Search Results (66)

Atmospheric aqueous-phase reactions have been recognized as an important source of secondary organic aerosols (SOAs). However, the unclear reaction kinetics and mechanics hinder the in-depth understanding of the SOA sources and formation processes. This study selected ten different substituted phenolic compounds (termed as PhCs) emitted from biomass burning as precursors, to investigate the kinetics using OH oxidation reactions under simulated sunlight. The factors influencing reaction rates were examined, and the contribution of reactive oxygen species (ROS) was evaluated through quenching and kinetic analysis experiments. The results showed that the pseudo-first-order rate constants (k_obs) for the OH oxidation of phenolic compounds ranged from 1.03 × 10⁻⁴ to 7.85 × 10⁻⁴ s⁻¹ under simulated sunlight irradiation with an initial H₂O₂ concentration of 3 mM. Precursors with electron-donating groups (-OH, -OCH₃, -CH₃, etc.) exhibited higher electrophilic radical reactivity due to the enhanced electron density of the benzene ring, leading to higher reaction rates than those with electron-withdrawing groups (-NO₂, -CHO, -COOH). At pH 2, the second-order reaction rate (k_{PhCs, OH}) was lower than at pH 5. However, the k_obs did not show dependence on pH. The presence of O₂ facilitated substituted phenols’ photodecay. Inorganic salts and transition metal ions exhibited varying effects on reaction rates. Specifically, NO₃⁻ and Cu²⁺ promoted k_{PhCs, OH}, Cl⁻ significantly enhanced the reaction at pH 2, while SO₄²⁻ inhibited the reaction. The k_{PhCs, OH} were determined to be in the range of 10⁹~10¹⁰ L mol⁻¹ s⁻¹ via the bimolecular rate method, and a modest relationship with their oxidation potential was found. Additionally, multiple substituents can suppress the reactivity of phenolic compounds toward •OH based on Hammett plots. Quenching experiments revealed that •OH played a dominant role in phenolic compound degradation (exceeding 65%). Electron paramagnetic resonance confirmed the generation of singlet oxygen (¹O₂) in the system, and probe-based quantification further explored the concentrations of •OH and ¹O₂ in the system. Based on reaction rates and concentrations, the atmospheric aqueous-phase lifetimes of phenolic compounds were estimated, providing valuable insights for expanding atmospheric kinetic databases and understanding the chemical transformation and persistence of phenolic substances in the atmosphere. Full article

Polydopamine (PDA) is an emerging biomimetic material that stimulates the distinctive physicochemical properties of the blue mussel byssus. In this study, we report a rapid and facile method for the decoration of gold nanoparticles (AuNPs) onto the mussel-inspired polydopamine nanospheres (PDA NSs) via cold atmospheric plasma treatment. After 10 min of plasma treatment, AuNPs with a size of 10.3 ± 2.0 nm were formed on the surface of PDA NSs. This reaction was performed without the need for any additional reducing agents, thereby eliminating the use of harsh chemicals during the process. The synthesized AuNP-decorated PDA nanohybrids (PDA-Au) exhibit effective catalytic activity for the decoloration of Rhodamine B, with a pseudo-first-order rate constant of 1.405 min⁻¹. The green synthesis approach in this work highlights the potential of plasma-assisted methods for decorating biomimetic materials with metallic nanoparticles for catalytic and environmental applications. Full article

