Search Results (569)

Persistent reactive azo dyes released from textile finishing are a serious threat to water systems, but effective methods using sunlight to break them down are still limited. Everzol Yellow 3RS (EY-3RS) is particularly recalcitrant: past studies have relied almost exclusively on physical adsorption onto natural or modified clays and zeolites, and no photocatalytic pathway employing engineered nanomaterials has been documented to date. This study reports the synthesis, characterization, and performance of a visible-active ternary nanocomposite, Cu₄O₃/ZrO₂/TiO₂, prepared hydrothermally alongside its binary (Cu₄O₃/ZrO₂) and rutile TiO₂ counterparts. XRD, FT-IR, SEM-EDX, UV-Vis, and PL analyses confirm a heterostructured architecture with a narrowed optical bandgap of 2.91 eV, efficient charge separation, and a mesoporous nanosphere-in-matrix morphology. Photocatalytic tests conducted under midsummer sunlight reveal that the ternary catalyst removes 91.41% of 40 ppm EY-3RS within 100 min, markedly surpassing the binary catalyst (86.65%) and TiO₂ (81.48%). Activity trends persist across a wide range of operational variables, including dye concentrations (20–100 ppm), catalyst dosages (10–40 mg), pH levels (3–11), and irradiation times (up to 100 min). The material retains ≈ 93% of its initial efficiency after four consecutive cycles, evidencing good reusability. This work introduces the first nanophotocatalytic strategy for EY-3RS degradation and underscores the promise of multi-oxide heterojunctions for solar-driven remediation of colored effluents. Full article

Water pollution caused by increasing industrial and human activity remains a serious environmental challenge, especially due to the persistence of organic contaminants in aquatic systems. Photocatalysis offers a promising and eco-friendly solution, but in the case of bismuth oxide (Bi₂O₃) there is still a limited understanding of how structural and morphological features influence photocatalytic performance. In this work, a straightforward hydrothermal synthesis method followed by controlled calcination was developed to produce phase-pure α- and β-Bi₂O₃ with tunable morphologies. By varying the hydrothermal temperature and reaction time, distinct structures were successfully obtained, including flower-like, broccoli-like, and fused morphologies. XRD analyses showed that the final crystal phase depends solely on the calcination temperature, with β-Bi₂O₃ forming at 350 °C and α-Bi₂O₃ at 500 °C. SEM and BET analyses confirmed that morphology and surface area are strongly influenced by the hydrothermal conditions, with the flower-like β-Bi₂O₃ exhibiting the highest surface area. UV–Vis spectroscopy revealed that β-Bi₂O₃ also has a lower bandgap than its α counterpart, making it more responsive to visible light. Photocatalytic tests using Rhodamine B showed that the flower-like β-Bi₂O₃ achieved the highest degradation efficiency (81% in 4 h). Kinetic analysis followed pseudo-first-order behavior, and radical scavenging experiments identified hydroxyl radicals, superoxide radicals, and holes as key active species. The catalyst also demonstrated excellent stability and reusability. Additionally, Methyl Orange (MO), a more stable and persistent azo dye, was selected as a second model pollutant. The flower-like β-Bi₂O₃ catalyst achieved 73% degradation of MO at pH = 7 and complete removal under acidic conditions (pH = 2) in less than 3 h. These findings underscore the importance of both phase and morphology in designing high-performance Bi₂O₃ photocatalysts for environmental remediation. Full article

