Search Results (9,527)

This study addresses the issue of insufficient product purity caused by the co-deposition of three major impurity ions—zinc, nickel, and lead—during the electrodeposition process of high-purity manganese. A targeted deep purification method for manganese sulfate electrolyte was developed using dithiocarbamate chelating agents (sodium dimethyldithiocarbamate, SDD). By optimizing key process parameters such as precipitant concentration, reaction temperature, reaction time, and solution pH, combined with density functional theory (DFT) calculations, to elucidate the selective impurity removal mechanism at the molecular level, a novel process for the efficient synergistic removal of Zn²⁺, Ni²⁺, and Pb²⁺ was established. The results showed that under the conditions of precipitant concentration of 1 g/L, solution pH of 6.5, reaction temperature of 55 °C, and reaction time of 2 h, the residual concentrations of Zn, Ni, and Pb in the electrolyte were all below 0.2 mg/L. DFT calculations revealed that SDD coordinates with metal ions through four sulfur atoms, and the absolute values of binding energies follow the order Ni²⁺ > Pb²⁺ > Zn²⁺ > Mn²⁺, indicating thermodynamically preferential capture of impurity ions. After purification, the manganese metal obtained by electrodeposition from the manganese sulfate solution achieved a purity exceeding 99.999%, with Zn, Ni, and Pb contents of 0.11 mg/kg, 0.038 mg/kg, and 0.05 mg/kg, respectively, meeting the raw material requirements for semiconductor-grade copper–manganese alloy targets. Full article

Scandate cathodes have garnered significant attention for their exceptional low-temperature, high-current-density emission characteristics. However, their widespread deployment in vacuum electronic devices is currently hindered by stringent vacuum requirements and susceptibility to ion bombardment. To enhance the engineering applicability of scandate cathodes, this study employs first-principles density functional theory (DFT) to model the surface microstructures of strontium (Sr)–scandium (Sc) co-doped systems. Guided by simulation predictions regarding surface elemental ratios, corresponding emission active materials and cathode samples were fabricated. A systematic comparison between theoretical calculations and experimental measurements reveals a critical trade-off: while increasing Sr content enhances structural stability (indicated by lower formation energies), it concurrently increases the work function. Consequently, an optimal Sr doping level of approximately 2 wt% is identified, which significantly improves emission current density without compromising stability. Cathodes fabricated with this optimized composition were tested in a practical electron gun configuration. Results demonstrate that under low-temperature conditions (1000 °C) and wide-pulse operation (2 ms), the cathode achieves an emission current density of 21.57 A/cm². These findings validate the efficacy of simulation-guided material design and highlight the potential of Sr-doped scandate cathodes for high-power microwave applications. Full article

Background: Amorphous drug formulations are commonly used to improve the solubility and bioavailability of poorly soluble molecular pharmaceuticals, yet less is known about their molecular conformations and local bonding interactions than their crystalline phases. Methods: High-energy X-ray diffraction structure factor measurements have been made on liquid and glassy nifedipine (NIF), felodipine (FEL), NIF 1:3 polyvinylpyrrolidone (PVP), and FEL 1:3 PVP wt.% mixtures. The corresponding X-ray pair distribution functions have been interpreted using empirical potential structure refinement using different models and density functional theory conformer calculations. Results: In both NIF and FEL, the NH···O inter-molecular hydrogen bonds between the pyridyl nitrogen and ester carbonyls are found to be considerably weaker than those observed in the crystalline polymorphs. For nifedipine, it is proposed that either inter-molecular NH…ON nitro bonds are present and/or a fraction (<20%) of conformational changes, with the aryl ring flipped, occur in the liquid state. For felodipine, the models indicate significant disorder associated with the methyl and ethyl side chains in the liquid state, with the main peak intensity at 3.0 Å arising from intra-molecular Cl-Cl atom pairs. When nifedipine molecules are incorporated into PVP, our models show they possess stronger NH···O bonds to the PVP polymer than felodipine molecules, which have stronger affinity for bonding to the polymer than to other felodipine molecules. Conclusions: The amorphous forms of both NIF and FEL show much weaker hydrogen bonding than found in their crystalline phases. Liquid NIF also exhibits configurations which are not observed in the crystal phases. Full article