UiO-type Zr-BDC MOFs have garnered the interest of the scientific community due to their exceptional diversity in composition, structure, and chemical environment, as well as their high thermal and chemical stabilities. This work demonstrates the sustainable synthesis of a series of nanocrystalline/semicrystalline UiO-66(Zr) metal–organic frameworks (MOFs) under facile conditions—specifically at room temperature, in water, with high yield, and without the use of modulators or toxic byproducts. The synthesis involves either deprotonating the linker or utilizing various ratios of water and DMF as solvents. The as-prepared materials obtained from both synthesis strategies share key structural features with conventional UiO-66(Zr) in their short- and medium-range physicochemical properties, while exhibiting significant differences in crystallinity and textural properties. Nonetheless, the materials generally lack long-range order (semicrystalline), in particular these synthesized following the deprotonation strategy. However, the materials prepared using mixed solvent strategy seem to exhibit characteristics of nanocrystalline UiO-66(Zr). Overall, both approaches successfully addressed various synthesis challenges related to the highly sought-after Zr-based metal–organic frameworks (MOFs). Some of these MOF materials were tested for the photodegradation of rhodamine B (RhB) under mercury light irradiation, evidencing high photocatalytic efficiency of up to 75 ± 0.078% within 120 min under the pseudo-first-order model. This suggests an interaction between the photocatalyst and the RhB dye, involving electron injection from RhB and the ability for ligand-to-metal charge transfer (LMCT), which enhances the efficient photocatalytic degradation of RhB. The trapping experiments indicated that superoxide radicals (•O₂⁻) and photogenerated holes (h⁺) are crucial in the photodegradation of RhB. Moreover, the materials showed good recyclability across five tested cycles. A plausible photocatalytic reaction mechanism has been proposed to explain these findings. Full article

Idesia polycarpa Maxim. is a woody oil crop with great potential for edible oil production. While crude oil is rich in pigments, traditional bleaching methods have limited effectiveness in improving its color. In this study, a metal-organic framework (MOF) material, MIL-88B(Fe), was synthesized and used for the bleaching of Idesia polycarpa Maxim. oil. The adsorption selectivity of MIL-88B(Fe) and the adsorption process of carotenoids and chlorophyll were investigated. The results demonstrated that the synthesized MIL-88B(Fe) exhibited excellent bleaching capability, achieving a bleaching rate of 97.67% in 65 min. It showed a strong adsorption effect on pigments, particularly carotenoids. The content of lutein decreased from 118.27 mg/kg to 0.01 mg/kg after 65 min of bleaching. The squalene and phytosterol contents in the oil were minimally affected by the bleaching process, while the free fatty acid content slightly increased due to the high reaction temperature and the adsorbent properties. The adsorption process of MIL-88B(Fe) was best described by a pseudo-first-order kinetic model, indicating that the adsorption was a spontaneous and endothermic chemical process. Moreover, MIL-88B(Fe) demonstrated good safety and reusability, making it a promising novel adsorbent for the bleaching of Idesia polycarpa Maxim. oil and other oils with a high pigment content for the vegetable oil industry. Full article

Dialdehyde cellulose fabric (DACF) membranes with varying degrees of oxidation were fabricated using periodate oxidation and were employed for the chemical adsorption of amino-groups containing dyes from wastewater. The aldehyde group contents of DACF membranes were adjusted by altering oxidation time, which was confirmed by titration experiments. The chemical structure and morphology of DACF membranes were characterized using ATR-FTIR, TGA, SCA, SEM, XPS, and XRD measurements. The optimized DACF membrane, which was treated for an oxidation time of 24 h and has an aldehyde content of 2.97 mmol/g, was used for the chemical adsorption of amino-containing dye molecules. This process relies on the Schiff base reaction between the amino groups of the target dye molecule and the aldehyde groups of the membrane. Two typical cationic dyes, fuchsin basic and chrysoidine, containing aromatic amino groups, were chosen to determine the adsorption capacity of the DACF membrane. The adsorption kinetics, isotherms, and thermal dynamics of the DACF membrane were investigated comprehensively, while both pseudo-first- and pseudo-second-order kinetics models fit well, indicating the complicated chemical/diffusion adsorption process, where the hydrophobic properties of the DACF membrane retarded the adsorption rate. The maximum adsorption capacities of the DACF membrane against fuchsin basic and chrysoidine were 108.69 and 46.29 mg/g, respectively, as determined by Langmuir isotherm simulations. Various competing ions such as Na⁺, Ca²⁺, Cl⁻, and SO₄²⁻ at high concentrations of 10,000 ppm were used to challenge the adsorption capability of the DACF membrane, with negligible effects observed. A new adsorption mechanism based on chemical/diffusion interaction was proposed. Bovine serum albumin (BSA), fuchsin basic, and chrysoidine were mixed to simulate the multicomponent wastewater containing dissolved organic nitrogen (DON) and demonstrated the adsorption process; the direct adsorption capacity of the DACF membrane was up to 63.0%. This work offers a new method for the highly efficient removal of organic pollutants by a chemical reaction approach. Full article

