Search Results (1,114)

Li-Argyrodite-type Li₆PS₅Cl solid electrolyte is one of the most extensively investigated and promising materials in the field of all-solid-state batteries. However, its interfacial stability against lithium metal anodes remains challenging. Herein, first-principles calculations were employed to probe the effects of Zr and F co-doping on the interfacial structural characteristics of Li₆P_0.9Zr_0.1S_4.9F_0.1Cl solid electrolytes in contact with lithium metal at the atomic scale. Systematic investigations were conducted on interfacial structural stability, electronic structure, lithium-ion transport properties, and stress–strain properties. Theoretical results demonstrate that the formation energy of sulfur on the lithium metal side in the Zr and F co-doped interface is significantly increased, which stems from the strong bonding interactions of Zr–S and P-F bonds. This effectively suppresses sulfur diffusion toward the lithium metal anode, thereby enhancing the interfacial structural stability. Moreover, Zr and F co-doping simultaneously improves both the lithium-ion migration capability and mechanical stress–strain properties at the interface. The maximum strain at the Li/Li₆PS₅Cl interface increases substantially from 6% to 12% with the implementation of Zr/F co-doping. The Li⁺ migration barrier at the interface exhibits a reduction of 36%. The insights from this study can serve as a design guideline for engineering high-performance solid electrolytes for all-solid-state batteries. Full article

1-Butyl-3-methylimidazolium (bmim) ionic liquids (ILs) are widely used for lignocellulose fractionation, yet their role extends beyond mere solvents. This study revealed that bmim-based ILs act as active chemical reagents, modifying the lignin structure in an anion-dependent manner. Thermal treatment (80–150 °C) of spruce dioxane lignin with [bmim]OAc, [bmim]Cl, and [bmim]MeSO₄ resulted in two distinct transformation pathways. In [bmim]MeSO₄, acidic catalysis dominates, leading to lignin condensation (increase in weight-average molecular weight, M_w, to 15.2 kDa at 150 °C) and intense sulfur incorporation (up to 9.9%) via anion-derived methylation/sulfation. Conversely, [bmim]OAc promotes depolymerization (decrease in M_w to 3.6 kDa) and efficient covalent bonding of the bmim cation to lignin (up to 10.8 cations per 100 aromatic units and a 6.5% nitrogen content at 150 °C), preventing condensation. Two-dimensional NMR and HPLC-HRMS analyses revealed the formation of a C–C bond between the C₂ atom of the imidazole ring and the α-carbon of the phenylpropane lignin fragments and allowed for the identification of a number of individual nitrogen-containing lignin oligomers in the [bmim]OAc-treated samples. Their formation likely proceeds via nucleophilic addition of the N-heterocyclic carbene (NHC), derived from the bmim cation by deprotonation with the highly basic acetate anion, to aldehyde groups. The action of [bmim]Cl primarily induces acid-catalyzed transformations of lignin with minimal covalent modification. These findings redefine imidazolium ILs as reactive media in biorefining, where their covalent interactions can influence the properties of lignin but complicate its native structure and the recyclability of the IL. Full article

We have fabricated amorphous tin oxide (a-SnO_x) thin-film transistors (TFTs) with Al₂O₃ gate insulator from deep eutectic solvents (DESs). DESs were formed using the chloride derivates of each precursor (SnCl₂, or AlCl₃) mixed with urea. The DESs were then used as precursors for the semiconductor and dielectric. Our target was to form extremely thin semiconductor film, and a sufficient high capacitance insulator. We characterized the physical and chemical properties of the DES-derived thin films by X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). We could evaluate that the highest content of metal–oxygen bonds was from the DES condition SnCl₂–urea = 1:3. At a low 300 °C budget temperature, we could fabricate a 3.2 nm thick a-SnO_x layer and 30 nm thick Al₂O₃, from which the TFT demonstrated a mobility of 80 ± 17 cm²/Vs, threshold voltage of −0.29 ± 0.06 V, and subthreshold swing of 88 ± 11 mV/dec. The proposed process is adequate with the back-end of the line (BEOL) process, but it is also eco-friendly because of the use of DESs. Full article

