Search Results (1,203)

Recent research on the design and synthesis of new and upgraded materials for secondary batteries is growing to fulfill future energy demands around the globe. Herein, by using DFT calculations, the thermodynamic and electrochemical properties of Na/Na⁺@C₁₂ complexes and then halogens (X⁻ = Br⁻, Cl⁻, and F⁻) as counter anions are studied for the enhancement of Na-ion battery cell voltage and overall performance. Isolated C₁₂ nanorings showed a lower cell voltage (−1.32 V), which was significantly increased after adsorption with halide anions as counter anions. Adsorption of halides increased the Gibbs free energy, which in turn resulted in higher cell voltage. Cell voltage increased with the increasing electronegativity of the halide anion. The Gibbs free energy of Br⁻@C₁₂ was −52.36 kcal·mol⁻¹, corresponding to a desirable cell voltage of 2.27 V, making it suitable for use as an anode in sodium-ion batteries. The estimated cell voltage of these considered complexes ensures the effective use of these complexes in sodium-ion secondary batteries. Full article

The demand for anion exchange membranes (AEMs) is growing due to their applications in water electrolysis, CO₂ reduction conversion and fuel cells, as well as water treatment, driven by the increasing energy demand and the need for a sustainable future. However, current AEMs still face challenges, such as insufficient permeability and stability in strongly acidic or alkaline media, which limit their durability and the sustainability of membrane fabrication. In this study, polyvinyl alcohol (PVA) and chitosan (CS) biopolymers are selected for membrane preparation. Zinc oxide (ZnO) and porous organic polymer (POP) nanoparticles are also introduced within the PVA-CS polymer blends to make mixed-matrix membranes (MMMs) with increased OH⁻ transport sites. The membranes are characterized based on typical properties for AEM applications, such as thickness, water uptake, KOH uptake, Cl⁻ and OH⁻ permeability and ion exchange capacity (IEC). The OH⁻ transport of the PVA-CS blend is increased by at least 94.2% compared with commercial membranes. The incorporation of non-porous ZnO and porous POP nanoparticles into the polymer blend does not compromise the OH⁻ transport properties. On the contrary, ZnO nanoparticles enhance the membrane’s water retention capacity, provide basic surface sites that facilitate hydroxide ion conduction and reinforce the mechanical and thermal stability. In parallel, POPs introduce a highly porous architecture that increases the internal surface area and promotes the formation of continuous hydrated pathways, essential to efficient OH⁻ mobility. Furthermore, the presence of POPs also contributes to reinforcing the mechanical integrity of the membrane. Thus, PVA-CS bio-based membranes are a promising alternative to conventional ion exchange membranes for various applications. Full article

An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO₂ supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO₂ supports, namely SnA (synthesized almost at room temperature), SnB (hydrothermally treated at 180 °C), and SnC (annealed at 600 °C), are systematically investigated, all loaded with 1 mol% Pt from H₂PtCl₆ under identical mild conditions. The chloride ions from the SnCl₄ precursors were efficiently removed via a strong-base anion exchange reaction, resulting in highly dispersed, crystalline ~5 nm cassiterite SnO₂ particles. All Pt/SnO₂ composites displayed mesoporous structures with type IVa isotherms and H₂-type hysteresis, with SP1a (Pt on SnA) exhibiting the largest surface area (122.6 m²/g) and the smallest pores (~3.5 nm). STEM-HAADF imaging revealed well-dispersed PtOx domains (~0.85 nm), while XPS confirmed the dominant Pt⁴⁺ and Pt²⁺ species, with ~25% Pt⁰ likely resulting from photoreduction and/or interactions with Sn–OH surface groups. Raman spectroscopy revealed three new bands (260–360 cm⁻¹) that were clearly visible in the sample with 10 mol% Pt and were due to the vibrational modes of the PtOx species and Pt-Cl bonds introduced due the addition and hydrolysis of H₂PtCl₆ precursor. TGA/DSC analysis revealed the highest mass loss for SP1a (~7.3%), confirming the strong hydration of the PtOx domains. Despite the predominance of oxidized PtOx species, SP1a exhibited the highest catalytic activity (k_app = 1.27 × 10⁻² s⁻¹) and retained 84.5% activity for the reduction of 4-NP to 4-AP after 10 cycles. This chloride-free low-temperature synthesis route offers a promising and generalizable strategy for the preparation of noble metal-based nanocatalysts on oxide supports with high catalytic activity and reusability. Full article