Textile dyes are considered to be one of the major sources of water pollution due to their complex chemical structures. Photocatalytic dye degradation is an eco-friendly method that uses light-activated catalysts to break down complex dye molecules in wastewater into harmless byproducts. In the present study, pure and N-doped g-C₃N₄ were synthesized using one-pot calcination. The fabrication of g-C₃N₄/TiO₂ and TC-g-C₃N₄/TiO₂ was accomplished by physical mixing. The prepared photocatalysts were used to treat the Orange-II-polluted wastewater. The structural properties, surface morphology, light-harvesting capability, and electrochemical properties were assessed using XRD, XPS, SEM, TEM, BET, DRS, PL, EIS, Mott–Schottky, and transient photocurrent response (TPCR) analyses. The improved charge separation and migration properties of g-C₃N₄/TiO₂ were confirmed by the PL, EIS, and TPCR results. TEM and XPS data confirmed the formation of a g-C₃N₄/TiO₂ composite. Enhanced photocatalytic decolorization was achieved for g-C₃N₄/TiO₂ compared with pure g-C₃N₄ or TiO₂. The 1 wt% g-C₃N₄/TiO₂ composite exhibited the highest (92.1%) decolorization efficiency during 60 min of UV irradiation. Furthermore, the pseudo-first-order reaction rate constant (k) of 1 wt% g-C₃N₄/TiO₂ was calculated to be 0.0213 min⁻¹, which was 2.5 times better than that obtained with bare TiO₂. Finally, for a better understanding of the g-C₃N₄/TiO₂ decolorization process, a possible reaction mechanism was proposed. Full article

Hexavalent chromium, one of the heavy metal pollutants in water, harms the ecological environment and human health. In this work, an aniline-p-phenylenediamine copolymer has been prepared by chemical oxidative polymerization to remove the hexavalent chromium (Cr(VI)) from wastewater. The results show that when the initial Cr(VI) concentration is 1.5 mg·L⁻¹, the removal percentage (RP%) of Cr(VI) could reach 94.84% after 180 s of treatment. The RP% of Cr(VI) increases with the dosage of copolymers and decreases with an increase in the initial Cr(VI) concentration. Additionally, the RP% of Cr(VI) removal reaches a maximum of 97.70% with a pH value of 1.0. The Cr(VI) removal kinetics of the copolymers follows a pseudo-first-order chemical reaction model. The X-ray photoelectron spectroscopy (XPS) results demonstrate that the Cr(VI) removal mechanism by the aniline-p-phenylenediamine copolymer is a redox reaction. The positive value of ΔH° and negative value of ΔG° affirm that the Cr(VI) removal process by aniline-p-phenylenediamine copolymer is endothermic, thermodynamically achievable, and spontaneous. Full article

This work aimed to develop an anionic cellulose nanofiber (CNF) bio-adsorbent from date palm tree waste and to investigate its removal efficiency compared to cationic methylene blue dye from contaminated water. Date palm pulp was first prepared from date palm leaves through acid hydrolysis using H₂SO₄, followed by hydrolysis in a basic medium using KOH, in which the process completely removed the components of hemicellulose, lignin, and silica. To obtain anionic CNF, the resulting pulp was further treated with H₂SO₄, followed by centrifugation. Biogel formation of the CNF suspension was promoted by sonication, where its removal efficiency of methylene blue dye was studied as a function of dye concentration, temperature, contact time, and pH value. In this work, we investigated two isotherms, i.e., Langmuir and Freundlich. The Langmuir model’s consistency with the experimental data suggests that the adsorption of methylene blue dye onto CNF is monolayer and surface-limited. The reported maximum removal efficiency of 5 mg/g at 60 °C indicates the optimal temperature for adsorption in this specific case. Additionally, a pseudo-second-order model and Elovich model were also utilized to obtain a better understanding of the adsorption mechanism, in which we found not just physical adsorption but also an indication of a chemical reaction occurring between methylene blue dye and CNF. According to the results, that pseudo-second-order model’s consistency with the experimental data suggests that the adsorption of methylene blue (MB) onto CNF is rate-limiting step involving chemisorption between the two. The study reveals that CNF adsorbents derived from renewable natural waste sources such as date palm leaves can be effective in removing cationic contaminants such as methylene blue dye. Full article

