Search Results (57)

In this study, the degradation of Nile Blue dye was investigated using homogeneous and heterogeneous photocatalytic methods based on the photo-Fenton reaction. More specifically, for homogeneous photocatalysis, the classical photo-Fenton (UV/Fe²⁺/H₂O₂) and modified photo-Fenton-like (UV/Fe²⁺/S₂O₈²⁻) systems were studied, while for heterogeneous photocatalysis, a commercial MOF catalyst, Basolite F300, and a natural ferrous mineral, geothite, were employed. Various parameters—including the concentrations of the oxidant and catalyst, UV radiation, and pH—were investigated to determine their influence on the reaction rate. In homogeneous systems, an increase in iron concentration led to an enhanced degradation rate of the target compound. Similarly, increasing the oxidant concentration accelerated the reaction rate up to an optimal level, beyond which radical scavenging effects were observed, reducing the overall efficiency. In contrast, heterogeneous systems exhibited negligible degradation in the absence of an oxidant; however, the addition of oxidants significantly improved the process efficiency. Among the tested processes, homogeneous techniques demonstrated a superior efficiency, with the conventional photo-Fenton process achieving complete mineralization within three hours. Kinetic analysis revealed pseudo-first-order behavior, with rate constants ranging from 0.012 to 0.688 min⁻¹ and correlation coefficients (R²) consistently above 0.90, confirming the reliability of the applied model under various experimental conditions. Nevertheless, heterogeneous techniques, despite their lower degradation rates, also achieved high removal efficiencies while offering the advantage of operating at a neutral pH without the need for acidification. Full article

The development of heterostructures incorporating photocatalysts optimized for visible-light activity represents a major breakthrough in the field of environmental remediation research, offering innovative and sustainable solutions for environmental purification. This study explores the photocatalytic capabilities of a SnFe₂O₄/g-C₃N₄ heterojunction nanocomposite, successfully synthesized from graphitic carbon nitride (g-C₃N₄) and tin ferrate (SnFe₂O₄) and applied to the degradation of the cationic dye brilliant cresyl blue (BCB) in an aqueous solution. These two components are particularly attractive due to their low cost and ease of fabrication. Various characterization techniques, including XRD, FTIR, SEM, and TEM, were used to confirm the successful integration of SnFe₂O₄ and g-C₃N₄ phases in the synthesized catalysts. The photocatalytic and photo-Fenton-like activity of the heterojunction composites was evaluated by the degradation of brilliant cresyl blue under visible LED illumination. Compared to the pure components SnFe₂O₄ and g-C₃N₄, the SnFe₂O₄/g-C₃N₄ nanocomposite demonstrated a superior photocatalytic performance. Furthermore, the photo-Fenton-like performance of the composites is much higher than the photocatalytic performances. The significant improvement in photo-Fenton activity is attributed to the synergistic effect between SnFe₂O₄ and g-C₃N₄, as well as the efficient separation of photoexcited electron/hole pairs. The recyclability of the SnFe₂O₄/g-C₃N₄ composite toward BCB photo-Fenton like degradation was also shown. This study aimed to assess the modeling and optimization of photo-Fenton-like removal BCB using the SnFe₂O₄/g-C₃N₄ nanomaterial. The main parameters (photocatalyst dose, initial dye concentration, H₂O₂ volume, and reaction time) affecting this system were modeled by two approaches: a response surface methodology (RSM) based on a Box–Behnken design and artificial neural network (ANN). A comparison was made between the predictive accuracy of RSM for brilliant cresyl blue (BCB) removal and that of the artificial neural network (ANN) approach. Both methodologies provided satisfactory and comparable predictions, achieving R² values of 0.97 for RSM and 0.99 for ANN. Full article

The discharge of wastewater containing persistent organic pollutants presents significant ecological and health challenges due to their toxicity and resilience. Recent advances in advanced oxidation processes (AOPs) and other remediation mechanisms, notably utilizing natural mineral materials (NMMs), offer promising solutions to these challenges. NMMs, with their cost-effectiveness, accessibility, eco-friendly nature, non-toxicity, and unique structural properties, have shown significant promise in environmental remediation and could effectively replace conventional catalysts in related applications. These minerals enable the activation of oxidants, generating reactive oxygen species crucial for the degradation of pollutants. This article reviews the mechanisms of NMMs in various AOPs, including photocatalysis, Fenton-like reactions, and persulfate-activation-based processes, and discusses the potential of these materials in enhancing pollutant degradation efficiency, with a focus on the activation of persulfates and the photo-induced redox processes. The synergy between photocatalytic properties and catalytic activation provided by NMMs offers a robust approach to managing water pollution without the drawbacks of secondary waste production, thus supporting sustainable remediation efforts. Full article

