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The interfacial structure and adsorption behavior of 1-butyl-3-methylimidazolium thiocyanate ionic liquids (ILs) aqueous solutions were investigated using sum-frequency generation vibrational spectroscopy (SFG-VS) and surface tension measurements. Polarization-dependent measurements revealed a dramatic increase in the SFG signal for both CH and CN stretching modes with increasing ILs concentration, reaching a maximum at a mole fraction of 0.01. This concentration dependence was accompanied by a dramatic drop in surface tension. Upon further increasing the concentration, surface tension varied slightly and reached a constant value, while the SFG signal decreased significantly. Quantitative polarization analysis showed that as the bulk concentration increased, the apparent molecular orientation of the SCN− transition dipole at the interface changed from 51° to 46°, and the tilt angle of CH3 group of the butyl chain attached to the imidazole cationic ring changed from 18° to 32°. The decrease in the SFG signal can be explained by the formation of a double layer adsorption structure at the air/water interface. It was also demonstrated that the anions were adsorbed at the interface simultaneously with the cationic group, rather than by successive adsorption as proposed in a previous study. Using the Shereshefsky model, the thermodynamic Gibbs free energy of adsorption deduced from surface tension data was compared with SFG results. [ABSTRACT FROM AUTHOR]

We have implemented a cluster-continuum method using density functional theory to model water clusters and various charged species derived from water. The two aims of this study are to determine the minimal basis required for proper modeling of water autoionization and to determine the minimum number of explicit water molecules required to properly model the energetics of solvation. The thermodynamics of water autoionization converge following a modified power law to deliver chemically accurate values of the Gibbs energy change for autoionization with tractably small clusters. Convergence is slower and not exponential as assumed in previous work. We identify the n = 21 set of clusters as the first effectively bulk water like clusters that can capture the energetic influence of both the first and second solvation shells. In this cluster, a water molecule is encapsulated in the center of a closed shell of other water molecules that hydrogen bond to form five-membered rings. The total energy change for clusters with n ≥ 21 calculated using both the RPBE-D3 and ωB97X-D exchange–correlation functionals with the 6-311+G** basis set is shown to deliver good approximations to the free energy change at 298 K. This is true even though neither functional models the individual enthalpy or entropy contributions particularly well. [ABSTRACT FROM AUTHOR]

In this study, we explored the phase stability of quaternary Mo 1 − x M x AlB (M = Cr, Fe, Mn, Nb, Sc, Ta, Ti, V, and W) solid solutions by employing a cluster expansion method to generate structures with different concentrations of M atoms. Using the first-principles calculations based on density functional theory, we predicted that these compounds exhibit a preference for either fully random structures or phase-segregated (M-rich regions) phases against the competing phases. To evaluate the Gibbs free energy of Mo 1 − x M x AlB alloys, we investigated the impact of various entropy contributions, including configurational, electronic, and vibrational entropy. Our study revealed that configurational entropy plays an important role in stabilizing the random phases observed in Mo 1 − x M x AlB compounds, highlighting its importance in understanding the thermodynamic behavior of these alloys. However, the vibrational and electronic entropy changes with respect to competing phases can stabilize or destabilize Mo 1 − x M x AlB depending on their sign. Our results indicate that, while W is soluble across the entire range of mixing ratios, Sc and Ti are completely insoluble in any ratio. On the other hand, Cr, Ta, Nb, and V can be successfully incorporated into the MoAlB lattice at varying fractions at elevated temperatures. The size, valence electron concentration, and electronegativity differences between Mo and M can be utilized as descriptors to identify stable Mo 1 − x M x AlB compounds. We extensively examined the structural, dynamical stability, thermal conductivity, and mechanical properties of Mo 1 − x M x AlB compounds. We analyze their dependence on the choice of the M element incorporated in the alloy. Our findings can guide the design and engineering of these materials to tailor their properties to specific applications based on the choice of the M element. [ABSTRACT FROM AUTHOR]

The isomerization of azobenzo-13-crown ether can be expected to be hindered due to the polyoxyethylene linkage connecting the 2,2′-positions of azobenzene. The mixed reference spin-flip time-dependent density functional theory results reveal that the planar and rotational minima of the first photo-excited singlet state (S1) of the trans-isomer pass through a barrier (2.5–5.0 kcal/mol) as it goes toward the torsional conical intersection (S0/S1) geometry (

Thermodynamic potentials play a substantial role in numerous scientific disciplines and serve as basic constructs for describing the behavior of matter. Despite their significance, comprehensive investigations of their topological characteristics and their connections to molecular interactions have eluded exploration due to experimental inaccessibility issues. This study addresses this gap by analyzing the topology of the Helmholtz energy, Gibbs energy, Grand potential, and Null potential that are associated with different isothermal boundary conditions. By employing Monte Carlo simulations in the NVT, NpT, and μVT ensembles and a molecular-based equation of state, methane, ethane, nitrogen, and methanol are investigated over a broad range of thermodynamic conditions. The predictions from the two independent methods are overall in very good agreement. Although distinct quantitative differences among the fluids are observed, the overall topology of the individual thermodynamic potentials remains unaffected by the molecular architecture, which is in line with the corresponding states principle—as expected. Furthermore, a comparative analysis reveals significant differences between the total potentials and their residual contributions. [ABSTRACT FROM AUTHOR]

Hydration and, in particular, the coordination number of a metal ion is of paramount importance as it defines many of its (bio)physicochemical properties. It is not only essential for understanding its behavior in aqueous solutions but also determines the metal ion reference state and its binding energy to (bio)molecules. In this paper, for divalent metal cations Ca 2 + , Cd 2 + , Cu 2 + , Fe 2 + , Hg 2 + , Mg 2 + , Ni 2 + , Pb 2 + , and Zn 2 + , we compare two approaches for predicting hydration numbers: (1) a mixed explicit/continuum DFT-D3//COSMO-RS solvation model and (2) density functional theory based ab initio molecular dynamics. The former approach is employed to calculate the Gibbs free energy change for the sequential hydration reactions, starting from [M( H 2 O)2]2+ aqua complexes to [M( H 2 O) 9]2+, allowing explicit water molecules to bind in the first or second coordination sphere and determining the most stable [M( H 2 O) n]2+ structure. In the latter approach, the hydration number is obtained by integrating the ion–water radial distribution function. With a couple of exceptions, the metal ion hydration numbers predicted by the two approaches are in mutual agreement, as well as in agreement with the experimental data. [ABSTRACT FROM AUTHOR]

According to the classic theory of nucleation around a charged particle, dipoles induced in the particle's neighbors by the charged nucleation center decrease the electric field around it. This reduces the system's Gibbs energy and thus increases the nucleation rate. Unlike the situation of a neutral gas and an already existing charged particle, in plasma, charging the center of nucleation is the result of the separation of charges (a negatively charged center and a positively charged surrounding). This process being similar to charging of a capacitor, it demands extra energy, and thus increases the Gibbs energy. As a result, the nucleation rate decreases in comparison with the nucleation rate in a neutral medium. In this work, the process of nucleation in a plasma is considered and the nucleation rate is calculated. It is shown that for the conditions typical for arcs used for the production of nanoparticles, the reduction in the nucleation rate is an order of magnitude or higher. [ABSTRACT FROM AUTHOR]

