surge in non-traditional metals like cobalt as emerging contaminant within IFA samples further attracts to address this issue. In response, the hydrometallurgical recycling of a cobalt-bearing IFA has been studied. Thereby, approximately 98 % zinc and 96 % cobalt were leached using a 1.0 mol/L H2SO4 solution at 90 °C and 1 h of leaching time. In-depth analysis of the leaching process unveiled metals' dissolution primarily via the ion-exclusion mechanism, as evidenced by lower diffusion coefficients (between 10−9 and 10−11 m2/s) and activation energies (9.6–14.9 kJ/mol). Above 99 % separation of zinc from the cobalt-bearing leach liquor was achieved by extraction with 1.0 mol/L D2EHPA at an equilibrium pH below 3.0, followed by stripping with a 2.0 mol/L H2SO4 solution. Cobalt, remained in the raffinate was efficiently precipitated by adding a 20 % excess dosage of oxalic acid to the stoichiometric ratio of C2O42−:Co2+, resulting in only 5 mg/L cobalt left in the solution when precipitation occurred at a pH of 2.8. Additionally, the conversion of CoC2O4 to high-purity Co3O4 was conducted through heat-treatment at 600 °C. The resulting Co3O4 was mixed with Li2CO3 at a Li/Co molar ratio of 1.1, yielding a LiCoO2 precursor that exhibited good electrochemical properties with a capacity of 128 mAh/g, thus affirming the high quality of the recycled cobalt. A comprehensive life-cycle assessment of the recycling process revealed that cobalt precipitation alone contributes approximately 50 % of the total global warming potential (GWP = 4.2624 kg CO2-eq). Notably, this value is remarkably lower than the GWP reported for primary cobalt production, highlighting the environmentally-friendly approach of this recycling endeavor.

Electrochemical behavior of aluminum in 1-ethyl-3-methylimidazolium chloroaluminate ionic liquids

The mechanism of electrochemical oxidation and reduction of aluminum in 1-ethyl-3-methylimidazolium-based (EMImCl) chloroaluminate ionic liquids is studied across the concentration range of N = 1.1–2.0 (N the molar ratio of AlCl3 to EMImCl) at temperatures between 303 K and 418 К. Anodic stationary polarization curves (SPCs) indicate that the process of anodic dissolution of aluminum is complicated by passivation. The current density in the passive region and the passivation potential decrease with a higher concentration of Al2Cl7– ion in the melt. To elucidate the processes taking place at the aluminum electrode, the relationship between the concentration of the ions in the vicinity of the electrode and the potential applied in the cathodic and anodic region was analyzed by in-situ Raman spectroscopy for the concentrations of N = 1.1 and 2.0. The resulting dependences of relative peak intensity vs. potential correlate with the cathodic and anodic polarization curves. In the anodic region the content of Al2Cl7– grows with the potential, while the concentration of AlCl4– ion decreases. In the cathodic region the opposite process is observed: the concentration of Al2Cl7– decreases and that of AlCl4–increases with growing potential. It is shown that a precipitate of AlCl3 forms on the electrode surface in the region of passive aluminum dissolution, which is responsible for the electrode passivation. Based on the results obtained, we propose a model for the process of aluminum oxidation/reduction preceded and followed by a chemical reaction of aluminum chloride formation for the cathodic and anodic process, respectively. Temperature dependences of diffusion coefficients are studied by chronopotentiometry. The results indicate that diffusion coefficients are not affected by the concentration across the temperature range studied. The activation energy for diffusion was found to be 13.65 kJ∙mol−1. Impedance spectroscopy was used to investigate the concentration and temperature dependences of exchange current density. The exchange currents increase with increasing aluminum chloride content in the melt. The transfer coefficient and electrochemical reaction rate constant were found to be α = 0.17 ± 0.04, ks = (1.7 ± 0.4)∙10−6 cm∙s−1, respectively. The activation energy for the electrochemical reaction rate constant does not depend on the concentration and was found to be 33.5 kJ∙mol−1.