This study investigates the synthesis and evaluation of ZnO/g-C₃N₄ composites as efficient green catalysts for advanced oxidation processes (AOPs) targeting the treatment of contaminated water. The composites were synthesized using a ternary deep eutectic solvent and physically–chemically characterized in detail, confirming their structural integrity and successful synthesis. Photocatalytic, photo-Fenton- and electro-Fenton-like experiments were conducted using Rhodamine B as a model contaminant to evaluate the catalytic performance, reuse and stability of the synthesized material. The synthesized ZnO/g-C₃N₄ composites demonstrated excellent photocatalytic activity under LED light (395 nm), achieving a pollutant removal of around 59% in 90 min. The combined effect of the designed catalyst and Fenton-like process, a photo-Fenton-like process, significantly improved this performance, achieving removal of close to 95% in 60 min due to the synergistic effects of the irradiation and H₂O₂ activation. Finally, the catalytic action of synthesized ZnO/g-C₃N₄ composites in the electro-Fenton-like process exhibited superior efficiency, achieving 90% removal within 45 min and kinetic constants four times higher than those of anodic oxidation alone. In addition, reuse studies confirmed the stability and catalytic activity of the composites for several cycles with high removal efficiencies, demonstrating their viability for long-term and scalable water treatment applications. These findings highlight the potential of ZnO/g-C₃N₄ composites synthesized through DES as a sustainable and cost-effective alternative for water remediation technologies. Full article

The development of efficient and sustainable photocatalysts for wastewater treatment remains a critical challenge in environmental remediation. In this study, a ternary photocatalyst, Cu-Cu₂O/g-C₃N₄, was synthesized by embedding copper-copper oxide heterostructural nanocrystals onto g-C₃N₄ nanosheets via a simple deposition method. Structural and optical characterization confirmed the successful formation of the heterostructure, which combines the narrow bandgap of Cu₂O, the high stability of g-C₃N₄, and the surface plasmon resonance (SPR) effect of Cu nanoparticles. The photocatalytic performance was evaluated through the degradation of Rhodamine B (RhB) in a photo-Fenton-like reaction system under visible light irradiation. Among the catalysts tested, the 30 wt% Cu-Cu₂O/g-C₃N₄ composite exhibited the highest catalytic efficiency, achieving a reaction rate constant approximately 3 times and 1.5 times higher than those of Cu-Cu₂O and g-C₃N₄, respectively. Mechanistic studies suggest that the heterostructure facilitates efficient charge separation and promotes the reduction of Cu²⁺ to Cu⁺, thereby enhancing ∙OH radical generation. The catalyst also demonstrated excellent stability and reusability across a wide pH range. These findings provide a new strategy for designing highly efficient photocatalysts for organic pollutant degradation, contributing to the advancement of advanced oxidation processes for environmental applications. Full article

Textile wastewater containing dyes poses significant environmental hazards. Advanced oxidative processes, especially the heterogeneous photo-Fenton process, are effective in degrading a wide range of contaminants due to high conversion rates and ease of catalyst recovery. This study evaluates the heterogeneous photodegradation of the azo dyes Acid Red 18 (AR18), Acid Red 66 (AR66), and Orange 2 (OR2) using magnetite as a catalyst. The magnetic catalyst was synthesized via a hydrothermal process at 150 °C. Experiments were conducted at room temperature, investigating the effect of catalyst dosage, pH, and initial concentrations of H₂O₂ and AR18 dye. Kinetic and thermodynamic studies were performed at 25, 40, and 60 °C for the three azo dyes (AR18, AR66, and OR2) and the effect of the dye structures on the degradation efficiency was investigated. At 25 °C for 0.33 mmolL⁻¹ of dye at pH 3.0, using 1.4 gL⁻¹ of the catalyst and 60 mgL⁻¹ of H₂O₂ under UV radiation of 16.7 mWcm⁻², the catalyst showed 62.3% degradation for AR18, 79.6% for AR66, and 83.8% for OR2 in 180 min of reaction. The oxidation of azo dyes under these conditions is spontaneous and endothermic. The pseudo-first-order kinetic constants indicated a strong temperature dependence with an order of reactivity of the type OR2 > AR66 > AR18, which is associated with the molecular size, steric hindrance, aromatic conjugation, electrostatic repulsion, and nature of the acid–base interactions on the catalytic surface. Full article