Mixing Gibbs energy and phase equilibria of aqueous solutions of polyglycine were studied theoretically by means of polymer reference interaction site model integral equation theory combined with the Gibbs–Duhem method. In addition to the ordinary liquid–liquid phase separation between dilute and concentrated solutions, the theoretical calculation predicted the coexistence of two coacervate phases, namely, the lower- and higher-density coacervates. The relative thermodynamic stabilities of these two phases change with the polymerization degree of polyglycine. The higher-density coacervate phase was rapidly stabilized by increasing the polymer length, and the lower-density phase became metastable at large polymers. The hydrogen bonds between the peptide chains were strengthened, and water was thermodynamically destabilized in the higher-density coacervate. A possible relation with the formation of amyloid fibril within a liquid droplet is also discussed. [ABSTRACT FROM AUTHOR]

Constructing metal-semiconductor interfaces by loading metal atoms onto two-dimensional material to build atomically dispersed single-atom catalysts (SACs) has emerged as a new frontier for improving atom utilization and designing multifunctional electrocatalysts. Nowadays, studies on black phosphorus nanosheets in electrocatalysis have received much attention and the successful preparation of metal nanoparticle/black phosphorus (BP) hybrid electrocatalysts indicates BP nanosheets can serve as a potential support platform for SACs. Herein, by using large-scale ab initio calculations, we explored a large composition space of SACs with transition metal atoms supported on BP monolayer (M-BP) and built a comprehensive picture of activity trend, stability, and electronic origin towards oxygen reduction and evolution reaction (ORR and OER) and hydrogen evolution reaction (HER). The results show that the catalytic activity can be widely tuned by reasonable regulation of metal atoms. Ni-, Pd-, and Pt-BP could effectively balance the binding strength of the target intermediates, thus achieving efficient bifunctional activity for OER and ORR. Favorable bifunctional catalytic performance for OER and HER can be realized on Rh-BP. Especially, Pt-BP exhibits promising trifunctional activity towards OER, ORR, and HER. Multiple-level corrections among overpotential, Gibbs free energy, orbital population, and d-band center reveal that the trend and origin of catalytic activity are intrinsically determined by the d-band center of metal sites. The thermodynamic and dynamic stability simulations demonstrate that the active metal centers are firmly anchored on BP substrate with intact M-P bonds. These findings provide a theoretical basis for the rational design of BP-based SACs toward promising multifunctional activity. [ABSTRACT FROM AUTHOR]

This paper presents an exploration of a specific type of a generalized multicomponent solution model, which appears to be first given by Saulov in the current explicit form. The assumptions of the underlying theory and a brief derivation of the main equation have been provided preliminarily for completeness and notational consistency. The resulting formulae for the Gibbs free energy of mixing and the chemical potentials are multivariate polynomials with physically meaningful coefficients and the mole fractions of the components as variables. With one additional assumption about the relative magnitudes of the solvent–solute and solute–solute interaction exchange energies, combining rules were obtained that express the mixed coefficients of the polynomial in terms of its pure coefficients. This was done by exploiting the mathematical structure of the asymmetric form of the solvent chemical potential equation. The combining rules allow one to calculate the thermodynamic properties of the solvent with multiple solutes from binary mixture data only (i.e., each solute with the solvent), and hence, are of practical importance. Furthermore, a connection was established between the osmotic virial coefficients derived in this work and the original osmotic virial coefficients of Hill found by employing a different procedure, illustrating the equivalency of what appears to be two different theories. A validation of the combining rules derived here has been provided in a separate paper where they were successfully used to predict the freezing points of ternary salt solutions of water. [ABSTRACT FROM AUTHOR]

The high activity and high selectivity in the catalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) under non-alkaline conditions has always been a significant challenge in the field of biomass utilization. In this work, a thermodynamically stabilized high-entropy alloy (HEA) structure with relatively low Pt content was synthesized via a simple impregnation–calcination procedure by tuning the mixing enthalpy and the Gibbs free energy of the metal-mixing system. The prepared HEA shows excellent catalytic performance in the aerobic oxidation of HMF into FDCA under base-free conditions. Experiments and DFT calculations revealed that molecular O2 can be easily activated into highly oxidative hydroxyl radicals (˙OH) in the presence of water over the HEA surface, and facilitates the oxidation of HMF to FDCA under base-free conditions. This work provides a valuable reference for similar aerobic oxidation processes in which alkaline promoters and noble metal catalysts are needed. [ABSTRACT FROM AUTHOR]

Traditional studies on boride cermet have rarely considered the effects of the synergistic interactions among their multiple components on their microstructure and properties. In this study, FeCrNiCo-boride cermet is prepared for the first time via hot-press sintering. The microstructure evolution and corrosion resistance of the cermet are investigated for sintering temperatures in the range of 1000–1300 °C. The results show that the phase comprises Mo 2 FeB 2 , MoB 2 , and FCC phases (including that of FeCrNiCo or various intermetallic solid solutions formed by FeCrNiCo decomposition). Owing to its low Gibbs free energy, Mo 2 FeB 2 occurs in the hard phase. Cr atoms dissolve into the crystal lattice and stabilise the Mo 2 FeB 2 crystals. A certain amount of MoB 2 is also present in the hard phase. The bond phase is formed by alloying elements and solid solutions. The cermet sintered at 1100 °C exhibits the least structural defects, highest cermet content, and best corrosion resistance; the porosity is 9.94 % and phase ratio of cermet is 48.9 %. The cermet phase has the smallest grain size of 5.96 μm. The equilibrium potential (E corr) is −0.52 V, corrosion current density (I corr) is 2.07 × 10−6 A/cm2, and open-circuit potential (OCP) in a 3.5 % NaCl solution is −0.34 V. [ABSTRACT FROM AUTHOR]

This work aims to investigate the combustion characteristics, kinetics triplets, and thermodynamic parameters of microporous triazine-based organic polymers. The polymers were prepared by the incorporation of aliphatic and aromatic diamines (e.g., 1,4-hexane diamine (Hex) and 1,4-phenylenediamine (Bz)) with triazine core (Tr) via polycondensation polymerization. Both polymers Tr–Hex-diamine and Tr–Bz-diamine are microporous with a surface area of 212 and 524 m2/g, respectively. The successful synthesis was confirmed from FTIR and solid-state 13C CP-MAS. The combustion index (SN), kinetic triplets, apparent activation energy (Ea), pre-exponential factor (A), and thermodynamic parameters were estimated from the thermal degradation profiles of the polymers (TGA) at different heating rates. At the maximum heating rate (20 °C/min) the SN of Tr–Bz-diamine is 2.08, while it reached 4.2 for Tr–Hex-diamine, which indicates the high rate of combustion of the aliphatic hexyl chains. The other kinetic and thermodynamic parameters were determined by applying model-free isoconversional methods including Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (OFW), and Kissinger. From KAS, the average Ea for Tr–Bz-diamine and Tr–Hex-diamine are 163.4 and 147.8 kJ/mol, while 169.2 and 151.7 kJ/mol from OFW calculations. These values are higher in the case of the Kissinger method. The degradation mechanism and the rate of decomposition were determined from the Coats–Redfern method and by applying the master plot methods. Comparing the Ea values of the CR method with the integral method shows the possibility of the chemical reaction F3 mechanism beside multiple parallel reactions as shown by the master plot. The pre-exponential factor (A) along with the thermodynamic parameters (e.g., heat of enthalpy, entropy, and Gibbs free energy) were also determined and found to be within the same range of all methods. [ABSTRACT FROM AUTHOR]