In this study, we report the development of a novel magnetized coal fly ash-supported nano-silver composite (AgNPs/MCFA) for dual-functional applications in wastewater treatment: the efficient degradation of methyl orange (MO) dye and broad-spectrum antibacterial activity. The composite was synthesized via a facile impregnation–reduction–sintering route, utilizing sodium citrate as both a reducing and stabilizing agent. The AgNPs/MCFA composite was systematically characterized through multiple analytical techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM). The results confirmed the uniform dispersion of AgNPs (average size: 13.97 nm) on the MCFA matrix, where the formation of chemical bonds (Ag-O-Si) contributed to the enhanced stability of the material. Under optimized conditions (0.5 g·L⁻¹ AgNO₃, 250 °C sintering temperature, and 2 h sintering time), AgNPs/MCFA exhibited an exceptional catalytic performance, achieving 99.89% MO degradation within 15 min (pseudo-first-order rate constant k_a = 0.3133 min⁻¹) in the presence of NaBH₄. The composite also demonstrated potent antibacterial efficacy against Escherichia coli (MIC = 0.5 mg·mL⁻¹) and Staphylococcus aureus (MIC = 2 mg·mL⁻¹), attributed to membrane disruption, intracellular content leakage, and reactive oxygen species generation. Remarkably, AgNPs/MCFA retained >90% catalytic and antibacterial efficiency after five reuse cycles, enabled by its magnetic recoverability. By repurposing industrial waste (coal fly ash) as a low-cost carrier, this work provides a sustainable strategy to mitigate nanoparticle aggregation and environmental risks while enhancing multifunctional performance in water remediation. Full article

Catalysts are ubiquitous in manufacturing industries and gas phase pollutant abatement but are not widely used in wastewater treatment, as high temperatures and concentrated waste streams are needed to achieve the reaction degradation rates required. Heating water is energy intensive, and alternative, low temperature solutions have been investigated, collectively known as advanced oxidation processes. However, many of these advanced oxidation processes use expensive oxidants such as perchlorate, hydroxy radicals or ozone to react with contaminants, and therefore have high running costs. This study has investigated microwave catalysis as a low-energy, low-cost technology for water treatment using NiO catalysts that can be heated in the microwave field to drive the decomposition of azo-dye contaminants. Using this methodology for the microwave-assisted degradation of two azo dyes (azorubine and methyl orange), conversions of >95% were achieved in only 10 s with 100 W microwave power. Full article

A ceramic–metal composite was synthesized using sol–gel and electrospinning methods to serve as a SERS substrate. The precursors used were tetraethyl orthosilicate, aluminum nitrate, and zirconium, and polyvinylpyrrolidone was added to electrospun nonwoven fibrous membranes. The membranes were sintered, decorated with silver nanoparticles. The enhancement substrates were made of fibers of cylindric morphology with an average diameter of approximately 190 nm, a smooth surface, and 9 nm spherical particles decorating the surface of the fibers. The enhancement capacity of the substrates was tested using pyridine, methyl orange, methylene blue, crystal violet, and Eriochrome black T at different concentrations with Raman spectroscopy to determine whether the size and complexity of the analyte has an impact on the enhancement capacity. Enhancement factors of 2.53 × 10², 3.06 × 10¹, 2.97 × 10³, 4.66 × 10³, and 1.45 × 10³ times were obtained for the signal of pyridine, methyl orange, methylene blue, crystal violet, and Eriochrome black T at concentrations of 1 nM. Full article

This study examines the environmental challenges posed by azo-dye pollutants and aluminum industrial waste. Aluminum oxide nanoparticles (P/Al₂O₃-NPs) were produced using a green method that utilized pharmaceutical packaging waste as an aluminum source and marine algae extract (Padina pavonica) as reducing and stabilizing agents and that was characterized by XRD, EDX, SEM, TEM, and zeta potential. Batch biosorption studies were performed to assess the effectiveness of P/Al₂O₃-NPs in removing CR dye from aqueous solutions. The results demonstrate that the particle sizes range from 58.63 to 86.70 nm and morphologies vary from spherical to elliptical. FTIR analysis revealed Al–O lattice vibrations at 988 and 570 cm⁻¹. The nanoparticles displayed a negative surface charge (−13 mV) and a pH_zpc of 4.8. Adsorption experiments optimized parameters for CR dye removal, achieving 97.81% efficiency under native pH (6.95), with a dye concentration of 30 mg/L, an adsorbent dosage of 0.1 g/L, and a contact time of 30 min. Thermodynamic studies confirmed that the process is exothermic and spontaneous. Kinetic data fit well with the pseudo-second-order model, while equilibrium data aligned with the Langmuir isotherm. The adsorption mechanism involved van der Waals forces, hydrogen bonding, and π–π interactions, as supported by the influence of pH, isotherm data, and FTIR spectra. Overall, the study demonstrates the potential of eco-friendly P/Al₂O₃-NPs to efficiently remove CR dye from aqueous solutions. Full article