Rapid socio-economic development and the impact of human activities have exerted tremendous pressure on the groundwater system of the Dawen River Basin (DRB), the largest tributary in the middle and lower reaches of the Yellow River. Hydrochemical studies on the DRB have largely centered on the upstream Muwen River catchment and downstream Dongping Lake, with some focusing solely on karst groundwater. Basin-wide evaluations suggest good overall groundwater quality, but moderate to severe contamination is confined to the lower Dongping Lake area. The hydrogeologically complex mid-reach, where the Muwen and Chaiwen rivers merge, warrants specific focus. This region, adjacent to populous areas and industrial/agricultural zones, features diverse aquifer systems, necessitating a thorough analysis of its hydrochemistry and origins. This study presents an integrated hydrochemical, isotopic investigation and EWQI evaluation of groundwater quality and formation mechanisms within the multiple groundwater types of the central DRB. Central DRB groundwater has a pH of 7.5–8.2 (avg. 7.8) and TDSs at 450–2420 mg/L (avg. 1075.4 mg/L) and is mainly brackish, with Ca²⁺ as the primary cation (68.3% of total cations) and SO₄²⁻ (33.6%) and NO₃⁻ (28.4%) as key anions. The Piper diagram reveals complex hydrochemical types, primarily HCO₃·SO₄-Ca and SO₄·Cl-Ca. Isotopic analysis (δ²H, δ¹⁸O) confirms atmospheric precipitation as the principal recharge source, with pore water showing evaporative enrichment due to shallow depths. The Gibbs diagram and ion ratios demonstrate that hydrochemistry is primarily controlled by silicate and carbonate weathering (especially calcite dissolution), active cation exchange, and anthropogenic influences. EWQI assessment (avg. 156.2) indicates generally “good” overall quality but significant spatial variability. Pore water exhibits the highest exceedance rates (50% > Class III), driven by nitrate pollution from intensive vegetable cultivation in eastern areas (Xiyangzhuang–Liangzhuang) and sulfate contamination from gypsum mining (Guojialou–Nanxiyao). Karst water (26.7% > Class III) shows localized pollution belts (Huafeng–Dongzhuang) linked to coal mining and industrial discharges. Compared to basin-wide studies suggesting good quality in mid-upper reaches, this intensive mid-reach sampling identifies critical localized pollution zones within an overall low-EWQI background. The findings highlight the necessity for aquifer-specific and land-use-targeted groundwater protection strategies in this hydrogeologically complex region. Full article

In shallow groundwater areas, the freeze–thaw process can easily exacerbate soil salinization. The variations and migrations of Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, SO₄²⁻, and HCO₃⁻ at the depth of 0–100 cm under shallow groundwater depth (2.63–2.87 m) during the freeze–thaw period were analyzed. And a multi-index comprehensive evaluation method based on factor analysis was employed to investigate the soil salinization degree. The results show that K⁺, Mg²⁺, and HCO₃⁻ exhibited surface enrichment during the freeze–thaw period, while Na⁺, Cl⁻, and SO₄²⁻ accumulated in the frozen layer during the freezing stage. However, there is no surface enrichment of Ca²⁺. During the freezing stage, Mg²⁺ and Cl⁻ exhibited the strongest migration capabilities among cations and anions, respectively. During the thawing stage, K⁺ and HCO₃⁻ were the cation and anion with the highest ionic migration capabilities, respectively. Total salinity (TS), Cl⁻, SO₄²⁻, HCO₃⁻, Na⁺, K⁺, Mg²⁺, and residual sodium carbonate (RSC) were identified as the dominant factors influencing the salinization degree during the freeze–thaw period. During the freezing stage, soil salt ions predominantly migrated from the unfrozen to the frozen layer, and the salinization degree in the frozen layer increased with the development of the frozen layer. In the thawing stage, soil salt ions migrated upward from the thawing front, and the salinization degree at the depth of 0–30 cm increased. This study provides insights for the prevention and control of soil salinization in arid regions. Full article