Perovskites can absorb solar energy and are extensively used in various catalytic and photocatalytic reactions. However, noble metal particles may enhance the catalytic, photocatalytic, and antibacterial activities. This study demonstrates the cost-effective green synthesis of the photocatalyst perovskite LaMnO₃ and its modification with noble metal Ag nanoparticles. The green synthesis of nanocomposite was achieved through a hydrothermal method employing aqueous extract derived from Citrus limon (L.) Burm peels. The properties of fabricated perovskites LaMnO₃ and LaMnO₃-Ag nanocomposites were evaluated and characterized by Ultraviolet-Visible spectroscopy (UV-Vis), Diffuse Reflectance Spectroscopy (DRS), X-ray diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FT-IR), High-Resolution Transmission Electron Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray spectroscopy (EDX) and Brunauer–Emmett–Teller (BET) surface area techniques. The particle size distribution % of LaMnO₃ and LaMnO₃-Ag was observed to be 20 to 60 nm after using TEM images. The maximum percentage size distribution was 37 nm for LaMnO₃ and 43 nm for LaMnO₃-Ag. In addition, LaMnO₃-Ag nanocomposite was utilized as a photocatalyst for the degradation of Rose Bengal (RB) dye and its antibacterial activities against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The surface area and band gap for perovskite LaMnO₃ nanoparticles were calculated as 12.642 m²/g and 3.44 eV, respectively. The presence of noble metal and hydrothermal-bio reduction significantly impacted the crystallinity. The BET surface area was found to be 16.209 m²/g, and band gap energy was calculated at 2.94 eV. The LaMnO₃ nanocomposite with noble metal shows enhanced photocatalytic effectiveness against RB dye (20 PPM) degradation (92%, R² = 0.995) with pseudo-first-order chemical kinetics (rate constant, k = 0.05057 min⁻¹) within 50 min due to the ultimate combination of the hydrothermal and bio-reduction technique. The photocatalytic activity of the LaMnO₃-Ag nanocomposite was optimized at different reaction times, photocatalyst doses (0.2, 0.4, 0.6, and 0.8 g/L), and various RB dye concentrations (20, 30, 40, and 50 ppm). The antibacterial activities of green synthesized LaMnO₃ and LaMnO₃-Ag nanoparticles were explored based on colony-forming unit (cfu) reduction and TEM images of bacterial and nanoparticle interactions for S. aureus and E. coli. An amount of 50 µg/mL LaMnO₃-Ag nanocomposite was sufficient to work as the highest antibacterial activity for both bacteria. The perovskite LaMnO₃-Ag nanocomposite synthesis process is economically and environmentally friendly. Additionally, it has a wide range of effective and exclusive applications for remediating pollutants. Full article

A nanostructured material, ordered mesoporous carbon (OMC), was synthesised in metal- and halide-free form and its use for the sequestration of crystal violet, a hazardous triphenylmethane dye, is reported for the first time. The OMC material is characterised using scanning transmission electron microscopy with energy-dispersive spectroscopy for chemical analysis, by Fourier-transform infrared spectroscopy, and by nitrogen gas physisorption. The ideal conditions for the uptake of crystal violet dye were determined in batch experiments covering the standard parameters: pH, concentration, contact time, and adsorbent dosage. Experimental data are validated by applying Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherms. The thermodynamic parameters, ΔH°, ΔG°, and ΔS°, are calculated and it has been found that the adsorption process is spontaneous and endothermic with increasing disorder. An in-depth analysis of the kinetics of the adsorption process, order of the reaction and corresponding values of the rate constants was performed. The adsorption of crystal violet over OMC has been found to follow pseudo-second-order kinetics through a film diffusion process at all temperatures studied. Continuous flow column operations were performed using fixed bed adsorption. Parameters including percentage saturation of the OMC bed are evaluated. The exhausted column was regenerated through a desorption process and column efficiency was determined. Full article

