Search Results (72)

Phosphorus is recognized as one of the primary contributors to eutrophication in freshwater ecosystems. Among the various strategies proposed to mitigate its impact, adsorption-based removal has emerged as one of the most widely adopted and effective approaches globally. In this study, Zn/Al-layered double hydroxides (LDHs) were synthesized by varying the molar ratio of cations to obtain materials with different cationic densities. The materials were additionally modified via a co-precipitation method to incorporate titanium dioxide (TiO₂) or zinc oxide (ZnO) nanoparticles to synthesize novel composite nanomaterials aimed at phosphate species removal from aqueous solutions. The resulting materials demonstrated orthophosphate adsorption capacities exceeding 45 mg/g in most cases. Adsorption kinetics were evaluated using pseudo-first order and pseudo-second order models, while equilibrium data were fit to the Langmuir and Freundlich isotherms. The results indicated that the pseudo-second order model and the Langmuir isotherm provided the best fit, suggesting that the adsorption process is predominantly chemisorption occurring on a homogeneous monolayer. These findings highlight the potential of TiO₂/ZnO–LDH composites as efficient adsorbents for phosphorus remediation in aquatic environments. Full article

Sulfur hexafluoride (SF₆) serves as an essential insulating and arc-extinguishing medium in power facilities, while it is an extremely potent greenhouse gas with an ultra-long atmospheric lifetime. To realize efficient medium-temperature harmless disposal of waste SF₆, two-dimensional stable C₄N monolayers were adopted as substrates to load ZnO and CuO nanoparticles for composite catalyst fabrication. XRD, TEM, and EDS characterizations confirmed the uniform dispersion of the metal oxides without destroying the C₄N two-dimensional skeleton. Comparative experiments proved that an NH₃ reducing atmosphere significantly accelerates SF₆ decomposition. The 3:1 CuO-modified catalyst achieved a maximum SF₆ conversion of 91%, and a CaO additive effectively restrained high-temperature sintering and irreversible HF halogen poisoning, boosting overall catalytic efficiency by approximately 30%. DFT adsorption simulations revealed totally different active centers: hollow sites dominate ZnO-C₄N with broad adsorption capacity for SO₂, SO₂F₂, and other fluorinated intermediates, whereas surface O sites of CuO-C₄N exhibit exclusive strong chemisorption toward SO₂. Combined with macroscopic kinetics and atomic-scale interfacial interaction rules, their distinct stepwise defluorination pathways were illustrated. This study offers solid experimental data and microscopic theoretical guidance for designing advanced C₄N-based catalysts for waste SF₆ abatement. Full article

This study focuses on sustainable atmospheric water harvesting (AWH) using film-containing green nanomaterials. Particular emphasis is given to chitosan as a sustainable biopolymer matrix due to its intrinsic hydrophilicity, biodegradability, film-forming ability and abundance of amino and hydroxyl functional groups that favor water adsorption and nanoparticle interaction. ZnO, SiO₂ and Fe-Zn-SiO₂ nanoparticles with abundant hydroxyl groups were synthesized from plant-based materials such as biomass from peanut and banana wastes, as well as plant extracts. Nanocomposite membranes containing nanoparticles with a high specific surface area and moisture-sensitive behavior were successfully developed. Results showed that bilayer films outperformed monolayer systems in water harvesting performance. In particular, the bilayer film composed of Chitosan/G-ZnO (10 wt.%) on the top layer and Chitosan/G-SiO₂ (10 wt.%) in the bottom layer displayed outstanding hydrophilic properties with water contact angles reduced to 42–43°. The material demonstrated an equilibrium adsorption capacity for water at 0.90 g/g and a passive yield of 1.5–2.2 mL/g per day. The improved adsorption behavior was attributed to the synergistic effect between the hydroxyl-rich oxide nanoparticles, the intrinsic water affinity of chitosan, and the layered porous structure. Moreover, the samples showed good thermal and mechanical stability and retained their structure after several uses. These findings highlight the potential of chitosan-centered green nanocomposites as sustainable materials for passive AWH applications. Full article