The enhancement of flavonoid content and antioxidant capacity in plants remains a significant area of focus in the investigation of plant-derived functional foods. This study systematically investigated the impact of exogenous zinc sulfate (5 mM ZnSO₄) stress on flavonoid content and antioxidant capacity in finger millet (Eleusine coracana L.) sprouts, along with its underlying molecular mechanisms. The results demonstrated that treatment with 5 mM ZnSO₄ significantly increased the flavonoid content in sprouts, reaching a maximum value of 5.59 μg/sprout on the 6th day of germination. ZnSO₄ stress significantly enhanced the activities of PAL, 4CL, and C4H, while also considerably upregulating the expression levels of flavonoid-biosynthesis-related genes. Physiological indicators revealed that ZnSO₄ stress increased the contents of malondialdehyde, hydrogen peroxide, and superoxide anion in the sprouts, while inhibiting sprout growth. As a stress response, ZnSO₄ stress enhances the antioxidant system by increasing antioxidant capacity (ABTS, DPPH, and FRAP), antioxidant enzyme activity (POD and SOD), and related gene expression (POD, CAT, and APX) in sprouts. This study provides experimental evidence for ZnSO₄ stress to improve flavonoid accumulation and antioxidant capacity in finger millet sprouts and provides important theoretical and practical guidance for the development of high-quality functional foods. Full article

Two-dimensional (2D) crystals which present unconventional stoichiometries on graphene surfaces in ambient conditions, such as Na₂Cl, Na₃Cl, and CaCl, have attracted significant attention in recent years due to their electronic structures and abnormal cation–anion ratios, which differ from those of conventional three-dimensional crystals. This unconventional crystallization is attributed to the cation–π interaction between ions and the π-conjugated system of the graphene surface. Consequently, their physical and chemical properties—including their electrical, optical, magnetic, and mechanical characteristics—often differ markedly from those of conventional crystals. This review summarizes the recent progress made in the fabrication and analysis of the structures, distinctive features, and applications of these 2D unconventional stoichiometry crystals on graphene surfaces in ambient conditions. Their special properties, including their piezoelectricity, metallicity, heterojunction, and room-temperature ferromagnetism, are given particularly close attention. Finally, some significant prospects and further developments in this exciting interdisciplinary field are proposed. Full article

This work represents the first use of a phosphonium salt-functionalized β-Cyclodextrin polymer (β-CDP) as a highly selective sensing membrane for monitoring the safety of drinking water against perchlorate ions (ClO₄⁻) using electrochemical impedance spectroscopy (EIS). Structural confirmation via ¹H NMR, ¹³C NMR, ³¹P NMR, and FT-IR spectroscopies combined with AFM and contact angle measurements demonstrate how the enhanced solubility of modified cyclodextrin improves thin film quality. The innovation lies in the synergistic combination of two detection mechanisms: the “Host-Guest” inclusion in the cyclodextrin cavity and anionic exchange between the bromide ions of the phosphonium groups and perchlorate anions. Under optimized functionalization conditions, EIS reveals high sensitivity and selectivity, achieving a record-low detection limit (LOD) of ~10⁻¹² M and a wide linear range of detection (10⁻¹¹ M–10⁻⁴ M). Sensing mechanisms at the functionalized transducer interfaces are examined through numerical fitting of Cole-Cole impedance spectra via a single relaxation equivalent circuit. Real water sample analysis confirms the sensor’s practical applicability, with recoveries between 96.9% and 109.8% and RSDs of 2.4–4.8%. Finally, a comparative study with reported membrane sensors shows that β-CDP offers superior performance, wider range, higher sensitivity, lower LOD, and simpler synthesis. Full article