Reconstructing brittle hydrides using pulsed electric current to restore the degraded performance of zirconium alloys

When zirconium alloy undergoes water corrosion reaction during the service process, it absorbs hydrogen to form brittle hydrides, which is one of the main reasons for the deterioration of the mechanical properties of zirconium alloy. There is an urgent need to find an effective method to regulate brittle hydrides to restore the properties of hydrogen-containing zirconium alloys. This study conducted electropulsing treatment on the hydrogen-charged nuclear grade Zr-4 alloy, and the results showed that the electropulsing process caused the hydrides to transform from large-sized brittle stripe-shaped δ-phase to the small-sized ζ-phase. The hydrogen content in the alloy is significantly reduced, which basically restores the mechanical properties of the alloy. However, in the comparative experiment of isothermal heat treatment at 400 °C, brittle hydrides did not dissolve and their mechanical properties did not recover. A mathematical model was established for the characteristics and morphological changes of strip hydrides, and the current density distribution and introduced free energy during the microstructure evolution process were calculated and analyzed. The calculation results indicate that the pulsed current promotes the decomposition of hydrides through the introduction of free energy, reduces the activation energy of hydrogen atom diffusion, accelerates the diffusion and desorption of hydrogen atoms, and realizes the repair of mechanical properties of hydrogen-charged zirconium alloy.

Deuterium permeation of low-activation vanadium alloys possible for reuse in a short time in fusion reactors

Low-activation vanadium (V) alloys are alternative to reduced-activation ferritic/martensitic steels for the blanket structural material. To make the reusage of the alloys possible in a short time, new-design concepts of V alloy have been suggested in National Institute for Fusion Science. In the present study, the deuterium permeation properties of the new-designed V alloys were investigated.The new-designed V-4Cr-4Ti alloy samples with high and low purity, named H44 and L44, respectively, were used. For comparison, the NIFS-HEAT-2 V alloy samples, named NH2 were also used.It was found from the permeation experiments that deuterium permeability coefficient of L44 was smaller than that of NH2, while the permeability coefficient of H44 was comparable with NH2. These results suggest the permeation coefficient of D of the new-designed V alloy was similar to those of the conventional V alloy, if Ti and O content was the same. Estimated activation energies of diffusion and permeation indicated that the permeation behaviors significantly depended on titanium oxides at the surface and in the bulk. Data obtained by a microscope with Auger electron spectroscopy indicated that the concentration and the composition of the oxide must change with air exposure during the maintenance and with hydrogen isotope exposure during the reactor operation. The obtained results suggest these changes of the concentration and the composition result in the change in the permeation characteristics of hydrogen isotopes.

Low voltage resistance switching characteristics of Cu/MoS2/Cu/ITO devices

The resistive switching behavior is observed in the Cu/MoS2/Cu/ITO structures, which has been deposited by magnetron sputtering. With the increase in MoS2 thickness, the resistive switching behavior is gradually weakened. The optimal device with a MoS2 thickness of 120[Formula: see text]nm has a lower Set voltage and Reset voltage, where Set voltage is 0.14–0.3[Formula: see text]V and Reset voltage is −0.24[Formula: see text]V to −0.08[Formula: see text]V. The device also has a resistive switching ratio of up to 105 high resistance state/low resistance state, a data retention time over 104[Formula: see text]s, and can endure more than 103 cycles. As the limiting current increases, the resistance switching (RS) characteristics of devices with MoS2 thickness of 200[Formula: see text]nm at both positive and negative biases are improved. There is no RS behavior in ITO/MoS2/ITO devices fabricated by the same method, which indicates that sulfur vacancies have little effect on the RS characteristics of Cu/MoS2/Cu/ITO devices. Moreover, since the migration barrier and diffusion activation energy of Cu in MoS2 are lower than those of sulfur vacancy, combined with the data fitting structure, it is shown that the RS behavior is formed because Cu ions control the connectivity and fracture of conductive filaments through the diffusion and migration of MoS2 layer.