High-sensitivity detection of formaldehyde is critically important for environmental protection and public health. Zinc oxide (ZnO) is a widely used core material for chemiresistive gas sensors; however, its conventional low-index facets suffer from a limited number of active sites, creating a bottleneck for further sensitivity enhancement. To overcome this limitation, this study pioneers the application of the highly reactive ZnO $\left[20\overline{2}1\right]$ high-index polar surface for formaldehyde detection. By leveraging its unique stepped atomic configuration and unprecedented density of coordination-unsaturated active sites, we systematically investigate the formaldehyde adsorption behavior and the underlying sensing mechanism using first-principles calculations based on density functional theory (DFT). The pristine ZnO $\left[20\overline{2}1\right]$ surface exhibits intrinsic metallic character. At a coverage of 1 monolayer (ML), the most stable G1 configuration achieves an adsorption energy of −1.54 eV per CH₂O molecule. Within a 2 × 1 supercell, formaldehyde adopts both associative and dissociative adsorption modes. At a lower coverage, formaldehyde forms a stable bidentate structure through dual C–O and Zn–O bonding interactions. Electronic structure analysis reveals significant orbital hybridization and interfacial charge redistribution upon adsorption. Notably, associative adsorption opens a bandgap of 0.04 eV at the Fermi level, inducing a metal-to-semiconductor transition. In contrast, dissociative adsorption results in pronounced n-type doping, thereby elucidating the microscopic origin of the resistivity decrease observed in ZnO-based sensors. Overall, this work highlights the structural advantages of high-index facets and demonstrates for the first time the superior formaldehyde adsorption capability of the ZnO $\left[20\overline{2}1\right]$ facet, providing robust theoretical guidance for the rational design of next-generation, high-performance gas-sensing materials. Full article

The sluggish kinetics of alkaline hydrogen oxidation reaction (HOR) and high cost of Pt–based catalysts have long hindered large–scale deployment of alkaline membrane fuel cells. Via first–principles calculations, we designed a series of 3d transition metal single atoms anchored on PdN₂ monolayer (TM–PdN₂, TM = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) and evaluated their alkaline HOR performance. Ti-, Cr-, Fe-, Co-, Ni-modified systems exhibit excellent thermodynamic and electrochemical stability under operating conditions. Single-atom doping tunes the p-band center of N and d-band center of metal sites, enabling precise modulation of H and OH adsorption strengths. Mechanistic analysis reveals HOR follows H₂ + 2OH* → H* + OH* + H₂O → 2H₂O, with the final step as rate-determining step. H adsorption contributes 3.45 times more to HOR activity than OH adsorption. Fe–PdN₂ delivers the best performance, with an ultra–low barrier of 0.11 eV and a rate constant of 2.82 × 10¹⁰ s^–1·site⁻¹, values that significantly outperform those of Pt(111) (0.22 eV, 4.5 × 10⁹ s⁻¹·site⁻¹). This work provides theoretical guidance for rational design of high–performance alkaline HOR electrocatalysts. Full article

The dielectric response provides an integral description of polarization mechanisms across frequency ranges and constitutes a key physical basis for understanding ferroelectric behavior. Here, we systematically investigate the broadband dielectric response of Group-II metal oxide (BeO, MgO, CaO, ZnO, and CdO) monolayers using first-principles calculation. In the low-frequency regime, ionic polarization governs the dielectric response. A distinctive feature is the LO–TO degeneracy at the Γ point accompanied by a V-shaped nonanalytic LO phonon dispersion. d-state hybridization increases with the metal atomic number, resulting in higher Born effective charge, which works together with phonon softening, reduced mass and unit cell area to significantly strengthen the ionic dielectric contribution. The quasiparticle band gap decreases with the metal atomic number, driving redshifts of the dielectric function and wide band optical response from the deep-ultraviolet to the near-infrared. Particularly, CdO exhibits the strongest electronic polarization, with an optical dielectric constant of 2.68 and a static refractive index of 1.64. This work establishes a complete dielectric spectrum from ionic to electronic polarization, providing theoretical guidance for polarization engineering and design of two-dimensional ferroelectric devices. Full article