The Nanmiao Emergency Groundwater Source Area, rich in H₂SiO₃, serves as a strategic freshwater reserve zone in western Jiangxi Province. However, the mechanisms underlying groundwater formation in this area remain unclear. This study applied a combination of statistical analysis, isotopic tracing, and hydrochemical modeling to reveal the hydrochemical characteristics and origins of groundwater in the region. The results indicate that Na⁺ and Ca²⁺ dominate the cations, while HCO₃⁻ and Cl⁻ dominate the anions. Groundwater from descending springs is characterized by low mineralization and weak acidity, with hydrochemical types of primarily HCO₃–Na·Mg and HCO₃–Mg·Na·Ca. Groundwater from boreholes is weakly mineralized and neutral, with dominant hydrochemical types of HCO₃–Ca·Na and HCO₃–Ca·Na·Mg, suggesting a deep circulation hydrogeochemical process. Hydrogen and oxygen isotope analysis indicates that atmospheric precipitation is the primary recharge source. The chemical composition of groundwater is mainly controlled by rock weathering, silicate mineral dissolution, and cation exchange processes. During groundwater flowing, water and rock interactions, such as leaching, cation exchange, and mixing, occur. This study identifies the recharge sources and circulation mechanisms of regional groundwater, offering valuable insights for the sustainable development and protection of the emergency water source area. Full article

Increasing water scarcity in arid regions has prompted the mining industry to develop strategies to maximize water recovery and reuse, especially in tailings treatment processes. In this context, the present investigation evaluated the effects of sodium polyacrylate (NaPA) on the compressibility and viscoelasticity of clayey tailings in the presence of hard water containing calcium and magnesium. To this end, clayey slurries were analyzed using rheological tests (rheograms and oscillatory viscoelasticity), zeta potential measurements, and compressibility tests using batch centrifugation. The yield stress was determined using the Herschel–Bulkley model, while the compressive yield stress (Py(Φ)) was calculated as a key indicator to characterize the degree of sediment consolidation. The results showed that NaPA, due to its anionic nature and high degree of ionization at pH 8, induces effective particle dispersion by increasing electrostatic repulsion and decreasing the interaction force between particles, which reduces both rheological parameters and compressive yield stress. For the 70/30 quartz/kaolin mixture, the yield stress decreased from 70.54 to 61.64 Pa in CaCl₂ and from 57.51 to 52.95 Pa in MgCl₂ in the presence of NaPA. It was also observed that suspensions in the presence of magnesium ions presented greater compressibility than those with calcium, attributable to the greater hydration radius of magnesium (10.8 Å), which favors less dense and more easily deformable network structures. Furthermore, a higher proportion of kaolin in the mixture resulted in higher yield stresses, a product of the clay’s laminar structure, colloidal size, and high surface area, both in the absence and presence of NaPA. Overall, the results show that incorporating NaPA significantly improves the compressibility and rheology of clayey tailings in hard water, offering a promising alternative for optimizing water recovery and improving tailings management efficiency in the context of water restrictions. Full article