Textile industry effluents contain several hazardous substances, such as dye-containing effluents, which pose environmental and aesthetic challenges. Presently, the microbial-based remediation process is in use. This study investigated the application of ferrous–ferric oxide (Fe₃O₄) nanoparticles, a readily formulated nanoadsorbent, to remove scattered dye molecules from industrial effluents. The ferrous–ferric oxide nanoparticles were prepared using a chemical co-precipitation method. The nanoparticles had 26.93 emu g⁻¹ magnetization, with sizes smaller than 20 nm, and possessed a highly purified cubic spinel crystallite structure. The catalytic activity of the iron oxide depended on the dose, photocatalytic enhancer, i.e., H₂O₂ level, pH of the reaction medium, and dye concentration. We optimized the Fenton-like reaction to work best using 1.0 g/L of ferrous–ferric oxide nanoparticles, 60 mM oxalic acid at pH 7.0, and 60 ppm of dye. Iron oxides act as photocatalysts, and oxalic acid generates electron–hole pairs. Consequently, higher amounts of super-radicals cause the rapid degradation of dye and pseudo-first-order reactions. Liquid chromatography–mass spectrometry (LC-MS) analysis revealed the ferrous–ferric oxide nanoparticles decolorized and destroyed Disperse Red 277 in 180 min under visible light. Hence, complete demineralization is observed using a photo-Fenton-like reaction within 3 h under visible light. These high-capacity, easy-to-separate next-generation adsorption systems are suggested to be suitable for industrial-scale use. Ferrous–ferric oxide nanoparticles with increased adsorption and magnetic properties could be utilized to clean environmental pollution. Full article

The recovery of valuable gold from wastewater is of great interest because of the widespread use of the precious metal in various fields and the pollution generated by gold-containing wastes in water. In this paper, a water-insoluble cross-linked adsorbent material (TE) based on cyanuric chloride (TCT) and ethylenediamine (EDA) was designed and used for the adsorption of Au(III) from wastewater. It was found that TE showed extremely high selectivity (D = 49,213.46) and adsorption capacity (256.19 mg/g) for Au(III) under acidic conditions. The adsorption rate remained above 90% eVen after five adsorption–desorption cycles. The adsorption process followed the pseudo-first-order kinetic model and the Freundlich isotherm model, suggesting that physical adsorption with a multilayer molecular overlay dominates. Meanwhile, the adsorption mechanism was obtained by DFT calculation and XPS analysis, and the adsorption mechanism was mainly the electrostatic interaction and electron transfer between the protonated N atoms in the adsorbent (TE) and AuCl₄⁻, which resulted in the redox reaction. The whole adsorption process was the result of the simultaneous action of physical and chemical adsorption. In conclusion, the adsorbent material TE shows great potential for gold adsorption and recovery. Full article

This study focuses on synthesizing and characterizing a graphene oxide/ZnTiO₃/TiO₂ (GO/ZTO/TO) composite to efficiently remove methylene blue (MB) from water, presenting a novel solution to address industrial dye pollution. GO and ZTO/TO were synthesized by the modified Hummers and sol–gel methods, respectively, while GO/ZTO/TO was prepared using a hydrothermal process. The structural and surface properties of the composite were characterized using various analytical techniques confirming the integration of the constituent materials and suitability for dye adsorption. The study revealed that GO/ZTO/TO exhibits an adsorption capacity of 78 mg g⁻¹ for MB, with only a 15% reduction in adsorption efficiency until the fifth reuse cycle. Furthermore, the study suggests optimal adsorption near neutral pH and enhanced performance at elevated temperatures, indicating an endothermic reaction. The adsorption behavior fits the Langmuir isotherm, implying monolayer adsorption on homogeneous surfaces, and follows pseudo-second-order kinetics, highlighting chemical interactions at the surface as the rate-limiting step. The photocatalytic degradation of MB by GO/ZTO/TO follows pseudo-first-order kinetics, with a higher rate constant than that of GO alone, demonstrating the enhanced photocatalytic activity of the composite. In conclusion, GO/ZTO/TO emerges as a promising and sustainable approach for water purification, through an adsorption process and subsequent photocatalytic degradation. Full article