Metal-free photocatalysis that produces reactive oxygen species (ROS) shows significant promising applications for environmental remediation. Herein, we constructed iodine-doped carbon nitride (I-CN) for applications in the photocatalytic inactivation of bacteria and the heterogeneous Fenton reaction. Our findings revealed that I-CN demonstrates superior photocatalytic activity compared to pure CN, due to enhanced light adsorption and a narrowed band gap. Antibacterial tests confirmed that I-CN exhibits exceptional antibacterial activity against both Escherichia coli and Staphylococcus aureus. The results showed that I-CN effectively generates superoxide radicals and hydroxyl radicals under light irradiation, resulting in enhanced antibacterial activity. In addition, I-CN can also be applied for a heterogeneous photo-Fenton-like reaction, achieving a high performance for the degradation of sulfamethoxazole (SMX), a typical antibiotic, via the photocatalytic activation of peroxymonosulfate (PMS). These results shed new light on the fabrication of metal-free nanozymes and their applications for disinfection and water decontamination. Full article

A binary Fe₂O₃/Fe₃O₄ mixed nanocomposite was prepared by phyto-mediated avenue to be suited in the photo-Fenton photodegradation of methylene blue (MB) in the presence of H₂O₂. XRD and SEM analyses illustrated that Fe₂O₃ nanoparticles of average crystallite size 8.43 nm were successfully mixed with plate-like aggregates of Fe₃O₄ with a 15.1 nm average crystallite size. Moreover, SEM images showed a porous morphology for the binary Fe₂O₃/Fe₃O₄ mixed nanocomposite that is favorable for a photocatalyst. EDX and elemental mapping showed intense iron and oxygen peaks, confirming composite purity and symmetrical distribution. FTIR analysis displayed the distinct Fe-O assignments. Moreover, the isotherm of the developed nanocomposite showed slit-shaped pores in loose particulates within plate-like aggregates and a mesoporous pore-size distribution. Thermal gravimetric analysis (TGA) indicated the high thermal stability of the prepared Fe₂O₃/Fe₃O₄ binary nanocomposite. The optical properties illustrated a narrowing in the band gab (Eg = 2.92 eV) that enabled considerable absorption in the visible region of solar light. Suiting the developed binary Fe₂O₃/Fe₃O₄ nanocomposite in the photo-Fenton reaction along with H₂O₂ supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. The solar-driven photodegradation reactions were conducted and the estimated rate constants were 0.002, 0.0047, and 0.0143 min⁻¹ when using the Fe₂O₃/Fe₃O₄ nanocomposite, pure H₂O₂, and the Fe₂O₃/Fe₃O₄/H₂O₂ hybrid catalyst, respectively. Therefore, suiting the developed binary Fe₂O₃/Fe₃O₄ nanocomposite and H₂O₂ in photo-Fenton reaction supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. After being subjected to four photo-Fenton degradation cycles, the Fe₂O₃/Fe₃O₄ nanocomposite catalyst still functioned admirably. Further evaluation of Fe₂O₃/Fe₃O₄ nanocomposite in photocatalytic remediation of contaminated water using a mixture of MB and pyronine Y (PY) dyestuffs revealed substantial dye photodegradation efficiencies. Full article