Multifunctional water-treatment materials urgently need to be developed to avoid normal organic matter, inorganic anions, resistant bacteria, and hazardous disinfection by-products in conventional drinking water treatment strategies. While quaternary ammonium pyridine resins (QAPRs) possess porous adsorption structures and incorporate antibacterial groups, enabling simultaneous water disinfection and purification, their limited bactericidal efficacy hinders broader utilization. Therefore, a deeper understanding of the structure-dependent antimicrobial mechanism in QAPRs is crucial for improving their antibacterial performance. Hexyl (C₆) was proved to be the optimal antibacterial alkyl in the QAPRs. A new antibacterial quaternary ammonium pyridine resin Py-61 was prepared by more surficial bactericidal N⁺ groups and higher efficient antibacterial hexyl, performing with the excellent antibacterial efficiency of 99.995%, far higher than the traditional resin Py-6C (89.53%). The antibacterial resin Py-61 completed the disinfection of sand-filtered water independently to produce safe drinking water, removing the viable bacteria from 3600 to 17 CFU/mL, which meets the drinking water standard of China in GB5749-2022 (<100 CFU/mL). Meanwhile, the contaminants in sand-filtered water were obviously removed by the resin Py-61, including anions and dissolved organic matter (DOM). The resin Py-61 can be regenerated by 15% NaCl solution, and keeps the reused antibacterial efficiency of >99.97%. As an integrated disinfection–purification solution, the novel antibacterial resin presents a promising alternative for enhancing safety in drinking water treatment. Full article

Wastewater contains dyes originating from textile industries, and above a certain concentration, they can become dangerous due to their high toxicity. Divalent and trivalent metal coagulants, usually aluminum- or iron-based, have been studied worldwide. However, tetravalent coagulants, such as tin chloride, have not yet been extensively studied for application in wastewater treatment. Therefore, in this study, three types of coagulants were examined: SnCl₄, Cs, and a hybrid composite (CS@Sn) in two different mass ratios, abbreviated hereafter as CS@Sn_5% and CS@Sn_50%. The formation of the suggested CS@Sn hybrid coagulants was confirmed by applying SEM, XRD, and FTIR techniques. The results showed that the optimum conditions for RB5 removal was the addition of 20 mg Sn/L SnCl₄ (97.8%) and 50 mg Sn/L of CS@Sn_50% (64.8%) at pH 3.0. In addition, SnCl₄ was found to be an effective coagulant for all the examined anionic dyes, but it was not as effective for cationic dyes. Moreover, the coagulants were then tested in two mixed-dye solutions, both anionic dyes (RB5/RR120) and anionic/cationic (RB5/MV), resulting in a synergistic effect in the first one and a competitive effect in the secon. Finally, the proposed coagulants were successfully tested on real wastewater samples from an untreated textile dyeing industry. Therefore, the coagulants presented in this work for the removal of several dyes are also capable of being used for wastewater treatment. Full article

The efficacy of water resource management and protection hinges on a profound understanding of the controlling factors and regulatory mechanisms that shape groundwater chemistry within aquifers. Despite this, our comprehension of how groundwater chemistry and ion sources vary across diverse aquifer types remained limited. To bridge this gap, our study conducted a detailed hydrochemical and statistical investigation of porous, fissured, and karst aquifers. By applying multivariate statistical techniques, including principal component analysis (PCA) and hierarchical cluster analysis (HCA), the hydrochemical characteristics and main ion sources of each aquifer type, as well as distinct controlling factors and regulation patterns, were determined. Notably, evaporation predominantly affected the hydrochemistry of porous aquifers, whereas mineral dissolution and rock weathering processes played a pivotal role in shaping the groundwater evolution of fissured and karst aquifers. HCO₃⁻ and SO₄²⁻ are the most common anions of all types, while Na⁺ is dominant in porous and fissured aquifers and Ca²⁺ is dominant in karst aquifers. The most common hydrochemical types identified were HCO₃-Ca·Mg (accounting for approximately 56.84%) and SO₄·Cl-Na (constituting approximately 21.75%). PCA results revealed that lateral recharge from fissured aquifers in hilly regions into the groundwater of porous aquifer, and wastewater discharge and agricultural fertilizer application, significantly impact the groundwater chemistry across all three aquifer types. It is worth noting that the dissolution of carbonate minerals, often influenced by human activities, had a profound effect on the hydrochemistry of each aquifer. Conversely, the dissolution of evaporitic minerals affected groundwater chemistry primarily through cation exchange processes. In summary, the hydrochemical characteristics of these aquifer types were predominantly shaped by a complex interplay of mineral dissolution, cation exchange, evaporation, and anthropogenic activities, with notable contributions from fissured aquifer recharge and pollution. These insights were critical for informing national-level strategies for groundwater resource protection and management. Full article