Antimony (Sb) contamination in water poses significant environmental and health risks due to its high toxicity, persistence and complex redox behavior. Magnetic spinel ferrites (MFe₂O₄) have shown promise for Sb removal; however, the intrinsic influence of divalent metal species (M²⁺) in regulating Sb(III)/Sb(V) adsorption performance and interfacial mechanisms remains poorly understood. In this study, MnFe₂O₄, ZnFe₂O₄ and NiFe₂O₄ nanoparticles were synthesized and systematically evaluated to elucidate how M²⁺ governs Sb immobilization behavior. Batch adsorption experiments revealed pronounced M–dependent selectivity. MnFe₂O₄ exhibited the highest Sb(III) adsorption capacity (229.89 mg·g⁻¹), whereas NiFe₂O₄ showed superior affinity toward Sb(V) (up to 257.07 mg·g⁻¹). Adsorption kinetics for both Sb species followed pseudo-second-order models, indicating chemically controlled processes. Isotherm analyses indicated predominantly monolayer complexation for Sb(III), while Sb(V) adsorption displayed mixed adsorption characteristics, reflecting surface heterogeneity. Mechanistic investigations based on FTIR and XPS analyses suggest that Sb(III) immobilization is dominated by inner-sphere complexation with surface Fe–O/Fe–OH groups, whereas Sb(V) adsorption involves synergistic coordination with both Fe–O and M–O (Mn–O/Ni–O) functional groups. XPS analysis of Sb-loaded ZnFe₂O₄ revealed the coexistence of Sb(III) and Sb(V) species after Sb(III) adsorption, indicating surface-confined partial oxidation; the extent of solution-phase conversion was not independently quantified. Therefore, the redox process is interpreted as an interfacial phenomenon rather than bulk oxidation in solution. These results clarify that M²⁺ species influence Sb removal behavior by modulating the reactivity of surface functional groups and interfacial redox characteristics, rather than merely altering adsorption capacity. This work provides spectroscopic insight into M-dependent structure–activity relationships in spinel ferrites and offers a theoretical basis for the rational design of magnetic adsorbents for selective and efficient Sb remediation. Full article

This study aims to evaluate the adsorption performance of ZnO- and TiO₂-coated clinoptilolite composites for the removal of methylene blue (MB) from aqueous solutions and to clarify the governing adsorption mechanisms. Batch adsorption experiments were systematically conducted to investigate the effects of initial pH (3–10), MB concentration (50–200 mg/L), adsorbent dosage (0.05–1.00 g/100 mL), contact time (5–300 min), and temperature (298–313 K). Equilibrium, kinetic, and thermodynamic analyses were employed to comprehensively describe the adsorption behavior. The results demonstrated that MB adsorption onto both composites followed the Langmuir isotherm model, indicating monolayer adsorption on homogeneous surfaces. The maximum adsorption capacities were determined as 56 mg/g for ZnO-coated clinoptilolite and 106 mg/g for TiO₂-coated clinoptilolite, confirming the superior adsorption affinity of the TiO₂-modified composite. Thermodynamic parameters further indicated that the adsorption process was spontaneous, feasible, and thermodynamically favorable within the investigated temperature range. Physicochemical characterization by FTIR, SEM, BET, and XRD confirmed the successful surface modification of clinoptilolite and the enhancement of its structural and textural properties. Overall, the findings suggest that ZnO- and TiO₂-coated clinoptilolite composites are efficient and sustainable adsorbents with strong potential for wastewater treatment applications. Full article

Metal ions exemplify one of the most harmful and environmentally detrimental contaminants of water systems. This work describes the creation of an innovative chelated carbon-doped nickel and titanium oxide (C-NiTiO₂) hybrid as an adsorbent for the effective elimination of metal ions. The dominance of the TiO₂ anatase phase with a ≈ 61 nm crystallite size was verified by XRD and Raman investigation. Morphology investigations exposed polygonal nanoparticles consisting of Ti, C, Ni, and O. The nanostructure exhibited a surface area of 17 m²·g⁻¹, a pore diameter of ≈1.5 nm, and a pore volume of 0.0315 cm³·g⁻¹. The nanostructure was evaluated for the elimination of Zn (II) ions from an aqueous solution. The metal ion adsorption onto the hybrid nanomaterial was described and comprehended using adsorption kinetics and equilibrium models. The adsorption data matched well with the pseudo-second-order kinetics and Langmuir adsorption models, indicating a monolayer chemisorption mechanism and achieving a maximum Zn (II) ion elimination of 369 mg·g⁻¹. Mechanistic investigation indicated film diffusion-controlled adsorption through inner-sphere complexation. The nanosorbent could be regenerated and reused for four rounds without appreciable activity loss, thus demonstrating its potential for water cleanup applications. Full article