Layered Ruddlesden-Popper (RP) neodymium nickelate oxide, Nd 2 NiO 4+δ , is considered a potential cathode material in solid oxide fuel cells. In this study, the equilibrium properties of NNO were investigated by using quasi-equilibrium oxygen release to contract the isothermal equilibrium diagram "lg pO 2 – (4+δ) – T". Furthermore, the kinetic properties of NNO were studied by oxygen partial pressure relaxation to determine the equilibrium oxygen exchange rate (R 0), chemical diffusion coefficient in oxide (D chem), and surface exchange rate constant (k chem). The Brønsted-Evans-Polanyi-type linear free energy relationship was shown to exist between the standard Gibbs energy of the reaction and the activation energy of the reaction rate constant. [ABSTRACT FROM AUTHOR]

A carefully designed C and S co doped Co 2 VO 4 /CoP heterojunction strategy was constructed using a synergistic approach of hydrothermal and vapor deposition. This strategy requires the synergistic improvement of thermodynamic performance by adjusting electronic structure and nanoscale kinetic improvements, resulting in efficient dual functionality for seawater decomposition. [Display omitted] The endeavor to architect bifunctional electrocatalysts that exhibit both exceptional activity and durability heralds an era of boundless potential for the comprehensive electrolysis of seawater, an aspiration that, nevertheless, poses a substantial challenge. Within this work, we describe the precise engineering of a three-dimensional interconnected nanoparticle system named S C doped Co 2 VO 4 /CoP (S C Co 2 VO 4), achieved through a meticulously arranged hydrothermal treatment sequence followed by gas-phase carbonization and phosphorization. The resulting S C Co 2 VO 4 electrode exhibits outstanding bifunctional electrocatalytic stability, attributed to the strategic anionic doping and abundant heterogeneous interfaces. Doping not only adjusts the electronic structure, enhancing electron transfer efficiency but also optimizes the surface-active sites. This electrode prodigiously necessitated an extraordinarily minimal overpotential of merely 92 and 350 mV to attain current densities of 10 and 50 mA cm−2 for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1 M KOH solution. Noteworthily, when integrated into an electrolyzer for the exhaustive splitting of seawater, the S C P-Co 2 VO 4 manifested an exceptionally low cell voltage of 2.08 V@50 mA cm−2 and showcased a durability that eclipses that of most hitherto documented nickel-based bifunctional materials. Further elucidation through Density Functional Theory (DFT) analyses underscored that anion doping and the inherent heterostructure adeptly optimize the Gibbs free energy of intermediates comprising hydrogen, chlorine, and oxygen (manifested as OH, O, OOH) within the HER and OER paradigms, thus propelling the electrochemical kinetics of seawater splitting to unprecedented velocities. These revelations unfurl a pioneering design philosophy for the creation of cost-effective yet superior catalysts aimed at the holistic division of water molecules, charting a course towards the realization of efficient and sustainable hydrogen production methodologies. [ABSTRACT FROM AUTHOR]

[Display omitted] Exploiting highly efficient, cost-effective and stable electrocatalysts is key to decreasing hydrogen evolution reaction (HER) kinetics energy barrier. Herein, the alkaline HER kinetics energy barrier can greatly reduce by the joint strategies of the cation vacancy and heterostructure engineering, which is seldom explored and remains ambiguous. In this study, an efficient and stable copper foam-supported Cu 3 P-CoP heterostructure electrocatalyst with cation vacancy defects (defined as Cu 3 P-CoP-V Al /CF) was designed for HER via the successive coprecipitation, electrodeposition, alkali etching and phosphorization treatments. As anticipated, the as-obtained Cu 3 P-CoP-V Al /CF electrocatalyst reveals a remarkable catalytic activity for HER with a low overpotential of 205 mV at a current density of 100 mA·cm−2, a high turnover frequency value of 1.05 s−1 at an overpotential of 200 mV and a small apparent activation energy (E a) of 9 kJ·mol−1, while shows superior long-term stability at large current densities of 100 and 240 mA·cm−2. Systematic experiment and characterization data demonstrate that the formed cation vacancy could optimize the E a , leading to the decrease of the kinetic barriers of Cu 3 P-CoP/CF heterostructure, as well as the established heterogeneous interface induced a synergistic effect between biphasic components on boosting the kinetics toward HER. The results of density functional theory disclose that the synergistic effect of Cu 3 P-CoP heterostructure could decrease the energy barrier and optimize Gibbs free energy of hydrogen adsorption, resulting in the enhancement of intrinsic catalytic activity of Cu 3 P-CoP-V Al /CF. More significantly, the alkali-cell assembled by Cu 3 P-CoP-V Al /CF (cathode) and RuO 2 /CF (anode) behaves outstanding water splitting performance, delivering a current density of 10 mA·cm−2 at a relatively small applied voltage of 1.58 V, along with encouraging long-term durability. In addition, the alkaline Zn-H 2 O battery with Cu 3 P-CoP-V Al /CF as the cathode has been fabricated for the simultaneous generation of electricity and hydrogen, which displays a large power density of up to 4.1 mW·cm−2. The work demonstrates that rational strategy for the design of competent electrocatalysts can effectively accelerate the kinetics of HER, which supplies valuable insights for practical applications in overall water splitting. [ABSTRACT FROM AUTHOR]

[Display omitted] Electrochemical nitrate reduction reaction (NO 3 RR) offers a cost-effective and environmentally friendly method to simultaneously yield valuable NH 3 and alleviate NO 3 − pollution under mild operating conditions. However, this complicated eight-electron reaction suffers from low selectivity and Faradaic efficiency, which highlight the importance of developing efficient catalysts, but still a critical challenge. Here, a theoretical screening is performed on transition metal-tetragonal carbon nitride (TM@T-C 2 N) as active and selective electrocatalysts for NO 3 RR, where detailed reaction mechanisms and activity origins are explored. In addition, five-step screening criteria and volcano plots enable fast prescreening among numerous candidates. We identify that V@T-C 2 N and Cr@T-C 2 N are promising candidates with low overpotentials and high selectivity and stability. In particular, a significant negative correlation between the adsorption strength of nitrate and the Gibbs free energy for the last proton-electron coupling step (*NH 2 →*NH 3) was existed, which is considerably advantaged to track the activity trend and reveal the origin of activity. This work provides theoretical insights into the rational design of TM–N 4 /C catalysts for NO 3 RR and paves a valuable electrochemical screening framework for other multi-step reactions. [ABSTRACT FROM AUTHOR]