Mercury adsorption/oxidation plays a crucial role in mercury transformation during coal combustion. To gain an intuitive understanding of the adsorption/oxidation mechanisms between mercury and fly ash, changes in mercury speciation of fly ash before and after Hg adsorption were investigated using temperature-programmed decomposition–atomic fluorescence spectroscopy (TPD-AFS). The results directly reveal that the primary adsorption/oxidation mechanism between mercury and fly ash is the heterogeneous oxidation reaction of Hg⁰ to HgCl₂. The mercury adsorption capacity exhibits a strong positive correlation with both the unburned carbon (UBC) content and the specific surface area (SSA) of the fly ash, whereas the presence of metal oxides has a negligible effect on mercury adsorption. Higher inlet concentrations of Hg⁰ enhance mercury adsorption, while flue gas components such as N₂, O₂, and CO₂ have minimal influence on mercury adsorption. Full article

The rapid development of nanomedicine is driving extensive research and the synthesis of new nanomaterials. Biocompatible nanoparticles have the potential to serve as both imaging agents for medical diagnostics and carriers for targeted therapy. Among the various nanocomplexes investigated for cancer theranostics, gold nanoparticles stabilized by polyamidoamine (PAMAM) dendrimers have proven to be a promising platform. The unique physicochemical properties of gold nanoparticles, when combined with the branched architecture of PAMAM dendrimers, enhance stability, biocompatibility, and functionalization capability, enabling precise tumour targeting, improved imaging contrast, and controlled drug release. In this paper, we demonstrate the synthesis of gold nanoparticles stabilized by 2nd generation PAMAM dendrimers using three different methods: sonication, microwave, and unassisted techniques. The described synthesis approaches provide a rapid and straightforward method to achieve monodisperse particle size distribution and high colloidal stability up to 3 months. Physicochemical characterization of the nanocomplexes was carried out using ultraviolet-visible light spectroscopy, dynamic light scattering with zeta potential analysis, infrared spectroscopy, and atomic force microscopy. Furthermore, the effects of selected concentrations of PAMAM:HAuCl₄ nanoparticles for all types of synthesis on human breast adenocarcinoma and human osteosarcoma cell lines were investigated using cytotoxicity assays. The results of the conducted tests show cytotoxicity values at a similar level. However, the sample synthesized using the sonication technique exhibited the lowest toxicity. Full article

An experimental and theoretical investigation of the reaction between chlorine atoms and propane/deuterated propane (C₃H₈/C₃D₈) was performed. The experimental work aimed to determine absolute and site-specific rate constants for hydrogen and deuterium abstraction in the Cl + C₃H₈/C₃D₈ system. Measurements were conducted using the relative rate method at three temperatures between 298 and 387 K. Total rate constants for H/D abstraction by chlorine, as well as individual rate constants for abstraction from primary and secondary carbon sites, were obtained. The kinetic data for H abstraction agree well with previously reported literature values, confirming the reliability of the experimental approach. Notably, rate constants for the C₃D₈ + Cl reaction were determined for the first time, and the consistency of these results supports the reliability of the newly derived kinetic parameters. In the theoretical part of the study, hydrogen/deuterium abstraction from propane by atomic chlorine was analyzed within an atmospheric-chemistry context to clarify temperature dependence and site selectivity. Stationary points (SC, TS, PC, reactants, products) were optimized at MP2/aug-cc-pVDZ and verified by harmonic frequencies and intrinsic reaction-coordinate analyses. Eyring transition-state theory yielded 298–550 K rate constants with activation free energies referenced to SC. Our calculations indicate entrance-channel complex formation and effectively barrierless progress for most pathways; a small barrier appears only for RD1′. L-parameter evaluation classifies TS2 as reactant-like, and branching ratios identify –CH₂– abstraction (RX2) as dominant. These findings align with the experimental data. Full article

A new zirconium trichloride complex, supported by a monoanionic, pyrrole-based bisphosphinimine NNN-pincer ligand, [LZrCl₃] (L = 2,5-[ⁱPr₂P=N(4-ⁱPrC₆H₄)]₂NH(C₆H₂) (1), is reported. Comparison with a related iminopincer complex reveals significant differences in bond lengths and angles between the atoms around the metal centre, largely due to the more electron donating phosphinimine (R₃P=NR (R = alkyl, aryl)) functionality. The P=N bonds in complex (1•benzene) are longer than in the proteo ligand HL (L = 2,5-[Ph₂P=N(4-ⁱPrC₆H₄)]₂NH(C₆H₂)), which is consistent with phosphinimine coordination to a metal. This is the only reported zirconium complex with this specific ligand scaffold; no analogous complexes have been reported for other group 4 metals. This structure expands the library of Zr pincer complexes that bear tridentate ligand frameworks and sets the stage for the preparation of related complexes. Full article