Understanding the intrinsic Li–H₂ interaction, decoupled from substrate effects, is essential to rationalize the performance of lithium-decorated hydrogen storage materials. To address the current lack of a clean theoretical baseline, we characterized the sequential H₂ adsorption on the gas-phase Li₆ superatomic cluster using high-level density functional theory (DFT), complemented by Energy Decomposition Analysis (EDA), QTAIM, and NICS(0) calculations. Li₆ acts as a structurally rigid platform (RMSD < 0.032 Å) where ligand-induced polarization progressively strengthens its σ-aromaticity (NICS(0) from −2.917 to −13.98 ppm) and increases the HOMO–LUMO gap up to 5.05 eV. EDA identifies the binding as field-activated physisorption, electrostatically dominated (65–67%) and mechanistically distinct from Kubas coordination, as confirmed by QTAIM closed-shell interaction parameters. Negative cooperativity governs an effective loading capacity of n = 2 molecules under cryogenic conditions (T_eq = 143.76 and 114.64 K), while an entropic bottleneck renders higher loading non-spontaneous at all temperatures. These results establish Li₆(H₂)_n as a foundational gas-phase reference, providing a systematic, contamination-free descriptor set for the intrinsic Li–H₂ interaction. This framework is essential for isolating the electronic role of the lithium superatom and unambiguously identifying substrate-induced modulations in supported hydrogen storage materials. Full article

To investigate the influence of external ambient temperature on the transmission characteristics of laser propagation in an internal channel, a simulation model of laser transmission within a closed channel is established in this study. The model comprehensively considers factors including gas density, refractive index distribution, and thermal deformation of optical components. Based on optical transmission theory, the model is used to calculate the beam drift characteristics and the variation in the Strehl ratio at different temperatures. The results indicate that ambient temperature has a significant impact on beam stability and quality. At low temperature (−30 °C), speckle structures appear in the laser spot, with minor drift along the X direction but obvious negative drift along the Y direction, mainly caused by the sinking of cold air driven by gravity and the refractive index gradient. The beam drift decreases initially with increasing temperature, reaches its minimum at around 10 °C, and then increases gradually as the temperature continues to rise. The Strehl ratio initially increases during the early stage of temperature rise, but diminishes in the high-temperature range due to intensified gas disturbances, enhanced thermal lensing effects, and aggravated mirror surface deformation. Full article

In this work, sodium alginate (NaAlg) membranes were enhanced with synthesized zinc oxide (ZnO) nanoplates to enable efficient pervaporation dehydration of isopropyl alcohol (IPA). A comprehensive suite of characterisation techniques—scanning electron (SEM) and atomic force (AFM) microscopy, Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), contact angle and liquid uptake measurements—along with density functional theory (DFT) calculations, was employed to establish robust structure–property relationships and to elucidate filler–polymer interactions. Membranes with different ZnO contents were prepared, and membranes based on the optimal NaAlg-ZnO(5%) composite were cross-linked with CaCl₂ to improve stability in aqueous solutions, and supported membranes were developed for prospective applications by applying this composite onto the prepared porous cellulose acetate (CA) substrate. This developed cross-linked supported NaAlg-ZnO(5%)/CA membrane had a permeation flux increased by 2 times or more compared to a dense NaAlg membrane during dehydration of IPA (12–30 wt.% water) with a permeate water content above 99 wt.%. The integrated experimental–theoretical approach provides mechanistic insight into ZnO–NaAlg interactions and demonstrates the strong potential of these mixed matrix membranes for high-efficiency alcohol dehydration, offering a rational design paradigm for next-generation pervaporation membranes. Full article

Achieving high selectivity in the hydrogenation of CO₂ to light olefins remains challenging because of the complex reaction network and the difficulty of regulating key intermediates. Motivated by green-hydrogen-enabled power-to-chemicals pathways, we combine density functional theory (DFT) with first-principles microkinetic simulation (FPMS) to construct a quantitatively predictive reaction-energy landscape and elucidate structure–selectivity relationships. A comprehensive reaction network is established through energy-surface fitting, and steady-state rate constants are solved to capture the microkinetic competition between elementary steps. By introducing electronic density-of-states (DOS) modulation as a design variable, we directly correlate surface structural parameters with rate-controlling steps, thereby enabling targeted regulation of C–C coupling and hydrogen transfer processes. The calculated barrier for CO₂ adsorption to COOH* is 1.35 eV, while the transition state barrier for C–C coupling is 1.50 eV, corresponding to a reaction rate of 9.7 × 10³ s⁻¹; the olefin desorption rate reaches 1.7 × 10⁷ s⁻¹. Crucially, shifting the d-band center from −2.35 eV to −1.60 eV increases the C₂–C₄ olefin selectivity from 42.6% to 68.3%, establishing an actionable electronic structure lever for catalyst optimization. These results reveal the intrinsic mechanism by which surface electronic and geometric regulation governs intermediate stabilization and rate control, providing a verifiable, mechanism-based design principle for efficient CO₂-to-olefin catalysts aligned with green hydrogen deployment. Full article