This study explored the production and activation of biochar from rice straw residue for dye adsorption applications. Rice straw, a widely available but underutilized biomass, was processed to isolate lignin and generate biochar through pyrolysis at 450 °C and 550 °C. Activation using chemical agents (e.g., KOH and NaOH) was performed to enhance surface area and porosity. Among the tested conditions, KOH activation at a char-to-agent ratio of 1:3 produced activated carbon at 800 °C with the highest BET surface area (835.2 m²/g), and high fixed carbon (44.4%) after HCl washing. Thermogravimetric analysis was used to investigate pyrolysis kinetics, with activation energies determined using the Kissinger, Flynn–Wall–Ozawa, and Kissinger–Akahira–Sunose models. The brown solid showed a higher activation energy (264 kJ/mol) compared to isolated lignin (194 kJ/mol), indicating that more energy is required for decomposition. The AC was evaluated for the adsorption of methylene blue (MB) and methyl orange (MO) from aqueous solutions. Both dyes followed the Langmuir isotherm model, indicating that monolayer adsorption occurred. The maximum adsorption capacities reached 222 mg/g for MB and 244 mg/g for MO at 303 K, with higher values at elevated temperatures. Adsorption followed a pseudo-second-order kinetic model and was governed by a physisorption mechanism, as supported by thermodynamic analysis (ΔH < 20 kJ/mol and E_a < 40 kJ/mol). These findings demonstrate that KOH-activated biochar from rice straw residue is a high-performance, low-cost adsorbent for dye removal, contributing to sustainable biomass utilization and wastewater treatment. Full article

Ag/AgCl-decorated layered lanthanum oxide (La₂O₃) and niobium pentoxide (Nb₂O₅) plasmonic photocatalysts are fabricated through an ionic liquid-mediated co-precipitation method. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) techniques were used to illustrate the physicochemical properties of the materials. The photoactivity was evaluated for the degradation of Acid Blue 92 (AB92) azo dye, a typical organic contaminant from the textile industry, and U251 cancer cell inactivation. According to the results, Nb₂O₅–Ag/AgCl was able to remove >99% of AB92 solution in 35 min with the rate constant of 0.12 min⁻¹, 2.4 times higher than that of La₂O₃–Ag/AgCl. A pH of 3 and a catalyst dosage of 0.02 g were determined as the optimized factors to reach the highest degradation efficiency under solar energy at noon, which was opted to have the highest sunlight intensity over the reactor. Also, 0.02 mg/mL of Nb₂O₅–Ag/AgCl was determined to be of great potential to reduce cancer cell viability by more than 50%, revealed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and mitochondrial membrane potential (MMP) examinations. The mechanism of degradation was also discussed, considering the key role of Ag⁰ nanoparticles in inducing a plasmonic effect and improving the charge separation. This work provides helpful insights to opt for an efficient rare metal oxide with good biocompatibility as support for the plasmonic photocatalysts with the goal of environmental purification under sunlight. Full article

The authentication of high-value spices such as paprika and cinnamon is critical due to increasing food fraud. This study explored the potential of a multi-analytical approach, combined with chemometric tools, to differentiate 45 paprika and 46 cinnamon samples from the Slovenian market based on their geographic origin, production methods, and possible adulteration. The applied techniques included stable isotope ratio analysis (δ¹³C, δ¹⁵N, δ³⁴S), multi-elemental profiling, FTIR, and antioxidant compound analysis. Distinct isotopic and elemental markers (e.g., δ¹³C, δ³⁴S, Rb, Cs, V, Fe, Al) contributed to classification by geographic origin, with preliminary classification accuracies of 90% for paprika (Hungary, Serbia, Spain) and 89% for cinnamon (Sri Lanka, Madagascar, Indonesia). Organic paprika samples showed higher values of δ¹⁵N, δ³⁴S, and Zn, whereas conventional ones had more Na, Al, V, and Cr. For cinnamon, a 95% discrimination accuracy was achieved between production practice using δ³⁴S and Ba, as well as As, Rb, Na, δ¹³C, S, Mg, Fe, V, Al, and Cu. FTIR differentiated Ceylon from cassia cinnamon and suggested possible paprika adulteration, as indicated by spectral features consistent with oleoresin removal or azo dye addition, although further verification is required. Antioxidant profiling supported quality assessment, although the high antioxidant activity in cassia cinnamon may reflect non-phenolic contributors. Overall, the results demonstrate the promising potential of the applied analytical techniques to support spice authentication. However, further studies on larger, more balanced datasets are essential to validate and generalize these findings. Full article