Water scarcity and contamination have emerged as critical global challenges, requiring the development of effective and sustainable solutions for the treatment of contaminated water. Recently, functionalized polymer biomaterials have garnered significant interest because of their potential for a wide range of water treatment applications. Accordingly, this paper highlights the design of a new adsorbent material based on a cellulosic nonwoven textile grafted with two extracted biopolymers. The layer-by-layer grafting technique was used for the polyelectrolyte multi-layer (PEM) biosorbent production. Firstly, we extracted a Suaeda fruticosa polysaccharide (SFP) and confirmed its pectin-like polysaccharide structure via SEC, NMR spectroscopy, and chemical composition analyses. Afterward, the grafting was designed via an alternating multi-deposition of layers of SFP polymer and carrageenan crosslinked with 1,2,3,4-butanetetracarboxylic acid (BTCA). FT-IR and SEM were used to characterize the chemical and morphological characteristics of the designed material. Chemical grafting via polyesterification reactions of the PEM biosorbent was confirmed through FT-IR analysis. SEM revealed the total filling of material microspaces with layers of grafted biopolymers and a rougher surface morphology. The assessment of the swelling behavior revealed a significant increase in the hydrophilicity of the produced adsorbent system, a required property for efficient sorption potential. The evaluation of the adsorption capabilities using the methylene blue (MB) as cationic dye was conducted in various experimental settings, changing factors such as the pH, time, temperature, and initial concentration of dye. For the untreated and grafted materials, the greatest adsorbed amounts of MB were 130.6 mg/g and 802.6 mg/g, respectively (pH = 4, T = 22 C, duration = 120 min, and dye concentration = 600 mg/L). The high adsorption performance, compared to other reported materials, was due to the presence of a large number of hydroxyl, sulfonate, and carboxylic functional groups in the biosorbent polymeric system. The adsorption process fitted well with the pseudo-first-order kinetic model and Langmuir/Temkin adsorption isotherms. This newly developed multi-layered biosorbent shows promise as an excellent adsorption resultant and cheap-cost/easy preparation alternative for treating industrial wastewater. Full article

This work reports the influence of antimony substitution in a cerium molybdate lattice for improved dielectric and photocatalytic properties. For this purpose, a series of Ce_2−xSb_x(MoO₄)₃ (x = 0.00, 0.01, 0.03, 0.05, 0.07, and 0.09) were synthesized through a co-precipitation route. The as-synthesized materials were characterized for their optical properties, functional groups, chemical oxidation states, structural phases, surface properties, and dielectric characteristics using UV–Vis spectroscopy (UV–Vis), Fourier transform infrared (FTIR) and Raman spectroscopies, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, and impedance spectroscopy, respectively. UV–Vis study showed a prominent red shift of absorption maxima and a continuous decrease in band gap (3.35 eV to 2.79 eV) by increasing the dopant concentration. The presence of Ce–O and Mo–O–Mo bonds, detected via FTIR and Raman spectroscopies, are confirmed, indicating the successful synthesis of the desired material. The monoclinic phase was dominant in all materials, and the crystallite size was decreased from 40.29 nm to 29.09 nm by increasing the Sb content. A significant increase in the dielectric constant (ε′ = 2.856 $\times$ 10⁸, 20 Hz) and a decrease in the loss tan (tanδ = 1.647, 20 Hz) were exhibited as functions of the increasing Sb concentration. Furthermore, the photocatalytic efficiency of pristine cerium molybdate was also increased by 1.24 times against diclofenac potassium by incorporating Sb (x = 0.09) in the cerium molybdate. The photocatalytic efficiency of 85.8% was achieved within 180 min of UV light exposure at optimized conditions. The photocatalytic reaction followed pseudo-first-order kinetics with an apparent rate constant of 0.0105 min⁻¹, and the photocatalyst was recyclable with good photocatalytic activity even after five successive runs. Overall, the as-synthesized Sb-doped cerium molybdate material has proven to be a promising candidate for charge storage devices and a sustainable photocatalyst for wastewater treatment. Full article