In English

The total reorganization energy of the system and its components, the solvent reorganization energy and the transformation energy of reactants (water clusters [(H2O)nOH]-), during electrocatalytic hydrogen evolution on binary alloys of molybdenum with iron subgroup metals (Fe, Co, Ni) in an alkaline medium (30 wt. % NaOH solution) have been calculated. The calculated values of the solvent reorganization energy and the reorganization energy of water clusters are in agreement with the Marcus – Dogonadze – Kuznetsov theory. The dependence of the total reorganization energy of the system, the solvent reorganization energy, and the reorganization energy of discharging species (water clusters) on the electrolyte temperature has been calculated. It was shown that the total reorganization energy of the system and the activation energy of the electron-transfer reaction of electrocatalytic hydrogen evolution (HER) on binary alloys of molybdenum with iron subgroup metals in an alcaline vedium (30 wt. % NaOH solution) decrease linearly with increasing electrolyte temperature in the following order: Fe-54 at. % Mo &gt; Ni-54 at. % Mo &gt; Co-52 at. % Mo. The temperature dependences of the water cluster discharge reorganization energy and the activation energy on binary molybdenum alloys are linear and intersect in the boiling point region of 30 wt. % NaOH solution 384.7 K. At this temperature, the electrode process is limited by the diffusion of regenerating water clusters to the electrode surface. The calculated diffusion activation energy Ad is 9.9 kJ·mol–1. The value of the system reorganization energy lt is 39.8 kJ·mol–1, which is consistent with the theory of Markus – Dogonadze – Kuznetsov. Electrocatalytic activity of binary alloys of molybdenum with iron subgroup m

Enhanced Li+ and Mg2+ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

AbstractWith the widespread use of batteries, their increased performance is of growing in importance. One avenue for this is the enhancement of ion diffusion, particularly for solid‐state electrolytes, for different ions such as lithium (Li+) and magnesium (Mg2+). Unraveling the origin of better cation diffusion in confined ionic liquids (ILs) in a polymer matrix (ionogels) is compared to that of the IL itself. Ionic conductivity measured by electrochemical impedance spectroscopy for ionogels (7.0 mS cm−1 at 30 °C) is very close to the conductivity of the non‐confined IL (8.9 mS cm−1 at 30 °C), that is, 1‐ethyl‐3‐methyimidazolium bis(trifluorosulfonyl)imide (EMIM TFSI). An even better ionic conductivity is observed for confined EMIM TFSI with high concentrations (1 m) of lithium or magnesium salt added. The improved macroscopic transport properties can be explained by the higher self‐diffusion of each ion at the liquid‐to‐solid interface induced by the confinement in a poly‐vinylidenedifluoride (PVDF) polymer matrix. Upon confinement, the strong breaking down of ion aggregates enables a better diffusion, especially for TFSI anion and strongly polarizing cations (e.g., Li+, Mg2+.). The coordination number of these cations in the liquid phase confirmed that Li+ and Mg2+ interact with the polymer matrix. Moreover, it is a major result that the activation energy for diffusion is lowered.

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Solar drying of oregano leaves (Plectranthus amboinicus, Lour): Analysis of experimental performance under a tropical climate

Despite the multiple applications of the oregano ( Plectranthus amboinicus (Lour)), an important herbaceous plant because of its medicinal and culinary properties, limited research has been conducted on this species’ solar drying. Thus, the experimental drying of oregano leaves in a tropical climate was performed using direct and indirect solar drying and an electric oven in this research work. Also, mathematical modeling of the drying process, moisture diffusivity, activation energy, and colorimetric analysis (as a quality parameter) were accomplished to complement the experimental evaluation and understand the drying process behavior. The results show a shorter drying time obtained with the electric oven with 210 min reached at 65°C; however, the minimum solar drying time (250 min) was achieved with a maximum drying rate of 0.025 g water/g dry matter per minute and minimum final moisture between 0.28 and 0.13 g water/g dry matter was obtained with indirect solar dryer. Moreover, the models that better represented the experimental data were Modified Page, Page, and Logarithmic, with a maximum value of R2 obtained of 0.9980 corresponding to the Logarithmic model. Furthermore, a maximum effective diffusivity value of 1.81E-9 was obtained with direct solar dryer natural convection, while for the electric oven, were 1.14E-10, 2.280E-10, and 1.026E-09 for 45, 55, and 65°C, respectively. The activation energy for water diffusion in oregano leaves was 55.66 and 97.78 kJ/g mol for solar dryers and electric ovens, respectively, which were values very close to those reported in the literature. Finally, the colorimetric analysis exhibited a minimum color change value of 17.1 obtained for the indirect solar dryer, allowing better oregano preservation and maintaining its quality for the market, which makes it ideal for drying oregano in tropical climates and promotes solar drying use for sustainable growth of the region.