This work investigated the effects of gamma irradiation on the adsorption capacities of rice husk (RH) for the removal of Cu²⁺, Cr³⁺, and Zn²⁺ ions from aqueous solutions, with potential applications in wastewater remediation. RH samples were gamma-irradiated at doses up to 40 kGy and characterized using SEM-EDS, XRF, FTIR, XRD, and BET analyses. While morphological and textural changes remained subtle, FTIR and SEM-EDS confirmed the formation and intensification of oxygen-containing functional groups, including –OH, –COOH, and C=O, as well as increased exposure of silica (Si–O) on the surfaces, which substantially enhanced surface reactivity of RH toward metal ions. Batch adsorption experiments revealed that 40-kGy irradiated RH samples (RH-40) exhibited the highest removal efficiencies compared to non-irradiated and lower-dose samples (RH-0, RH-10, RH-20, and RH-30), specifically with improvements of 415% for Cu²⁺, 502% for Cr³⁺, and 663% for Zn²⁺ compared to RH-0, determined at the initial concentration of 10 mg/L. Kinetic studies also showed rapid adsorption within the first 10–15 min, dominated initially by boundary-layer diffusion, followed by chemisorption-driven equilibrium behavior. The pseudo-second-order (PSO) model provided an excellent fit for all metals (R² = 0.999), indicating maximum model-predicted kinetic capacities of 555.56 mg/g (Cu²⁺), 769.23 mg/g (Cr³⁺), and 434.78 mg/g (Zn²⁺). Langmuir isotherms also fitted well (R² = 0.941–0.995), with predicted monolayer capacities of 535.33 mg/g (Cu²⁺), 491.64 mg/g (Cr³⁺), and 318.88 mg/g (Zn²⁺). Freundlich modeling further indicated favorable heterogeneous adsorption, with K_F values of 42.614 (Zn²⁺), 20.443 (Cr³⁺), and 16.524 (Cu²⁺) and heterogeneity factors (n) greater than 1 for all metals. These overall results suggested that gamma irradiation substantially enhanced RH functionality that enabled fast and high-capacity heavy-metal adsorption through surface oxidation and carbon valorization. Gamma-irradiated RH, therefore, represented a promising, low-cost, and environmentally friendly biosorbent for wastewater treatment applications. Full article

This study addresses the environmental challenge of end-of-life tire accumulation, a major source of toxic metals such as lead and cadmium in marine ecosystems. As a sustainable solution, multicomponent metal-oxide nanoparticles (Fe₃O₄, ZnO, CaO, MgO, and minor CaCO₃) were green-synthesized from sugarcane bagasse and stabilized with blackberry (Rubus glaucus) extract. Structural characterization (XRD, SEM, TEM, and EDS) confirmed their crystalline inorganic composition. Pb²⁺ was almost completely removed (95–99%) within 15–30 min using 50–100 mg of nanoparticles, with ~80–90% efficiency at 75 mg. Cd²⁺ removal showed dose-dependent kinetics: ~90% removal occurred within 10 min at 75 mg, while 50 and 100 mg reached ~60–70% after 60 min. Equilibrium, kinetic, and thermodynamic analyses revealed that Pb²⁺ adsorption followed the Langmuir model (R² = 0.982) with monolayer chemisorption, whereas Cd²⁺ obeyed the Freundlich model (R² = 0.945), indicating heterogeneous multilayer adsorption. Pb²⁺ removal fitted a pseudo-second-order model (R² = 0.991), while Cd²⁺ followed a pseudo-first-order behavior (R² = 0.958). Thermodynamic parameters (ΔG° < 0, ΔH° > 0, ΔS° > 0) confirmed a spontaneous and endothermic process. Sugarcane-bagasse-derived Fe₃O₄–ZnO–CaO–MgO nanomaterials act as sustainable and effective adsorbents for marine heavy metal removal. Full article

The treatment of contaminants from road infrastructure poses significant challenges due to their variable composition and the high concentrations of chloride ions, heavy metals, and oil-derived substances. Traditional methods for protecting groundwater environments are often insufficient. A promising alternative is permeable reactive barrier (PRB) technology, which utilizes recycled materials and construction waste as reactive components within the treatment zone of the ground. This paper delves into the potential of employing a composite (MIX) consisting of modified construction aggregate (as recycled material) and activated carbon (example of reactive material) to address environmental contamination from a mixture of heavy metals and chloride. The research involved chemical modifications of the road aggregate, activated carbon, and their composite, followed by laboratory tests in glass reactors and non-flow batch tests to evaluate the kinetics and chemical equilibrium of the reactions. The adsorption process was stable and conformed to the pseudo-second-order kinetics and Langmuir, Toth, and Redlich–Peterson isotherm models. Studies using MIX from a heavy metal model solution showed that monolayer adsorption was a key mechanism for removing heavy metals, with strong fits to the Langmuir (R² > 0.80) and Freundlich models, and optimal efficiencies for Cd and Ni (R² > 0.90). The best fit, at Cd, Cu, Ni = 0.96, however, was with the Redlich–Peterson isotherm, indicating a mix of physical and chemical adsorption on heterogeneous surfaces. The Toth model was significant for all analytes, fitting Cl and Cd well and Pb and Zn moderately. The modifications made to the composite significantly enhanced its effectiveness in removing the contaminant mixture. The test results demonstrated an average reduction of chloride by 85%, along with substantial removals of heavy metals: lead (Pb) by 90%, cadmium (Cd) by 86%, nickel (Ni) by 85%, copper (Cu) by 81%, and zinc (Zn) by 79%. Further research should focus on the removal of other contaminants and the optimization of magnesium oxide (MgO) dosage. Full article