Polydimethylsiloxane (PDMS) elastomers with varying crosslink densities were synthesized using prepolymers with different molecular weights. The association constants (Ka) between a pyrene derivative (PySi) and naphthalenediimide derivative (NDISi) were measured in linear PDMS and PDMS elastomers. The shape of the absorption peak in the charge‐transfer (CT) band and the association constants were nearly independent of the crosslink density. Moreover, the temperature dependence of the association constants demonstrated consistent behavior across all PDMS media. This indicates that the structure of the CT complex and the Gibbs free energy of its formation in the PDMS are unaffected by the crosslink density, providing insights into the design of supramolecular architectures formed by the CT complex in a PDMS network. [ABSTRACT FROM AUTHOR]

This study investigates the adsorption behavior of anionic (Congo red, Eosin yellow) and cationic (Malachite green) dyes on synthesized TD polymer particles, highlighting the material's potential as an effective adsorbent for industrial wastewater treatment. Key operational parameters, including initial solution's pH, contact time, initial dye concentration, and temperature, were systematically evaluated to determine their influence on adsorption efficiency. The experimental data demonstrated that the Langmuir isotherm provided the best fit for all three dyes, indicating monolayer adsorption with maximum adsorption capacities of 153.8 mg/g for Malachite green, 49.36 mg/g for Congo red, and 227.9 mg/g for Eosin yellow. Kinetic analysis revealed that the adsorption of Malachite green and Congo red followed pseudo‐second‐order kinetics, while Eosin yellow adsorption was better described by the intra‐particle diffusion model. Thermodynamic assessments, including Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°), confirmed the spontaneous and endothermic nature of the adsorption processes for Malachite green and Eosin yellow, contrasting with the exothermic behavior observed for Congo red. These findings underscore the versatility and effectiveness of TD polymer particles in removing both anionic and cationic dyes from aqueous solutions. Further research could explore material optimization and real‐world applications to broaden their utility in sustainable water treatment strategies. [ABSTRACT FROM AUTHOR]

The letter comments on a study that prepared P-type zeolite from coal fly ash for adsorption of heavy metals like Cr3+, Ni2+, and Co2+. The research focused on understanding the thermodynamics of the adsorption process, revealing an enthalpy-entropy compensation phenomenon. By analyzing the data, a predictive model was developed to estimate the adsorption of other heavy metals onto the zeolite. The study suggests that the zeolite may effectively remove heavy metals like In, Mo, Zn, As, and Fe, contributing to environmental safety. [Extracted from the article]

2D semiconductor nanomaterials have received significant attention as photocatalysts for solar‐to‐hydrogen conversion due to their robust light absorption capacity, large specific surface area, and superior electron transport characteristics. Nevertheless, it is challenging to develop 2D quaternary copper‐based sulfides (QCSs) with functional integration of conducive structural features for photocatalysis from multiple elements and intricate control conditions. Herein, ultrathin 2D alloyed Cu−Ga−Zn−S (CGZS) curved nanobelts (NBs) are fabricated by using a facile one‐pot colloidal method. Subsequently, the derived Cu31S16‐CGZS Janus heterostructures are designed by increasing Cu concentrations. The formation mechanism of 2D curved alloys and Janus heterostructures is systematically investigated. Without cocatalysts, curved alloyed CGZS NBs demonstrated superior photocatalytic activities of 1264.2 µmol g−1 h−1 compared to Janus heterostructured Cu31S16−CGZS (463.1 µmol g−1 h−1) under visible light (> 400 nm). Experimental and theoretical results unveiled that the improved photocatalytic activities of curved CGZS NBs can be attributed to enhanced charge–carrier separation efficiency resulting from high crystallinity and ultrathin 2D structure, abundant active sites from curved structure, high‐active (0001) crystal facet with the lowest reaction Gibbs energy, work function, and metal‐like properties. This work offers new insights into functional integration into ultrathin 2D QCSs with enhanced visible‐light photocatalytic performance. [ABSTRACT FROM AUTHOR]

Both the sluggish sulfur redox reaction (SRR) kinetics and lithium polysulfides (LiPSs) shuttle effect limit the practical application of Li‐S batteries. Designing heterostructure sulfur hosts has emerged as an effective way to address these two issues with one material. However, the principles of heterostructures reinforced Li‐S batteries remain inadequately understood. Here, it is demonstrated for the first time that increasing the entropy of heterostructure can promote its SRR catalytic activity and alleviate the LiPSs shuttling. By a simple solution‐based strategy, a highly chaotic MXene‐based heterostructure (HCMH, TiS2/TiN/TiO2/Ti3C2Tx) is fabricated. The smart integration of "high entropy", heterostructure, and MXene endow the HCMH catalyst with significantly improved performance, demonstrated by a much smaller Tafel slope of 62.9 mV dec−1 and a higher electron transfer number of 7.10, compared with the moderately chaotic MXene‐based heterostructure (MCMH, TiO2/TiN/Ti3C2Tx) and MXene. DFT theoretical calculations reveal that introducing new phases lowers the Gibbs energy barriers of both rate‐limiting Li2S2/Li2S reduction and Li2S decomposition. Upon the addition of only 5 wt.% HCMH to the sulfur cathode, both the reversible capacity and rate capability of Li‐S cells are greatly improved, which further highlights the importance of the high entropy "cocktail effect" in the design of SRR electrocatalysts in the future. [ABSTRACT FROM AUTHOR]

In this work, two silver/copper‐based coordination compounds {[Ag(tty)]⋅NO3}n (1) and {[Cu2Cl2(tty)2(H2O)2]⋅Cl⋅NO3 ⋅ (H2O)2}n (2) (tty=1,2,4,5‐tetra(1H‐1,2,4‐triazol‐1‐yl))benzen), were synthesized using the different metal salts under the hydrothermal condition. Structural analyses show that compound 1 features tilted L‐shaped 1D Ag chains structure and compound 2 presents a 2D layer with free Cl−, NO3− and water molecules. The experimental results reveal that 1 displays considerably high thermal stability with the thermal decomposition temperature above 337 °C compared to compound 2, which further exemplifies that the framework structures may have a crucial effect on the resultant thermal stability. Additionally, the non‐isothermal kinetics parameters were evaluated at different heating rates by Kissinger's and Ozawa‐Doyle's methods. Importantly, the kinetic triplets (the apparent activation energy (Ea), the preexponential factor (logA) and the mechanism function (ƒ(α)) and the related thermodynamic parameters (the Gibbs energy of activation, ▵G≠, the enthalpy of activation, ▵H≠, and the entropy of activation, ▵S≠) of the thermal decomposition processes are discussed and calculated in detail. [ABSTRACT FROM AUTHOR]

Electrochemical two‐electron water oxidation reaction (2e− WOR) driven by renewable energy offers an attractive route to produce H2O2, while the corresponding electrocatalyst still requires further improvement for the activity, selectivity, and the resulting H2O2 yield. Surface‐interface engineering of electrocatalysts has great potential to advance 2e− WOR performance. This review provides a succinct yet comprehensive insight into the functional mechanisms of surface‐interfacial properties affecting 2e− WOR performance on electrocatalyst. The Gibbs free energy theoretical framework related to surface electronic structure and interfacial reactive kinetics mechanism related to electrolyte, electrode–electrolyte interface structure, and interfacial microenvironment properties are firstly discussed. Afterward, various surface‐interface engineering strategies toward high performance electrocatalysts including the regulation of surface electronic structure, the electrode–electrolyte interface structure, and the interfacial microenvironment have been overviewed. Rational manipulations of the above surface‐interfacial engineering strategies are critical to design highly efficient 2e− WOR electrocatalysts, leading to the development of the green H2O2 production. [ABSTRACT FROM AUTHOR]