The composite photocatalyst FeOOH/g-C₃N₄ was prepared through thermal polycondensation and co-precipitation methods, followed by XRD, SEM and UV-vis characterization. The stability of FeOOH/g-C₃N₄ was explored by the recycling test. The active species in the reaction system were investigated by the capture experiment. The results indicated that the optimal preparation condition for g-C₃N₄ involved calcination at 600 °C for 4 h. XRD analysis revealed that g-C₃N₄ exhibits a high-purity phase, and Fe in FeOOH/g-C₃N₄ exists in a highly dispersed amorphous state. SEM analysis showed that FeOOH/g-C₃N₄ has a rough surface with an irregular layered structure. Element composition analysis confirmed that the content of elements in the prepared catalyst is consistent with the theoretical calculation. FeOOH/g-C₃N₄ possesses the largest specific surface area of 143.2 m²/g and a suitable pore distribution. UV-vis DRS analysis showed that the absorption intensity of FeOOH/g-C₃N₄ is stronger than that of g-C₃N₄. When the catalyst dosage was 1.0 g/L, the H₂O₂ dosage was 4 mmol/L, the PNP initial concentration was 10 mg/L and the initial pH value was 5, the PNP removal could reach 92% in 120 min. Even after 5 cycles, the efficiency of PNP removal by FeOOH/g-C₃N₄ remains nearly 80%. The capture experiment indicated that both •OH and •O₂⁻ play roles in the photocatalytic degradation of PNP, with •OH being more significant. These findings affirm that FeOOH has been successfully incorporated into g-C₃N₄, resulting in a conspicuous catalytic effect on the degradation of PNP in the visible light-assisted Fenton-like reaction. Full article

Following the goals of the circular economy, this work demonstrates that an industrial by-product can be used in environmental remediation. Metallurgical slag and citric acid were used to form an Fe:Cit complex by simultaneously carrying out the lixiviation of the iron and the chelating stages with an 87% iron recovery. This complex was evaluated in the photo-Fenton process to produce HO^• through salicylic acid dosimetry or salicylic acid hydroxylation, producing 0.13 ± 0.1 mM HO^• after 30 min of operation; such a value is three orders of magnitude higher than the one reported for the metallurgical slag (as a heterogeneous catalyst, 22 μM) in the photo-Fenton-like process. The system was tested for its ability to degrade a mixture of drugs, including dexamethasone (DEX), naproxen (NAP), and ketorolac (KTR), which are often used to treat the symptoms of COVID-19. The drug degradation tests were performed in two stages. In the first stage, the Fe:Cit complex from the metallurgical slag was compared to the one formed by analytical-grade reactants; the drug degradation was faster for the former, with the major difference being observed at 5 cm and 500 W/m². Here, 85–90% of the drugs was degraded in 5 min using Fe:Cit from slag, while at least 20 min was necessary to achieve such degradation with the analytical reagent, conceivably because of the trace compounds being lixiviated from the slag. Then, the effects of the liquid depth (5, 10, and 15 cm) and irradiance (250, 500, and 750 W/m²) were tested; the pseudo-first-order kinetic degradation constants for the three model pollutants were in the range of 0.009 > k_D > 0.09 min⁻¹, showing that degradation is more feasible for DEX than for NAP and KRT because the radical attack feasibility is related to the molecular structures. 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 use of hydrogen peroxide (produced in situ or ex situ) as the main agent in oxidative processes of environmental pollutant removal is widely studied. The degradation of water pollutants, such as dyes, pharmaceuticals, cosmetics, petroleum derivatives, and even pathogens, has been successfully obtained by different techniques. This review gives an overview of the more recent methods developed to apply oxidative processes mediated by H₂O₂ and other reactive oxygen species (ROS) in environmental catalysis, with particular attention to the strategies (Fenton-like and Bio-Fenton, photo- and electro-catalysis) and the materials employed. A wide discussion about the characteristics of the materials specifically studied for hydrogen peroxide activation, as well as about their chemical composition and morphology, was carried out. Moreover, recent interesting methods for the generation and use of hydrogen peroxide by enzymes were also presented and their efficiency and applicability compared with the Fenton and electro-Fenton methods discussed above. The use of Bio-Fenton and bi-enzymatic methods for the in situ generation of ROS seems to be attractive and scalable, although not yet applied in full-scale plants. A critical discussion about the feasibility, criticalities, and perspectives of all the methods considered completes this review. Full article