Eugenol-based azo dyes illustrate how bio-sourced compounds like eugenol can be transformed through synthetic processes into functional and colorful compounds. The main purpose of the present work was to develop new responsive colorimetric sensors for metal cations based on eugenol-derived azo compounds. The incorporation of the azo group into the eugenol framework allows for strong electronic interactions with metal cations, leading to distinct color changes observable to the naked eye. These azo-eugenol dyes exhibit shifts in their UV-Vis absorption spectra upon complexation with metal cations such as copper (Cu²⁺) and lead (Pb²⁺), making them effective sensors for environmental and analytical applications. The eugenol-based azo dyes were subjected to photophysical studies to understand selectivity, response time, and stability in relation to metal cations, which will be a starting point for the monitoring of toxic metal contaminants in aqueous environments. Full article

One-dimensional TiO₂ nanotube arrays (TNAs) were vertically aligned and obtained via the electrochemical anodization method. In this study, Bi₂S₃-TiO₂-SiO₂/TNA heterojunction photocatalysts were successfully prepared with different amounts of Bismuth(III) sulfide (Bi₂S₃) loading on the TNAs by the successive ionic layer adsorption and reaction (SILAR) method and characterized by X-ray diffraction (XRD) patterns, field-emission scanning electron microscope–energy-dispersive spectroscopy (FESEM-EDS), Fourier transform infrared (FTIR) spectra, ultraviolet-visible diffuse reflectance spectra (UV–Vis/DRS), and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic performances of the samples were investigated by degrading Basic Yellow 28 (BY 28) under visible-light irradiation. Optimization of the condition using the response surface methodology (RSM) and central composite rotatable design (CCRD) technique resulted in the degradation of BY 28 dye, showing that the catalyst with 9.6 mg/cm² (designated as Bi₂S_3(9.6)-TiO₂-SiO₂/TNA) showed the maximum yield in the degradation process. The crystallite size of about 17.03 nm was estimated using the Williamson–Hall method. The band gap energies of TiO₂-SiO₂/TNA and Bi₂S_3(9.6)-TiO₂-SiO₂/TNA were determined at 3.27 and 1.87 eV for the direct electronic transitions, respectively. The EIS of the ternary system exhibited the smallest arc diameter, indicating an accelerated charge transfer rate that favors photocatalytic activity. Full article

The release of synthetic dyes like Basic Red 46 (BR46) from industrial wastewater has raised growing concerns due to their toxicity, long-term persistence, and resistance to standard biological treatment methods. In this work, we developed and tested a pilot-scale electrocoagulation–ozonation (EC–O) hybrid system aimed at removing BR46 from aqueous solutions. The system integrates electrocoagulation, using iron electrodes, with ozone-based advanced oxidation processes, facilitating a combination of coagulation, adsorption, and oxidative breakdown of dye molecules. The response surface methodology (RSM) with a central composite design (CCD) was applied to optimize the treatment process, focusing on five variables: current density, flow rate, ozone dosage, ozonation time, and initial dye concentration. The quadratic model exhibited strong predictive power, with an adjusted R² of 0.9897 and a predicted R² of 0.9812. The optimal conditions identified included a current density of 70 A/m², flow rate of 1.6 L/min, ozone dose of 2.0 g/h, and an ozonation time of 20 min, achieving a predicted removal efficiency of 91.67% for a solution with BR46 at an initial concentration of 300 mg/L. Experiments conducted under these conditions confirmed the model’s reliability, with observed removal rates exceeding 90% and deviations under 2%. The EC–O system had a treatment capability of 26.19 L/h and an energy consumption of 3.04 kWh/m³. These findings suggest that the EC–O system is an effective and scalable option for treating dye-contaminated wastewater, offering faster and more efficient results than conventional techniques. Full article