The stable adsorption configurations, electronic structures, and dissociation properties of 2-chlorophenol on pristine and Al-decorated ZnO monolayer are investigated using density functional theory (DFT). Our results indicate that the interaction between 2-chlorophenol and pristine ZnO monolayer is weak, while Al-modified ZnO monolayer can significantly enhance the adsorption of 2-chlorophenol. Therefore, compared to the pristine ZnO monolayer, the ZnO monolayer modified with Al is more sensitive to 2-chlorophenol molecules. Moreover, both pristine ZnO and Al decorated ZnO monolayers exhibit lower barriers for the dissociation of 2-chlorophenol molecules. These results provide a deeper understanding of the adsorption and dissociation performance of the ZnO monolayer for 2-chlorophenol molecules, which will contribute to the further application of ZnO in the fields of catalysts and gas sensing. Full article

A room-temperature synthesis was used to prepare ZIF-76 by combining the organic linker imidazole and 5-chlorobenzimidazole, with the addition of NaOH as a modulator. The synthesis process was optimized by modifying the existing method, which includes the introduction of heating, different types of solvent, and adjustment to the reactant ratio. The synthesized MOFs were characterized to evaluate their crystallinity, textural properties and surface morphology. The result demonstrated that the introduction of heat led to the formation of ZnO whereas the replacement of DEF–DMF with methanol resulted in the production of amorphous material. Moreover, a change in precursor ratio led to the production of ZIF-76 with a low yield and surface area. Meanwhile, CO₂ adsorption was performed in a pressure range of 0–1.2 bar at 298.15 K. Notably, ZIF-76_B with a low surface area exhibited a greater CO₂ uptake capacity of 1.43 mmol/g compared to ZIF-76_A, which recorded 1.29 mmol/g. Furthermore, the isotherm and kinetic models were applied to fit the experimental CO₂ adsorption data. The analysis of the adsorption models indicated that the CO₂ adsorption was primarily governed by a monolayer formation on a homogeneous surface. Nevertheless, there was a slight diversion in terms of predicted q_m with experimental data, which could be attributed to the adsorption not yet reaching equilibrium. Additionally, the kinetic model was applied to the initial stage of adsorption in the pressure range of 0–0.24 bar. The Elovich model was found to fit better with the CO₂ uptake capacity data of ZIF-76_A and ZIF-76_B suggesting that the adsorption process may involve multiple mechanisms. Full article

The present study aimed to investigate the ability of an aqueous extract derived from mustard seed meal to counteract the effects of E. coli endotoxin lipopolysaccharide (LPS) on the intestinal epithelium. Caco-2 cells were cultured together with HT29-MTX and used as a cellular model to analyze critical intestinal parameters, such as renewal, integrity, innate immunity, and signaling pathway. Byproducts of mustard seed oil extraction are rich in soluble polysaccharides, proteins, allyl isothiocyanates, and phenolic acids, which are known as powerful antioxidants with antimicrobial and antifungal properties. Cells were seeded at a ratio of nine (Caco-2) to one (HT29-MXT) and treated for 2 h with mustard meal extract (ME, dilution 1/50) and zinc oxide (ZnO, 50 μM) after reaching 80–100% confluence. Then, they were challenged with 5 μg/mL E. coli-LPS and incubated for another 4 h. The results show that LPS did not alter the cell viability but decreased proliferation compared to the control, ME and ZnO treatments. LPS altered the cell membrane integrity and monolayer permeability by decreasing the transepithelial electrical resistance and tight-junction protein expression. In addition, LPS increased the activity of LDH and the expression of Toll-like receptors. The mechanisms by which LPS induces these disturbances involves the overexpression of PKC, p38 MAPK, and NF-κB signaling molecules. The pretreatment with mustard meal and ZnO succeeded in counteracting the impairment of epithelial renewal, the damage of the membrane integrity and permeability as well as in restoring the gene expression of tight-junction proteins. Full article