Allotropy structures may induce different electronic and optical properties, which implies that one can acquire novel performance by screening its allotropy structures. Here, we demonstrate that two In 2 S 3 allotropy monolayers with excellent photocatalytic performance for water splitting to produce hydrogen are screened from 1038 In 2 S 3 allotropy monolayers. The phonon dispersions are calculated for 39 allotropes with the lowest formation energies, which confirms that 16 allotropes have dynamic stability, including the only one reported in the literature. The results of overpotentials of band edges demonstrate that 8 allotropes match the potential requirements of overall water splitting. The thermodynamic stability of these allotropes is further confirmed for the obtained allotropes. Then, two allotropes with maximum solar-to-hydrogen efficiency of 17.78% and 29.32% are screened. The Gibbs free energy with the solvent effect indicates that one allotrope can proceed photocatalytic hydrogen/oxygen evolution reactions spontaneously. Therefore, the newfound In 2 S 3 allotropy monolayers have potential applications in photocatalytic overall water splitting for hydrogen generation. [Display omitted] • 8 In 2 S 3 monolayers for photocatalytic HER/OER are screened from 1038 allotropes. • The maximum η STH ′ of 29.32% is attributed to the In 2 S 3 -VIII monolayer. • Photocatalytic HER/OER can spontaneously proceed with In 2 S 3 -VI/VIII monolayers. • η STH ′ of In 2 S 3 -VI monolayer can be boosted from 17.78% to 30.16% by adjusting pH. [ABSTRACT FROM AUTHOR]

In light of the promise of electrolytic water-to-hydrogen technology, it is urgent to develop bifunctional catalysts capable of simultaneous hydrogen/oxygen evolution reactions (HER/OER). This paper prepared a self-supported NiCoFeMoP/NF catalyst, which constructed Ni–Co–P nanoarray on nickel foam and modulated the electronic structure by doping Fe (2.0 wt%) and Mo (6.9 wt%). The results indicated that, in the hydrogen evolution reaction, the overpotential of the NiCoFeMoP/NF catalyst at a current density of −100 mA cm−2 was 146 mV, which was lower than that of the Pt/C electrode. In the oxygen evolution reaction, the overpotential of the NiCoFeMoP/NF catalyst at a current density of 50 mA cm−2 was 260 mV, which was lower than that of the RuO 2 electrode. In the overall water splitting, the NiCoFeMoP/NF catalyst required only 1.558 V to reach a current density of 10 mA cm−2 and exhibited exceptional stability. Experimental and computational results demonstrate that the electronic structure of Ni–Co–P can be modulated by incorporating Fe and Mo elements. This modification optimizes the Gibbs free energy of HER/OER intermediates, expedites the kinetic process of water splitting, and enhances the catalytic activity. [Display omitted] • Prepared Flower-petal-shaped Ni–Co–P nano-array bifunctional electrocatalysts. • Fe and Mo doping optimize the surface electron density of electrocatalysts. • A voltage of 1.558 V drives 10 mA cm−2 current in overall water splitting. • Interpreted the electronic modulate mechanism by density functional theory (DFT). [ABSTRACT FROM AUTHOR]

Noble-metal-free CO2 reduction systems based on cobalt phthalocyanine (CoPc) and its derivatives have demonstrated remarkable photocatalytic performances; however, their structure-activity relationship with electronic tuning remains unexplored. Herein, we now provide a systematic study to investigate the electron effects of substituents on the CoPc family in photocatalytic CO2 reduction, where a Cu(I) heteroleptic photosensitizer is utilized. The highest performance can be achieved using cobalt tetracarboxylphthalocyanine in light-driven CO2-to-CO reduction, with a maximum turnover number of 2950 at 450 nm and an outstanding apparent quantum yield of 63.5% at 425 nm, over ten times the activity with the tetra-dimethylamino-substituted CoPc derivative. The favorable electron-withdrawing effects have been further verified by DFT calculations and cyclic voltammetry, which reduces the overpotential required for CO2 reduction and decreases the Gibbs free energy of the catalyst active intermediates, particularly the CO-desorption energetics. [ABSTRACT FROM AUTHOR]

Surface pressure (π)–molecular area (A) isotherms were gathered to characterize the packing of binary mixed Langmuir monolayers of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphoethanolamine (DOPE) and one of two Gemini surfactants (GS), N,N‐bis(dimethyloctadecyl)‐1,7‐nonanediammonium dibromide (18‐7‐18) or 1,9‐bis(octadecyl)‐1,1,9,9‐tetramethyl‐5‐amino‐1,9‐nonanediammonium dibromide (18‐7NH‐18) of varying molar fractions. Information about miscibility behavior was derived from the π–A curves by examining the excess free energy of mixing (ΔGexc) that was calculated through the surface area additivity rule. Surface compressibility modulus (Cs−1) was also used to characterize intermolecular interactions. Mutual interactions between GS and DOPE were analyzed in terms of excess Gibbs energy of mixing and the value of this parameter depended strongly on the composition of the mixed film. GS and DOPE are generally miscible as DOPE reduces intermolecular repulsion between highly charged GS molecules leading to the formation of more densely packed mixed monolayers. However, GS and DOPE are immiscible in equimolar mixtures due to tail group packing mismatch between saturated and unsaturated alkyl chains. The prevalence of attractive synergistic interactions in the monolayers studied differs from a previous finding of antagonistic mixing behavior in GS/DOPE micelles. These results contribute to the understanding of GS‐lipid interactions and packing that are critical to the in vitro and in vivo stability of liposomes composed of these molecules used for non‐viral gene therapy applications. [ABSTRACT FROM AUTHOR]

In this work, we study the proximity effects in a single- and two-band superconducting three-dimensional heterostructure, described by two condensates (condensate 1 and condensate 2) in the presence of an external magnetic field perpendicular to the heterostructure. The distance between the interfaces of both condensates is given by the parameter λ ′ . We solve the time-dependent Ginzburg-Landau equations considering a Josephson-like coupling to explore properties such as magnetization, Gibbs free energy, and the Abrikosov vortex state. We propose three cases: case 1, both condensates are composed of a single-band; case 2, the condensates are composed of two bands; and case 3, condensate 1 has a single-band and condensate 2 has two bands. As a result, we highlight the variation of the first critical field and the novel vortex configurations induced by the proximity effect between the superconducting condensates. This phenomenon substantially influences the arrangement of vortices in each of the superconducting bands. [ABSTRACT FROM AUTHOR]