6-Aminopyridine-3,5-dicarbonitriles and 3,6-diamino-5-cyanothieno[2,3-b]pyridines are well known as compounds with a broad spectrum of bioactivity. In particular, such thienopyridines are known as inhibitors of scrapie prion infection replication and accumulation, as well as selective inhibitors of malaria plasmodia kinase-3 with a pronounced antimalarial effect. To expand the range of such compounds, we studied the reaction of 3,6-diaminothieno[2,3-b]pyridine-5-carbonitriles with chloroacetyl chloride. The analysis of the Fukui indices showed that in these compounds the amino group at the C(3) atom is the most reactive. In fact, the reaction with ClCH₂C(O)Cl leads to the predicted product. Other reactions of thienopyridines as well as data on the biological activity of the products are discussed. Full article

The electronic effects of Lewis acids (LAs) in reducing the activation energies of Alder-ene (AE) reactions have been studied within the Molecular Electron Density Theory (MEDT). To this end, the AE reactions of 2-methylbutadiene (2MBD) with formaldehyde (CHO) in the presence of three LAs with increasing acidic character, BH₃, BF₃, and AlCl₃, have been studied. Topological analysis of the electron density and the evaluation of the DFT-based reactivity indices indicate that LAs do not modify the electronic structure of the carbonyl group but markedly increase the electrophilic character of CHO. LAs not only strongly accelerate the AE reactions, but also modify the molecular mechanisms, changing them from a non-concerted two-stage one-step mechanism to a two-step one. Topological analyses of the electron density at the transition state structures (TSs) indicate that while the formation of the new C-C single bond has begun, the departure of the hydrogen has not yet started. A Relative Interacting Atomic Energy (RIAE) analysis of the activation energies allows the establishment of the electronic effects of LAs on the AE reactions. LAs increase the global electron density transfer (GEDT) occurring in polar AE reactions; this phenomenon markedly stabilizes the CHO framework at the TSs, decreasing the RIAE relative energies. Full article

This study investigates the torrefaction of polyvinyl chloride (PVC) and cellulose, two major constituents of agricultural waste, with the aim of improving chlorine removal and enhancing the energy quality of the resulting solid products. Thermodynamic simulations using HSC Chemistry 9.0 were first conducted to predict equilibrium compositions, particularly chlorine-containing species. Thermogravimetric analysis (TGA) and coupled TGA-FTIR were employed to monitor mass loss and identify gaseous chlorine compounds. Based on these preliminary results, torrefaction experiments were carried out at temperatures of 250–300 °C and durations of 30–90 min. The results demonstrate a significant synergistic effect between cellulose and PVC during co-torrefaction, achieving 97% chlorine removal under optimal conditions (9:1 cellulose-to-PVC ratio, 250 °C, 30 min). This effective dechlorination helps mitigate Cl-induced corrosion and reduces the risk of dioxin formation in industrial applications, enabling the sustainable upcycling of PVC-contaminated biomass into clean solid fuels. Torrefaction temperature exerted a stronger influence than time on mass loss, yielding approximately 40% solid residue at 300 °C. While both solid and energy yields decreased with increasing temperature and time, the O/C and H/C atomic ratios decreased by 56% and 48%, respectively, indicating a substantial improvement in fuel properties. The observed synergy is attributed to cellulose-derived hydroxyl radicals promoting PVC dehydrochlorination. This process offers a scalable and economically viable pretreatment route for PVC-containing biomass, potentially reducing boiler corrosion and hazardous emissions. Full article