The global problem of microplastics in the environment is “inspiring” scientists to find environmentally friendly and economically viable methods to remove these pollutants from the environment. Advanced oxidation processes are among the most promising methods. In this work, the potential of Fenton, photo-Fenton, and Fenton-like processes for the degradation of microplastics from low-density polyethylene (LDPE), polypropylene (PP), and poly(vinyl chloride) (PVC) in water suspensions was investigated. The influence of three parameters on the efficiency of the degradation process was tested: the pH of the medium (3–7), the mass of added iron (10–50 times less than the mass of microplastics), and the mass of added H₂O₂ (5–25 times more than the mass of added iron). The effectiveness of the treatment was monitored by FTIR-ATR spectroscopy. After 60-min treatments, the PP microparticles were found to be insensitive. In the Fenton treatment of PVC and the photo-Fenton treatment of LDPE and PVC, changes in the FTIR spectra related to the degradation of the microplastics were observed. In these three cases, the treatment parameters were optimized. It was found that a low pH (3) and a high iron mass (optimal values were 1/12 and 1/10 of the mass of the microplastics for LDPE and PVC, respectively) favored all three. The degradation of LDPE by the photo-Fenton treatment was favored by high H₂O₂ concentrations (25 times higher than the mass of iron), while these concentrations were significantly lower for PVC (11 and 15 times for the Fenton and photo-Fenton treatment, respectively), suggesting that scavenging activity occurs. Full article

Metal oxide semiconductor-based photocatalysis and advanced oxidation processes (AOPs) are effective in treating various recalcitrant pollutants such as organic dyes present in industrial wastewater streams. AOPs rely on the highly reactive hydroxyl radicals (OH^•) that facilitate the non-selective destruction of most organic pollutants. Here, we present the novel synthesis of mesoporous FeTiO₃ catalyst via a simple, hard template-free, aqueous-solution-based hydrothermal synthesis method. The surfactant, tetradecyltrimethylammonium bromide (TTAB), was used as the structure-directing agent, the removal of which led to the formation of the mesoporous structure. The catalyst was characterized by thermo-gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Branauer–Emette–Teller analysis (BET), X-ray diffraction (XRD), and scanning electron microscope (SEM) techniques. The obtained catalyst has been studied for its photocatalytic application in the presence of H₂O₂ towards the degradation of organic dyes as representative pollutants, namely, rhodamine B (RhB) and methylene blue (MB) under direct solar light irradiation. The various characterizations confirm the formation of mesoporous FeTiO₃ with a pore size of ≈7.5 nm and a specific surface area of 65 ± 5 m²/g. The influence of H₂O₂ oxidant on the removal of the said dyes has also been studied at various concentrations in the presence of the synthesized catalyst to determine the optimum dosage of H₂O₂. The catalyst was efficient in the complete synergistic adsorption-led photo-Fenton-like removal of MB in just 30 min of irradiation time, while the 96% RhB was degraded in 240 min. Moreover, this catalyst has also shown potential for fluoride adsorption that reaches up to more than 50% in 90 min. Full article

Sulfamethoxazole (SMX) is a widely used antibiotic to treat bacterial infections prevalent among humans and animals. SMX undergoes several transformation pathways in living organisms and external environments. Therefore, the development of efficient remediation methods for treating SMX and its metabolites is needed. We fabricated a photo-Fenton catalyst using an UIO-66 (Zr) metal–organic framework (MOF) dispersed in diatomite by a single-step solvothermal method for hydroxylation (HO-UIO-66). The HO-UIO-66-0/DE-assisted Fenton-like process degraded SMX with 94.7% efficiency; however, HO-UIO-66 (Zr) is not stable. We improved the stability of the catalyst by introducing a calcination step. The calcination temperature is critical to improving the catalytic efficiency of the composite (for example, designated as HO-UIO-66/DE-300 to denote hydroxylated UIO-66 dispersed in diatomite calcined at 300 °C). The degradation of SMX by HO-UIO-66/DE-300 was 93.8% in 120 min with 4 mmol/L H₂O₂ at pH 3 under visible light radiation. The O1s XPS signatures signify the stability of the catalyst after repeated use for SMX degradation. The electron spin resonance spectral data suggest the role of h⁺, •OH, •O₂⁻, and ¹O₂ in SMX degradation routes. The HO-UIO-66/DE-300-assisted Fenton-like process shows potential in degrading pharmaceutical products present in water and wastewater. Full article