Ti3C2, one typical MXene, has great potential to be coupled with various transition metals. Herein, a novel and effective catalyst is developed by synergistically loading VCoCOx onto Ti3C2‐modified nickel foam (VCoCOx–Ti3C2@NF). Field emission scanning electron microscope and high‐resolution transmission electron microscopy are employed to characterize the morphology and structure. As expected, the catalyst optimized by response surface methodology attains overpotentials of 290 and 64 mV and Tafel slopes of 82 and 79 mV dec−1 for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. By using the bifunctional VCoCOx–Ti3C2@NF catalyst, the water splitting current density achieves 10 mA cm−2 in 1.0 mol L−1 KOH electrolyte at cell voltage of 1.52 V, comparable with the noble metal electrolyzer Pt@C@NF||RuO2@NF (1.57 V). Furthermore, the resulting catalyst exhibits excellent cycling durability after 120 h of continuous catalysis, which retains 103.8% and 105.4% of potential (V vs reversible hydrogen electrode) for OER and HER, respectively. Density functional theory calculation reveals that the Gibbs free energy barriers for the OER and HER intermediates are reduced due to the integration of VCoCOx with Ti3C2@NF. The fabricated VCoCOx–Ti3C2@NF catalyst is a promising electrochemical material for clean energy production. [ABSTRACT FROM AUTHOR]

Klebsiella oxytoca JCM 1665 was subjected to extracellular rhodanese production using a submerged fermentation technique. The organism was further engineered for higher cyanide tolerance and rhodanese yield using ethylmethanesulfonate as a mutagen. Mutagenesis resulted in an improved mutant with high cyanide tolerance (100 mM) and rhodanese yield (26.7 ± 0.67 U/mL). This yield was 4.34-fold higher than the wild strain (6.15 ± 0.65 U/mL). At temperatures ranging from 30 to 80 °C, the first-order thermal denaturation constant (Kd) for free enzyme increases from 0.00818 to 0.0333 min−1 while the immobilized enzyme increases from 0.003 to 0.0204 min−1. The equivalent half-life reduces from 99 to 21 minutes and 231 to 35 minutes, respectively. Residual activity tests were used to assess the thermodynamic parameters for both enzyme preparations. For the free enzyme, the parameters obtained were enthalpy (29.40 to 29.06 kJ.mol−1), entropy (−194.24 to −197.50 J.mol−1K−1) and Gibbs free energy (90.20 to 98.80 kJ.mol-1). In addition, for immobilized rhodanese, we obtained enthalpy (40.40 to 40.07 kJ.mol−1), entropy (−164.21 to − 165.20 J.mol−1K−1) and Gibbs free energy (91.80 to 98.40 kJ.mol−1. Regarding its operational stability, the enzyme was able to maintain 63% of its activity after being used for five cycles. Immobilized K. oxytoca rhodanese showed a marked resistance to heat inactivation compared to free enzyme forms; making it of utmost significance in many biotechnological applications. [ABSTRACT FROM AUTHOR]

Purpose: This study aims to develop eco-friendly corrosion inhibitors for aluminum in acidic media by evaluating the corrosion inhibition properties of corn leaf extract (CLE) using response surface methodology (RSM) and experiments. Design/methodology/approach: The RSM was combined with experiments to evaluate the corrosion inhibition properties of CLE on aluminum in acid media. Findings: The effectiveness of the inhibition increased with increasing inhibitor concentration and time but decreased with increasing temperature. The corrosion inhibition mechanism revealed the corrosion process is spontaneous exothermic physical adsorption. Thermodynamic parameters revealed an activation energy between 32.1 and 24.7 kJ/mol, energy of adsorption between −14.53 and −65.07 and Gibbs free energy of −10.12 kJ/mol which indicated the CLE exothermically spontaneously physisorbed. A model was generated to estimate the effect of the process parameters (inhibitor concentration, reaction time and temperature) using the RSM. Optimization of the process factors was also carried out using the RSM. The percentage inhibition efficiency obtained experimentally (85.61%) was closely comparable to 84.89% obtained by the theoretical technique (RSM). The SEM observations of the inhibited and uninhibited Al samples demonstrated that CLE is an effective corrosion inhibitor for aluminum in acid media. Originality/value: Results herein provide novel information on the possible application of CLEs as effective eco-friendly corrosion inhibitors. [ABSTRACT FROM AUTHOR]

In this study, we propose a method for estimating liquid–liquid equilibrium with ab initio molecular dynamics (MD) simulation. Additionally, we determined the non‐random two‐liquid model parameters for the systems applicable to the extraction design using a commercial software. The minimized energy of separate liquid phases yielded equilibrium data from a more versatile procedure than the existing MD simulation. Although many experimental measurements with the parameters have been published, the parameters are not always compatible with the software. The performances are graphically illustrated for example systems including ionic liquid and deep eutectic solvent, and the results indicated that the proposed procedures of the estimation and the model parameter determination were satisfactory. [ABSTRACT FROM AUTHOR]

Densities (ρ), speeds of sound (u), and viscosities (η) were derived for three distinct binary mixtures comprising allyl alcohol in conjunction with chlorinated methanes. The Exploration ranged from 303.15 K to 313.15 K, at atmospheric pressure across all composition. The empirical data from the measurements formed the foundational basis for the determination of excess molar volume, excess isentropic compressibility, viscosity deviation and excess Gibbs free energy with the activation of viscous flow. We computed partial molar and infinite dilution properties for each binary system. The results are interpreted in the forming complexes, chemical forces and specific interactions with binary mixtures. The implication drawn from the application of the Jouyban-Acree model are expounded, taking into account the mean relative deviation (MRDs) and individual relative deviation (IRD) between the calculated and experimental densities, speed of sound, and viscosities as a criterion for accuracy criterion. FTIR studies validate experimental findings in investigated mixtures. [ABSTRACT FROM AUTHOR]

Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of 4-Hydroxy-4-methyl-pentan-2-one with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol, and 1-amino propan-2-ol were calculated at temperatures ranging from 303.15 to 313.15 K and atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and infinite dilution molar partial properties are also calculated for each binary system. Heteroassociates molecules forming complexes and chemical forces with specific interactions can be discussed from the results. The Prigogine–Flory–Patterson theory is used to identify the most important interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion. FTIR studies confirm the experimental findings of the investigated mixtures. [ABSTRACT FROM AUTHOR]

Densities (ρ), speeds of sound (u) and viscosities (η) were measured for three binary mixtures of propargyl alcohol with tetra chloromethane, trichloromethane, and dichloromethane from 303.15 K to 313.15 K at atmospheric pressure across the composition range. Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow were calculated. Partial molar properties and infinite dilution molar partial properties were also determined for each system. Results suggest heteroassociates forming cross complexes and chemical forces with specific interactions. PFP theory was used to identify the predominant molecular interactions. The Jouyban–Acree model findings were discussed, considering mean relative deviation (MRDs) and individual relative deviation (IRD) between calculated and experimental data. FTIR studies were included to corroborate the experimental findings. [ABSTRACT FROM AUTHOR]

Excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy for activation of viscous flow for binary mixtures of propargyl alcohol (J) with benzyl aldehyde (J1), benzylamine (J2) and benzyl alcohol (J3) components with selected compositions were determined from the measured values of densities (ρ), viscosities (η), and speeds of sound (u) of pure components and their mixtures from 303.15 K to 313.15 K. The effect of various functional groups on the excess properties has been discussed in terms of attractive forces between the components. The results of the Jouyban-Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion.FTIR studies have also been added to confirm the experimental findings of the investigated mixtures [ABSTRACT FROM AUTHOR]

Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of allyl alcohol with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol (aminomethyl propanol), and 1-amino propan-2-ol (isopropanol amine) were calculated at temperatures ranging from 303.15 to 313.15K and at atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and partialmolar properties at infinite dilution are also calculated. The Prigogine–Flory–Patterson (PFP) theory is applied to identify the predominant molecular interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation (MRDs) and individual relative deviation (IRD) between the calculated and experimental parameters as an accuracy criterion. FTIR studies have also been added to confirm the experimental findings of the investigated mixtures. [ABSTRACT FROM AUTHOR]

The thermodynamic and transport properties of binary mixtures of N-methyl benzyl amine (NMBA) with halo methane compounds at temperatures from 303.15 K to 313.15 K were investigated. The study analysed the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy for activation of viscous flow using measured densities (ρ), viscosities (η), and speeds of sound (u). The research also examined the impact of the inductive effect on excess properties concerning intermolecular attractive forces between the respective constituents. Furthermore, the Jouyban–Acree model was employed to correlate density, speed of sound, and viscosity with composition and obtained good agreement. [ABSTRACT FROM AUTHOR]

Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow for binary mixtures of Hexylene glycol (2-methyl-pentanediol-2,4 or MPD) with aliphatic ketones (4-hydroxy-4-methyl-pentan-2-one (J1), 4-methyl-pentan-2-one (J2), and pentan-2-one (J3)) components selected compositions were determined from the measured values of densities (ρ), viscosities (η), and speeds of sound (u) of pure components and their mixtures from 303.15 K to 313.15 K. The results were analysed in terms of intermolecular interactions or hydrogen bonding or hetero-association interactions in the binary mixtures. Finally, the Prigogine-Flory-Patterson (PFP) theory is applied to identify the most predominant molecular interaction. The results of the Jouyban-Acree model are discussed in terms of mean relative deviation (MRDs) and individual relative deviation (IRD) between calculated and experimental densities, speeds of sound, and viscosities as an accuracy criterion. [ABSTRACT FROM AUTHOR]

In an attempt to expand the utility of natural compounds in catalysis, a novel heterogeneous catalyst derived from Gum Arabic, a natural polysaccharide, was synthesized by its modification with chlorosulfuric acid and subsequent magnetization. Material characterization confirmed the successful modification and magnetization of GA. Hammet method also approved increase of acidity of gum upon functionalization with chlorosulfuric acid. According to Response Surface Methodology optimization, this catalyst exhibited high activity for the conversion of fructose to 5-hydroxymethylfurfural under mild conditions, achieving a 96% yield at 85 °C within 73 min using 30 wt% catalyst loading. The kinetic study indicated an activation energy of 89 kJ/mol. Thermodynamic parameters were determined, with enthalpy, entropy, and Gibbs free energy values of 86.11 kJ/mol, − 29.45 J/mol, and 96.65 kJ/mol, respectively. Furthermore, the catalyst displayed excellent recyclability, retaining over 87% activity for five consecutive cycles, and a heterogenous nature as confirmed by hot filtration test. This study demonstrates the potential of the as-prepared catalyst for sustainable 5-hydroxymethylfurfural production, highlighting its high activity, recyclability, and environmentally friendly nature. [ABSTRACT FROM AUTHOR]

BACKGROUND: In the designed study, the moisture sorption isotherm and thermodynamic properties of refractance‐window‐dried egg white powder (EWP), egg yolk powder (EYP) and whole egg powder (WEP) were determined. RESULTS: The adsorption isotherm of egg powders was classified as type II, giving a sigmoidal shape. Peleg showed the highest goodness of fitting for egg powder. The monolayer moisture content of egg powders varied between 0.02 and 0.09 g g−1. According to the thermodynamic analysis, an increase in moisture content led to a decrease in net isosteric heat of sorption (qst), and the highest decrease was observed in EWP. The qst of EWP was calculated as 18 637 kJ mol−1, while it decreased to 3104 kJ mol−1 at 0.2 g g−1 moisture content. Like qst, sorption entropy decreased from 52.07 to 7.14 J mol−1 K−1 with increasing water activity (aw) for EWP. Increasing temperature caused a decrease in spreading pressure and was higher in EWP samples. Increasing moisture content and temperature also decreased Gibbs free energy level. CONCLUSION: Moisture sorption isotherm (MSI) is used to predict the amount of bound water in a material at a specific relative humidity and temperature. To inhibit chemical and microbiological spoilage, the drying process must continue until the monolayer moisture content is reached. In this study, the monolayer moisture content of powdered eggs for safe storage was demonstrated by MSI. Additionally, by determining the thermodynamic functions of egg powder, valuable information was obtained related to predicting the energy requirement in drying processes. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Al2O3‐based composite seal with 10 wt% Al powder addition (A10) possesses excellent plastic and mechanical performance under wide temperature range of solid oxide fuel cell. The thickening phenomenon of A10 seal between 250°C–400°C and 600°C–750°C is caused by the thermal expansion of organic additives and the volume expansion when solid–liquid Al react with oxygen to form Al2O3. The thickness change rate reaches the maximum which is about 5% at 300°C and is about 4.46% at 650°C. The Gibbs free energy for reaction between Al and Al2O3 in the temperature range of 523–1 023 K is all less than 0, which is proved by the fact that A10 exhibits excellent self‐expansion and thermodynamic properties in the solid oxide fuel cell operating temperature. [ABSTRACT FROM AUTHOR]

In this work, the physiochemical properties of the drug, isoproterenol hydrochloride, were analyzed in the presence of β-cyclodextrin in an aqueous medium to gain a better understanding of the prevailing interactions among solute–solvent systems with the help of viscosity and conductivity studies. From viscosity measurements, the viscosity B -coefficient along with its transfer parameter was calculated using the Jones–Dole equation. In addition to this, the activation parameters such as Δ μ 1 o # , Δ μ 2 o # , Δ S 2 o # , and Δ H 2 o # were evaluated and discussed to gain a better understanding of the mechanism of viscous flow in terms of transition state theory. Along with this, conductivity studies were performed to investigate the thermodynamics of the ternary system in terms of changes in Gibbs free energy. Also, the delayed critical aggregate concentration of the ternary system supports favourable interaction between the studied drug and β-cyclodextrin molecules. [ABSTRACT FROM AUTHOR]

Understanding of dicofol's behavior in soil is crucial for more precise pest control and minimal environmental effect. Therefore, the goal of this study was to assess how the physicochemical characteristics of 10 selected soils effects the sorption and degradation of dicofol behavior. The behavior of dicofol, including its adsorption and desorption properties as well as its rates of hydrolysis and photolysis degradation, was thoroughly examined via definitive studies. Standard batch equilibration mode for sorption revealed that it was dependent on the physical and chemical properties of the soil. Exothermic and spontaneous adsorption processes, which were characterized by a negative Gibbs free energy value, were convincingly proven by thermodynamic study. The current investigation's ΔG estimations varied from −18.6 kjmol−1 for soil-6 to −24.25 kjmol−1 for soil-9. The soil-7 with a notable organic matter content (1.81%) showed the maximum adsorption, and subsequently producing a C-type isotherm that was analyzed using a linear and Freundlich model. An analytical process using UV-VIS spectrophotometry to determine the fate of dicofol in soil matrices. Hydrolysis and photolysis studies yielded minimum half-lives of 13.4 and 1.32 days, respectively. It has been demonstrated that dicofol molecules interact strongly with soils, principally via physio-sorption mechanisms. In contrast to its strong soil affinity and permanence, dicofol exhibits a counterintuitive behavior that makes it vulnerable to sunlight-induced deterioration. Future studies will concentrate on enhancing these pathways to assist sustainable pesticide management strategies and creative pollution mitigation techniques. [ABSTRACT FROM AUTHOR]