Metathesis reactions of Ag[C(CN)₃] with anhydrous YbCl₃ dissolved in water combined with stoichiometric amounts of the alkali-metal salts A[C(CN)₃] (A = Na or K) yield the non-isotypic tetragonal compounds NaYb[C(CN)₃]₄ (P4/nnc with a = 1188.37(9) pm, c = 1232.41(9) pm) and KYb[C(CN)₃]₄ (P4/nbm with a = 1179.26(9) pm, c = 668.73(5) pm). Both crystal structures contain a three-dimensional framework (Niggli formula: $\begin{array}{c}3\\ \infty \end{array}${(Yb[C(CN)₃]_8/2)⁻}) with Yb³⁺ in square antiprismatic coordination of terminal nitrogen atoms (d(Yb–N) = 241–242 pm) from eight planar star-shaped tricyanomethanide anions [C(CN)₃]⁻. The Na⁺ or K⁺ cations occupy vacancies, which provide them with a tetrahedral coordination sphere of nitrogen (d(Na–N) = 239 pm vs. d(K–N) = 276 pm) from four [C(CN)₃]⁻ anions. This difference results from secondary contacts with the central carbon atoms (d(Na–C) = 361 pm vs. d(K–C) = 367 pm) of four different [C(CN)₃]⁻ units, which do not contribute to NaYb[C(CN)₃]₄, but effectuate a lot in the case of KYb[C(CN)₃]₄. The Raman spectrum recorded for NaYb[C(CN)₃]₄ corroborates the presence of a pseudo-D_3h-symmetric tricyanomethanide anion [C(CN)₃]⁻ and the absence of water. Full article

This study systematically benchmarks the performance of four single soft magnetic powders—water-atomized Fe–Si–Cr (FeSiCr), silica-coated reduced iron powder (RIP), silica-coated carbonyl iron powder (CIP), and phosphate-coated CIP (CIP-P)—to establish quantitative relationships between powder attributes, deformation substructure, and high-frequency loss for molded power inductors (100 kHz–1 MHz). We prepared toroidal compacts at 200 MPa and characterized them by initial permeability (μ_i), core-loss (P_cv(f)), partitioning (P_cv(f) = K_hf + K_ef², K_h, $K_{\mathrm{e}}$: hysteresis and eddy-current loss coefficients), and EBSD (electron backscatter diffraction)-derived microstrain metrics (Kernel Average Misorientation, KAM; low-/high-angle grain-boundary fractions). Corrosion robustness was assessed using a 5 wt% NaCl, 35 °C, 24 h salt-spray protocol. Our findings reveal that FeSiCr achieves the highest μ_i across the frequency band, despite its lowest compaction density. This is attributed to its coarse particle size (D₅₀ ≈ 18 µm) and the resulting lower intragranular pinning. The loss spectra are dominated by hysteresis over this frequency range, with FeSiCr exhibiting the largest K_h, while the fine, silica-insulated Fe powders (RIP/CIP) most effectively suppress K_e. EBSD analysis shows that the high coercivity and hysteresis loss in CIP (and, to a lesser extent, RIP) are correlated with dense, deformation-induced subgrain networks, as evidenced by higher mean KAM and a lower low-angle grain boundary fraction. In contrast, FeSiCr exhibits the lowest KAM, with strain confined primarily to particle contact regions. Corrosion testing ranked durability as FeSiCr ≳ CIP ≈ RIP ≫ CIP-P, which is consistent with the Cr-rich passivation of FeSiCr and the superior barrier properties of the SiO₂ shells compared to low-dose phosphate. At 15 A, inductance retention ranks CIP (67.9%) > RIP (55.7%) > CIP-P (48.8%) > FeSiCr (33.2%), tracking a rise in effective anisotropy and—for FeSiCr—lower M_s that precipitate earlier roll-off. Collectively, these results provide a microstructure-informed selection map for single-powder formulations. We demonstrate that particle size and shell chemistry are the primary factors governing eddy currents (K_e), while the KAM-indexed substructure dictates hysteresis loss (K_h) and DC-bias superposition characteristics. This framework enables rational trade-offs between magnetic permeability, core loss, and environmental durability. Full article