Y₅F₃[AsO₃]₄ crystallizes needle-shaped in the tetragonal space group P4/ncc with the lattice parameters a = 1143.80(8) pm, c = 1078.41(7) pm and c/a = 0.9428 for Z = 4. The yttrium-fluoride substructure linked via secondary contacts forms a three-dimensional network $\begin{array}{c}3\\ \infty \end{array}${[Y₅F₃]¹²⁺} and the remaining part consists of ψ¹-tetrahedral [AsO₃]³⁻ units, which leave lone-pair channels along [001]. In contrast, platelet-shaped Y₅Cl₃[AsO₃]₄ crystals adopt the monoclinic space group C2/c with the lattice parameters a = 1860.56(9) pm, b = 536.27(3) pm, c = 1639.04(8) pm and β = 105.739(3)° for Z = 4. Condensation of [(Y1,2)O₈]¹³⁻ polyhedra via four common edges each leads to fluorite-like $\begin{array}{c}2\\ \infty \end{array}$ {[(Y1,2)O $\begin{array}{c}e\\ 8/2\end{array}$ ]⁵⁻} layers spreading out parallel to the (100) plane. Their three-dimensional linkage occurs via the (Y3)³⁺ cations with their Cl⁻ ligands on the one hand and the As³⁺ cations with their lone-pairs of electrons on the other, which also form within [AsO₃]³⁻ anions lone-pair channels along [010]. Both colorless compounds can be obtained by solid-state reactions from corresponding mixtures of the binaries (Y₂O₃, As₂O₃ and YX₃ with X = F and Cl) at elevated temperatures of 825 °C, most advantageously under halide-flux assistance (CsBr for Y₅F₃[AsO₃]₄ and ZnCl₂ for Y₅Cl₃[AsO₃]₄). By replacing a few percent of YX₃ with EuX₃ or TbX₃, Eu³⁺- or Tb³⁺-doped samples are accessible, which show red or green luminescence upon excitation with ultraviolet radiation. Full article

Rationally designing and synthesizing chemosensors capable of simultaneously detecting both anions and cations via water content modulation is challenging. In this study, we synthesized and characterized a novel triazine calixarene derivative-based iodide and copper ion-selective fluorescent “turn-off” sensor. This dual-channeled fluorescent probe is able to recognize Cu²⁺ and I⁻ ions simultaneously in aqueous systems. The fluorescent sensor s4 was synthesized by displacement reaction of acridine with 1, 3-bis (dichloro-mono-triazinoxy) benzene in acetonitrile. Mass spectrometry (MS), UV-vis, and fluorescence spectra were acquired to characterize the fluorescence response of s4 to different cations and anions, while infrared (IR) spectroscopy and isothermal titration calorimetry (ITC) were employed to study the underlying selectivity mechanism of s4 to Cu²⁺ and I⁻. In detail, s4 displayed extremely high sensitivity to Cu²⁺ with over 80% fluorescence decrement caused by the paramagnetic nature of Cu²⁺ in the aqueous media. The reversible fluorescence response to Cu²⁺ and the responses to Cu²⁺ in the solution of other potential interferent cations, such as Li⁺, Na⁺, K⁺, Ca²⁺, Cd²⁺, Zn²⁺, Sr²⁺, Ni²⁺, Co²⁺ were also investigated. Probe s4 also exhibited very good fluorescence selectivity to iodide ions under various anion (F⁻, Cl⁻, Br⁻, NO₃⁻, HSO₄⁻, ClO₄⁻, PF₆⁻, AcO⁻, H₂PO₄⁻) interferences. In addition to the fluorescent response to I⁻, s4 showed a highly selective naked-eye-detectable color change from colorless to yellow with the other tested anions. Full article