Free barium (Ba) is critical to the formation of the active layer on the surface of dispenser cathode, which is contributed to the electron emission properties of the cathode. The Ba in the active layer of the dispenser cathode is generated by the chemical reaction between aluminate compounds and tungsten (W) under vacuum and high temperature. Nowadays, the effect of aluminate compounds on the generation of free Ba is not clear. In this work, aluminate impregnants called 411, 532 and 612 impregnants were prepared by coprecipitation method. The structure of the dominate compounds in 411, 532 and 612 impregnants were determined with density functional theory (DFT) calculation and Rietveld structure refinement. It was found that the dominate compounds of 411, 532 and 612 impregnants are Ba 3.5 Ca 0.5 Al 2 O 7 , Ba 5 CaAl 4 O 12 and Ba 3 CaAl 2 O 7 , respectively. Then, the temperature dependence of the thermodynamic properties, such as Debye temperature, entropy, heat capacity and enthalpy, of the aluminate compounds were calculated. Based on the thermodynamic properties, the potential chemical reaction between aluminate compounds and W are energetically determined by deviation Gibbs energy. The effects of different aluminate compounds on the free Ba generation were evaluated with the equilibrium Ba(g) amounts that generated by the chemical reactions between aluminate compounds and W. It is shown that the equilibrium Ba(g) amounts generated by Ba 3.5 Ca 0.5 Al 2 O 7 is higher than that by Ba 5 CaAl 4 O 12 and Ba 3 CaAl 2 O 7 , implying the superiority of electron emission performance of Ba 3.5 Ca 0.5 Al 2 O 7. The electron emission densities of the dispenser cathodes that impregnated with the 411, 612 and 532 impregnants are 5.06, 4.31 and 4.05 A/cm2, respectively. It is revealed that the Ba 3.5 Ca 0.5 Al 2 O 7 has superiority in generating free Ba, which agreed well with thermodynamic simulation results. [ABSTRACT FROM AUTHOR]

The study investigates the solubility of carbon dioxide (CO 2) in three ionic liquids [BMP][Tf 2 N] (1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide), [HMP][Tf 2 N] (1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide) and [OMP][Tf 2 N] (1-octyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide). The research is conducted over a temperature range of 303.15 to 363.15 K. The phase equilibria of the binary systems are predicted using the Peng-Robinson (PR) equation of state, the Wilson (WS) mixing rule and the UNIFAC activity coefficient model. The interaction parameter k ij is regressed from the vapor-liquid equilibrium (VLE) experimental data. The study also calculates the excess Gibbs free energy (GE), excess enthalpy (HE), and excess entropy (SE) for these systems. The research results indicate that the length of the alkyl chain in the cation has a significant effect on the excess properties of the CO 2 -ionic liquid systems. As the alkyl chain length increases, the excess Gibbs free energy and excess enthalpy decrease, while the excess entropy increases. The CO 2 -[OMP][Tf 2 N] system exhibits stronger interactions between CO 2 and the ionic liquid, indicating a higher capacity for CO 2 absorption. The study results are helpful for optimization of CO 2 capture processes and the broader comprehension of fluid phase equilibria in complex systems. [ABSTRACT FROM AUTHOR]

Silicon carbide (SiC) is a widely used component for thermal protection system (TPS) design. This material is often used either as a coating layer to protect beneath carbon‐based material against oxidation or as a ceramic matrix for composite materials used in the hypersonic leading edges. A numerical equilibrium model for SiC‐coated material ablation is developed in this study to compute the material response of coated TPS in hypersonic relevant aerothermal environment. The developed model is based on an equilibrium approach similar to the carbon graphite oxidation framework for ablative charring materials. The equilibrium wall composition is calculated based on the minimization of the Gibbs free energy. The proposed method can capture numerically the transition from passive to active oxidation while maintaining a low computational cost and good numerical stability. Implementation of the model in the Porous Material Analysis Toolbox based on OpenFOAM code permits to compare against previous literature test cases. By comparing the surface temperature obtained from the model with the experimental data, it is observed that the numerical model gives a good estimation providing accurate surface temperature prediction. [ABSTRACT FROM AUTHOR]

Air pollution as a result of intensified anthropogenic activity leads to the elevated cases of respiratory diseases. One of them is occupational asthma, which is described in this study by ecological aetiology. The mechanism of action of pollutants (allergens) on the mast cells - structural elements of symbiotic adaptation between humanity, environment, and the Technosphere - is systematized. Human immunity is described symbiotically and homeostatically by the expression of Gibbs energy, which is the main energetic moment of this complex unit Noosphere-BiosphereTechnosphere. The pathophysiological mechanisms of asthma with the creation of the complexes “mast+IgE” are also described by the quantitative expression of Gibbs free energy. Regarding this expression, decisions can be made for the combating of high levels of pollutants in the atmosphere as well as regarding prophylactic and therapeutic measures. [ABSTRACT FROM AUTHOR]

We successfully decorated metallic 1T phase WS 2 (1T-WS 2) on the surface of ZnIn 2 S 4 and investigated the synergistic effect of 1T-WS 2 on ZnIn 2 S 4. Under simulated solar irradiation, the optimal hydrogen production rate of 1T-WS 2 /ZnIn 2 S 4 reaches 30.90 mmol/h g−1, which is 3.38 times higher than that of single ZnIn 2 S 4. [Display omitted] Improving the separation efficiency of carriers is an important part of enhancing photocatalytic activity. Herein, we successfully decorated metallic 1T phase tungsten disulfide (1T-WS 2) on the surface of zinc indium sulfide (ZnIn 2 S 4) and investigated the synergistic effect of 1T-WS 2 on ZnIn 2 S 4. The characterization results show that 1T-WS 2 improves the light absorption capacity and utilization efficiency, increases the catalytic active site, improves the photogenerated charge separation efficiency, and optimizes the reduction potential of ZnIn 2 S 4. Theoretical calculations show that compared with ZnIn 2 S 4 , 1T-WS 2 /ZnIn 2 S 4 has a smaller adsorption Gibbs free energy of the intermediate state H*, which is conducive to the catalytic reaction. Under simulated solar irradiation, the hydrogen (H 2) production rate of 1T-WS 2 /ZnIn 2 S 4 with a loading of 12 wt% reaches 30.90 mmol h−1 g−1, which is 3.38 times higher than that of single ZnIn 2 S 4 (9.13 mmol h−1 g−1). In addition, the apparent quantum efficiency of 1T-WS 2 /ZnIn 2 S 4 with a loading of 12 wt% reaches 21.14 % under monochromatic light at a wavelength of λ = 370 nm. This work analyzes the light absorption and carrier separation to the catalytic site, and elucidates the mechanism for the enhancement of the photocatalytic hydrogen production performance. [ABSTRACT FROM AUTHOR]