While macroscopic stress significantly impacts the performance of metallic components, the underlying atom–electron coupling mechanisms governed by distinct crystal symmetries remain insufficiently understood. To address this gap, this work systematically investigates the structural and electronic evolution of representative metallic materials under applied stress. Experimentally, X-ray diffraction (XRD) revealed complex macroscopic residual stress distributions in cold rolled titanium alloy and silicon steel. Motivated by these engineering observations, first-principles density functional theory (DFT) calculations were conducted to uncover the underlying physical mechanisms. Specifically, the responses of face-centered cubic (FCC) aluminum and copper, body-centered cubic (BCC) iron, and hexagonal close-packed (HCP) titanium crystals were investigated under tension and compression using the RPBE functional. Stress-dependent elastic properties, density of states (DOS), band structures, and phonon spectra were calculated. Results show that tension softens all metals (Al becomes mechanically unstable), whereas compression stiffens their lattices. Electronically, tensile loading sharpens DOS peaks near the Fermi level and shifts conduction bands closer to it, whereas compression smooths DOS peaks and shifts bands away. Phonon analysis indicates Cu and Ti remain dynamically stable, while Al and Fe exhibit phonon mode softening under high tension. These stress-induced changes highlight crucial atom–electron coupling mechanisms, providing a theoretical basis for tailoring metallic performance via stress engineering. Full article

Understanding pressure-induced isosymmetric phase transitions in molecular crystals requires consideration of both structural and thermodynamic factors, particularly in hydrogen-bonded systems. In this work, periodic density functional theory (DFT) calculations were employed to investigate the pressure-dependent behavior of L-serine and to elucidate the origin of its experimentally observed phase transition between Phase I and Phase IV. Geometry optimizations performed at ambient pressure and 8.8 GPa reproduce the compression of the crystal lattice and the pressure-driven stabilization of Phase IV. However, no spontaneous reorientation of the hydroxyl groups is observed, indicating that the transition is not accessible within a purely static framework. To further explore the stability of the system, a series of modified crystal structures with different hydroxyl group orientations was generated and analyzed, revealing a complex energy landscape at ambient conditions that becomes significantly simplified under compression. Phonon calculations within the quasi-harmonic approximation demonstrate that the experimentally observed Phase I structure is not stabilized by enthalpy but by vibrational entropy, whose contribution increases with temperature. These results show that the phase transition in L-serine is governed by an interplay between lattice energy, hydrogen-bond rearrangement, and vibrational effects, and highlight that an accurate description of polymorphic stability in such systems requires inclusion of both static and dynamic contributions. Full article

To address severe mine pressure disasters induced by the coupling of mining-induced dynamic stress and impact disturbance during close-distance coal seam mining, this paper takes the No. 8 and No. 9 close-distance coal seams in the 119 mining area of a coal mine in Ningxia, China, as the engineering background. Theoretical analysis and FLAC^3D numerical simulation methods were adopted to systematically study the evolution of overburden structure, the manifestation law of mine pressure caused by mining disturbance, and the dynamic response mechanism of roadway surrounding rock under impact load. The findings demonstrate: ① Based on key block theory and elasticity mechanics theory, the stress transfer mechanism of the complete bearing type overburden rock in close-range coal seams was clarified. The calculation model of floor plastic zone depth and additional stress was derived, and the influence mechanism of the bearing state of interlayer rock strata on the stability of underlying coal seam roadways was revealed. ② Comparative numerical simulations of mining schemes revealed that both schemes formed a “goaf pressure relief-workface-coal pillar” load-bearing configuration with “upward subsidence and downward bulging” basin-shaped settlement. Scheme A exhibited significantly increased stress peaks and interlayer plastic zones due to repeated mining-induced stress, substantially elevating the risk of strong mine pressure manifestation and surrounding rock instability. ③ Under 8 MPa cosine impact load with a vibration frequency of 50 Hz (peak particle vibration velocity of 9.57 m/s), compared with the unsupported roadway, the bolt–cable collaborative support system reduced the peak displacement of surrounding rock by over 35% and decreased the shock wave propagation velocity by more than 40%, effectively suppressing the expansion of plastic zones and the transfer of impact energy, while significantly enhancing the impact resistance of the roadway. This study not only provides a systematic theoretical basis for close-distance coal seam mining and rock burst prevention but also offers scientific guidance and technical reference for surrounding rock control and dynamic disaster prevention of roadways in similar close-distance coal seam mining projects, which is of important engineering value for ensuring the safe and efficient mining of underground coal resources. Full article