A tandem UV–Vis and fluorescence spectroscopy method was developed for the detection of Pd(II) ions in ethanol. The formation of a complex between Pd(II) ions and tropaeolin OO (TR OO) is accompanied by a change in the color of the solution and evolution of the characteristic UV–Vis as well as fluorescence spectra. The optimal detection conditions were achieved at a 3:1 (mL/mL) volume ratio of Pd(II) to TR OO, at 50 °C. UV–Vis spectroscopy enabled the detection of complex formation process over time, while fluorescence spectroscopy allowed a rapid response within 10 min. The limit of detection (LOD) of Pd(II) ions using UV–Vis spectrophotometry was 10 μmol/dm³ at 535 nm. For spectrofluorimetric detection, the LOD was 10 μmol/dm³, with an emission signal observed at 630 nm after 10 min. The kinetics studies showed a stepwise complex formation pathway, supported by DFT calculations. The performance of the method was verified in the presence of interfering metal ions, including Li(I), Na(I), Al(III), Ni(II), Mg(II), Ca(II), Co(II), and Zn(II), confirming its applicability in complex matrices. This approach provides efficient palladium determination in organic solvents, contributing to sustainable practices in metal recycling. Full article

Nowadays, nitrate ions and azo dyes are a significant source of water pollution due to their high toxicity, persistence, and potential to be carcinogenic. Both contaminants are the result of anthropogenic sources, such as sewage or industrial wastewater discharge; the first one results also as a consequence of the intensive use of fertilizers. In this work we report the use of a new quaternized pentablock copolymer (PTBr) for the removal of nitrate ions and methyl orange (MO) dye from water by adsorption processes. Morphological, chemical, and thermal properties of the pentablock copolymer were investigated, respectively, by scanning electron microscopy (SEM), Attenuated Total Reflectance Infrared Spectroscopy (ATR-FTIR) (FT-IR), and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) analyses. Anionic removal ability and adsorption rate in water solutions containing either a single contaminant species or a mix of the two contaminants were studied by UV–VIS absorbance spectroscopy as a function of time and initial concentration. The presence of imidazole groups confers on PTBr a positive charge and a hydrophilic character that are responsible for an effective removal of anions from water. PTBr film reports an adsorption efficiency of 10.15 mg/g for nitrate removal and this value is in line with others reported in the literature. In the case of the simultaneous presence of nitrate and MO, it is found that nitrate ions removal is slightly affected by the presence of the dye, since both contaminants compete for electrostatic interaction with imidazole groups. On the contrary, the dye removal does not show significant change with or without the presence of nitrate ions, probably due to other kinds of interaction that it can establish with the polymer surface (π-π interaction). The adsorption process and the related mechanisms are described using kinetic and isothermal models. Despite a certain reduction in the adsorption efficiency for one of the investigated contaminants, the results confirm the possibility of using the quaternized pentablock copolymer for the co-adsorption of both inorganic and organic anions. Full article

The use of natural materials as adsorbents and the environmentally friendly removal of pollutants and azo dyes from water are important topics today. The goal of this research work was to assess the utility of Luffa cylindrica (L. cylindrica) as a natural and non-conventional adsorbent for azo dyes in water on a large scale (2 L). An azo dye (AD) at a concentration of 0.250 g/L was removed from the solution at a rate of 63.07% using 10.0 g/L doses of L. cylindrica, and the maximum adsorption capacity of L. cylindrica was 25.25 mg/g. L. cylindrica desorbed 95.8% of the AD in 0.1 M NaOH. Thermodynamically, the adsorption occurs through pseudo-second-order kinetics and the behaviors adjust better to the Langmuir isotherm. The analysis of variance (p-value < 0.05) shows that the contact time and the concentration of AD significantly influence the adsorption capacity and removal of AD. Few studies have examined the environmentally friendly removal of azo dyes from water using a natural non-conventional adsorbent. Full article