This work prepared SnO₂ coatings on 304 stainless steel via the sol–gel and dip-coating techniques, using tin (II) chloride (SnCl₂) and tin (II) oxalate (SnC₂O₄) as precursors. The crystal structure analyzed by X-ray Diffraction (XRD) confirmed the cassiterite-type SnO₂ in both cases. The corrosion resistance in a 3 wt.% NaCl solution was evaluated by polarization resistance (Rp) and anodic potentiodynamic polarization. Coatings derived from the SnC₂O₄ precursor demonstrated exceptional performance, reducing the corrosion rate by up to three orders of magnitude (from 0.0973 mpy for uncoated steel to 0.00015 mpy), corresponding to a protection efficiency of 99.8%. In contrast, coatings from the SnCl₂ precursor increased the corrosion rate. X-ray Photoelectron Spectroscopy (XPS) analysis confirmed that this detrimental effect was due to the presence of chlorine (5.54 wt.%), which acted as an initiation site for pitting corrosion. Atomic force microscopy (AFM) and XRD of the effective SnC₂O₄-derived coatings revealed a homogeneous surface with low roughness and a textured cassiterite structure. The primary limitation of this work is that the sol–gel synthesis route using SnCl₂ is unsuitable for corrosion protection in chloride environments due to the incorporation of aggressive chlorine ions, whereas the chlorine-free SnC₂O₄ precursor yields highly protective SnO₂ coatings. Full article

The rapid growth in electronic waste (e-waste) generation highlights the urgent need for efficient and environmentally sustainable methods for metal recovery. This study focuses on the selective recovery of valuable metals from multilayer ceramic capacitors (MLCCs), commonly found in printed circuit boards (PCBs) of post-consumer electronics. MLCCs were manually recovered from dismantled computer PCBs, thermally treated, pulverized, and characterized using X-ray fluorescence and X-ray diffraction techniques. To evaluate green alternatives to traditional acid leaching, three deep eutectic solvents (DESs) based on choline chloride (ChCl) were prepared: citric acid (CA), glycerol (GLY), and a ternary (GLY-CA) mixture of both (GLY-CA). Leaching experiments were conducted over a 24 h period and analyzed using atomic absorption spectroscopy. The results showed complete recovery (100%) of copper using both CA and the GLY-CA mixture, while nickel recovery reached 100% with CA and moderate levels with GLY-CA. Zinc recovery was also high (99%) with both CA and GLY-CA. Iron showed a maximum recovery of 60%, potentially due to its occurrence in various chemical forms. The ternary DES (GLY-CA) demonstrated lower viscosity, improving handling and operational efficiency. These findings highlight the potential of citric-acid-based and ternary (GLY-CA) DESs as effective, low-toxicity leaching agents for the recovery of critical metals from MLCCs. Full article

N-chlorotaurine (Tau-Cl) is a mild oxidizing haloamine formed from the reaction of hypochlorous acid (HOCl) with taurine (2-amino-ethanesulfonic acid). It is widely used as a topical antiseptic. In this study, we investigated haloamines derived from the neurotransmitter γ-aminobutyric acid, specifically GABA chloramine and bromamine (GABA-Cl, GABA-Br), as well as their halogenated γ-aminobutyric acid ethyl esters (GABAet-Cl, GABAet-Br). Due to their higher hydrophobicity, the esterified haloamines were more potent oxidants in the presence of lyophilic surfactant micelles, demonstrating their greater ability to access hydrophobic environments. By using fluorescent azapentalenes as molecular targets incorporated into sodium dodecyl sulfate (SDS) micelles, the second-order oxidation rate constants (k₂) resulted in 1.15 × 10² and 1.10 × 10⁴ M⁻¹min⁻¹ for GABA-Cl and GABAet-Cl, respectively. As expected, due to the presence of a bromine atom, GABAet-Br was even more reactive (4.50 × 10⁶ M⁻¹min⁻¹). The ability of GABAet-Br to access hydrophobic sites was demonstrated by comparing the reaction rate using micelles generated by different surfactants such as SDS (4.5 × 10⁶ M⁻¹min⁻¹), cetyltrimethylammonium chloride (CTAC, 2.5 × 10⁴ M⁻¹min⁻¹), and triton X-100 (TX-100, 3.9 × 10³ M⁻¹min⁻¹). GABAet-Cl and GABAet-Br exhibited higher bactericidal activity against Staphylococcus aureus and Escherichia coli, probably due to their increased lipophilicity and improved penetration into microorganisms compared to GABA-Cl and GABA-Br. The enhancement of the oxidation capacity by GABAet-Cl and GABAet-Br represents a new direction in the exploration and application of haloamines as antiseptic agents. Full article