Two-dimensional antimonene has recently emerged as a promising electrocatalytic platform; however, its oxygen reduction reaction (ORR) activity and modulation strategies remain largely unexplored. Herein, density functional theory (DFT) calculations are employed to systematically investigate ORR catalysis on antimonene co-doped with transition metal (TM) and nonmetal (C, P) dual atoms. The results reveal that Pd@C–Sb, Pt@C–Sb, and Pd@P–Sb exhibit remarkably enhanced ORR activity, delivering low overpotentials of 0.31 V, 0.32 V, and 0.38 V, respectively, significantly outperforming their single-atom-doped counterparts. Mechanistic analyses demonstrate that nonmetal dopants induce strong synergistic interactions with TM centers, leading to charge redistribution and effective regulation of the TM d-band center, which optimizes the adsorption energetics of key ORR intermediates. Notably, the number of d-electrons of TM atoms is identified as a reliable electronic descriptor governing intermediate binding strength and catalytic activity. Furthermore, ab initio molecular dynamics simulations confirm the excellent thermodynamic stability of the optimized dual-atom catalysts. This work elucidates the atomic-scale origin of synergistic enhancement in dual-atom-doped antimonene and provides a rational design strategy for high-performance ORR electrocatalysts based on two-dimensional main-group materials. Full article

Background/Objectives: Paracetamol is a widely analgesic and antipyretic drug; however, its limited anti-inflammatory efficacy and safety concerns motivate the search for novel non-opioid alternatives. In this study, a series of 4-hydroxyphenylamino-naphthoquinones were designed as paracetamol-inspired analogs and synthesized via a solvent-free, silica-assisted Michael addition, providing a sustainable and efficient synthetic route. Methods: The compounds were evaluated using an integrated strategy combining in silico prediction, density functional theory calculations, molecular docking, ADMET profiling, and in vivo phenotypic pharmacological assays. Results: In vivo evaluation revealed pronounced peripheral antinociceptive activity in the acetic acid-induced writhing model and robust anti-inflammatory effects in carrageenan-induced paw edema, comparable to those of naproxen. These findings suggest a predominantly peripheral mechanism consistent with anti-inflammatory and antinociceptive profiles linked to cyclooxygenase inhibition. A normalization-based multi-criteria analysis integrating peripheral, anti-inflammatory, central, and antipyretic endpoints enabled transparent phenotypic prioritization within the series. Under this framework, compound 7 emerged as the most balanced peripheral–anti-inflammatory candidate, whereas compound 8, evaluated experimentally as a regioisomeric mixture, showed comparatively stronger central antinociceptive activity in the hot plate test. Antipyretic activity in an LPS-induced fever model was limited and not sustained. Conclusions: Overall, these findings indicated that the 4-hydroxyphenylamino-naphthoquinone scaffold emerges as a promising non-opioid platform for peripheral inflammatory pain, supporting further investigation of its pharmacological and mechanistic properties. Full article

Traditional evaluations of revetment projects primarily focus on structural safety and economic analysis, which cannot comprehensively reflect the overall effectiveness of such projects. To address this issue, this paper establishes a comprehensive evaluation index system for ecological revetments based on ecosystem theory and sustainable development principles. The system is tailored for the Pinglu Canal Ecological Revetment Demonstration Project. It assesses three key aspects: structural stability, ecological health, and socioeconomic benefits. Subjective weights were calculated using the Fuzzy Analytic Hierarchy Process (FAHP). Objective weights were determined by optimizing the Projection Pursuit (PP) model with the Tent-improved Crocodile Ambush Optimization Algorithm (TCAOA). Game theory was employed to compute the combined weights. The evaluation grade of the ecological revetment project was subsequently determined using a cloud model. The results show that the cloud eigenvalues of the project’s comprehensive evaluation are (1.096, 0.209, 0.047), and the application effectiveness is rated as “Excellent”. The cloud expected values for structural stability, ecological health, and socioeconomic benefits are 1.02, 1.18, and 1.15, respectively. All of these values are at the “Excellent” level. Compared with GA-PP and PSO-PP, TCAOA-PP converges faster and more stably. It requires only 347 iterations, achieves a coefficient variation of 3.8%, and reduces computation time by 23%. By revealing the nonlinear coupling relationships among indicators, the model presented in this paper provides a methodological foundation for establishing an evaluation framework that is ecologically interpretable for bank protection. This study has important practical significance for promoting the high-quality development of inland waterways and the construction of ecological revetments. Full article

High-speed photodetectors with extended dynamic ranges are critical for emerging optical systems like LiDAR. This paper presents a design methodology for a modified uni-traveling-carrier photodetector (MUTC-PD) that integrates a physics-based analytical model with numerical simulations. The existing analytical models for MUTC-PDs rely on approximations that may not hold under high injection levels and high frequencies, leading to discrepancies between theoretical predictions and practical observations. To address this limitation, we re-examine the governing equations and derive a corrected frequency response analytical model based on drift–diffusion theory by decomposing the device into distinct transport regions, enabling a physically meaningful optimization of the epitaxial layer structure to maximize theoretical intrinsic bandwidth. The calculated results closely match the simulated bandwidth (maximum error less than 6%), demonstrating consistent peak positions and trends. Subsequently, numerical simulations reveal the dynamic evolution of the device’s bandwidth under varying incident optical intensities. The results demonstrate that the intrinsic bandwidth initially increases to a peak of 325.82 GHz at $7\times {10}^4\mathrm{W}/{\mathrm{cm}}^2$ under −3.5 V, attributed to the drift-enhancement effect driven by the self-induced quasielectric field. Beyond this optimal regime, the space charge effect causes internal field collapse and significant bandwidth degradation. This study establishes bandwidth maintenance capability under high injection as a key metric for linearity, offering a transparent theoretical and practical framework for designing a high-speed MUTC-PD. Full article

Polyhalite, K₂SO₄•MgSO₄•2CaSO₄•2H₂O, a ternary evaporite mineral, is commonly found in evaporitic rock salt strata, where it acts as an indicator mineral for potash evaporite deposits. As a directly exploitable mineral potash fertilizer, polyhalite serves as an important substitute for potassium resources. The thermodynamic properties of polyhalite remain poorly characterized experimentally; consequently, current estimates predominantly rely on predictive modeling and indirect experimental approaches. The Raman spectra of free SO₄²⁻ vibrational modes in various sulfate minerals are sensitive to the local symmetry and hydrogen-bonding environment within crystal hydrates, and are directly influenced by the surrounding crystal field. This sensitivity makes Raman spectroscopy a powerful tool for investigating and identifying the crystal structures of sulfate minerals. In this work, the thermodynamic and Raman vibrational properties of polyhalite were investigated using density functional theory (DFT). Phonon calculations at the optimized geometry were employed to compute polyhalite’s key thermodynamic properties—specific heat, entropy, enthalpy, Gibbs free energy, and Debye temperature—over a temperature range of 0–1000 K. The results showed that: (1) the computed volume exhibited minimal error, approximately 0.87%, compared to experimental data; (2) the calculated values for the isobaric heat capacity and entropy were 420.72 and 531.39 J·mol⁻¹·K⁻¹ at 298.15 K, respectively; and (3) the calculated value for the free energy of formation at 298.15 K was −5670 kJ·mol⁻¹. The computed Raman spectrum results showed that the typical spectral features of polyhalite are: (1) ν1 for 1024 cm⁻¹, symmetric stretching mode; (2) ν2 for 464 cm⁻¹, symmetry bending mode; and (3) ν4 for 627 cm⁻¹, anti-symmetry bending mode. Full article