Search Results (25)

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

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

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

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

Advanced oxidation processes (AOPs) have been postulated as viable, innovative, and efficient technologies for the removal of pollutants from water bodies. Among AOPs, photo-Fenton processes have been shown to be effective for the degradation of various types of organic compounds in industrial wastewater. Monometallic iron catalysts are limited in practical applications due to their low catalytic activity, poor stability, and recyclability. On the other hand, the development of catalysts based on copper oxides has become a current research topic due to their advantages such as strong light absorption, high mobility of charge carriers, low environmental toxicity, long-term stability, and low production cost. For these reasons, great efforts have been made to improve the practical applications of heterogeneous catalysts, and the bimetallic iron–copper materials have become a focus of research. In this context, this review focuses on the compilation of the most relevant studies on the recent progress in the application of bimetallic iron–copper materials in heterogeneous photo–Fenton-like reactions for the degradation of pollutants in wastewater. Special attention is paid to the removal efficiencies obtained and the reaction mechanisms involved in the photo–Fenton treatments with the different catalysts. Full article

This work aimed to demonstrate Cu₂O/Al₂O₃ as a catalyst of the photo-Fenton process in the UV and visible spectra. Cu₂O nanoparticles were synthesized by laser ablation in liquid and supported on Al₂O₃. The catalytic activity of the resulting solid was assessed in the mineralization of bisphenol A (BPA). The studied variables were type of Al₂O₃$\left(\alpha \mathrm{and} \gamma \right)$, Cu content (0.5 and 1%), and H₂O₂ concentration (1, 5, and 10 times the stoichiometric amount). The response variables were BPA concentration and total organic carbon (TOC) removal percentage. The presence of Cu₂O nanoparticles (11 nm) with an irregular sphere-like shape was confirmed by transmission electron microscopy (TEM) and their dispersion over the catalytic surface was verified by energy-dispersed spectroscopy (EDS). These particles improve ·OH radical production, and thus a 100% removal of BPA is achieved along with ca. 91% mineralization in 60 min. The BPA oxidation rate is increased one order of magnitude compared to photolysis and doubles that for H₂O₂ + UV. An increase of 40% in the initial oxidation rate of BPA was observed when switching from α-Al₂O₃ to γ-Al₂O₃. 4-hydroxybenzaldehyde, 4-hydroxybenzoic acid, acetaldehyde, and acetic acid are the BPA oxidation by-products identified using LC/MS and based on this a reaction pathway was proposed. Finally, it was also concluded that the synthesized catalyst exhibits catalytic activity not only in the UV spectrum but also in the visible one under circumneutral pH. Therefore, Cu₂O/Al₂O₃ can be recommended to conduct a solar photo-Fenton reaction that can degrade other types of molecules. Full article

The degradation of various preservatives used in the cosmetics industry, including five parabens and their most employed substitute, methylisothiazolinone (MIT), was investigated. A mild photo-Fenton process was applied using low iron concentrations (5 mg/L) at a pH of five, instead of the traditional acidic value of three. At these conditions, the paraben degradation was very low after one hour of reaction and it was necessary to present humic-like substances (HLS) acting as iron chelators to improve the process. Values obtained when MIT was treated were very low, also in the presence of HLS, indicating that their complexing effect was not acting properly. When MIT was added to the mixture of parabens an inhibitory effect was found in the presence of HLS. A possible complex between iron and MIT was suggested and the studies of hydrogen peroxide consumption and Job’s plot technique confirmed this hypothesis. Evidence of the formation of this inactive complex, so far never reported, will be essential in future work when dealing with this compound using Fenton processes. Furthermore, this fact points out the importance of using mixtures of model contaminants instead of a single one or a group of the same family, since their ability to form active or inactive complexes with iron can strongly change the behavior of the whole system. Full article

In the current work, novel graphene quantum dots (GQDs)-doped goethite (α-FeOOH) nanocomposites (GQDs/α-FeOOH) were prepared by following a feasible hydrolysis method and applied for ciprofloxacin (CIP) removal. Results showed that the CIP degradation efficiency was significant (93.73%, 0.0566 min⁻¹) in the GQDs/α-FeOOH + H₂O₂ + Vis system using much lower amounts of H₂O₂ (0.50 mM), which is 3.9 times the α-FeOOH + H₂O₂ + Vis system. It was found that •OH, ${\mathrm{O}}_2^{•-}$, and ¹O₂ were mainly responsible for CIP degradation in the GQDs/α-FeOOH photo-Fenton system. GQDs/α-FeOOH demonstrated broad-spectrum UV–vis-IR responsiveness in the degradation of ciprofloxacin as a function of the doping of GQDs. Additionally, GQDs/α-FeOOH showed outstanding durability (recyclability up to 3 cycles with a lower iron leaking amount, 0.020 mg L⁻¹), a broad range of application pH, and a pretty acceptable catalytic efficacy in a variety of surface water matrices. Overall, GQDs/α-FeOOH have been shown to be an effective photocatalyst for the remediation of emerging contaminants via the workable exploitation of solar energy. Full article

Hollow transition metal oxides have important applications in the degradation of organic pollutants by a photo-Fenton-like process. Herein, uniform, highly dispersible hollow CuFe₂O₄/C nanospheres (denoted as CFO/C-PNSs) were prepared by a one-pot approach. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images verified that the CFO/C-PNS catalyst mainly presents hollow nanosphere morphology with a diameter of 250 ± 30 nm. Surprisingly, the photodegradation test results revealed that CFO/C-PNSs had an excellent photocatalytic performance in the elimination of various organic contaminants under visible light through the efficient Fenton catalytic process. Due to the unique hollow structure formed by the assembly of ultra-small CFO/C subunits, the catalyst exposes more reaction sites, improving its photocatalytic activity. More importantly, the resulting magnetically separable CFO/C-PNSs exhibited excellent stability. Finally, the possible photocatalytic reaction mechanism of the CFO/C-PNSs was proposed, which enables us to have a clearer understanding of the photo-Fenton mechanism. Through a series of characterization and analysis of degradation behavior of CFO/C-PNS samples over antibiotic degradation and Cr(VI) reduction, •OH radicals generated from H₂O₂ decomposition played an essential role in enhancing the reaction efficiency. The present work offered a convenient method to fabricate hollow transition metal oxides, which provided impetus for further development in environmental and energy applications. Highlights: Novel hollow CuFe₂O₄/C nanospheres were prepared by a facile and cost-effective method. CuFe₂O₄/C exhibited excellent photo-Fenton-like performance for antibiotic degradation. Outstanding photocatalytic performance was attributed to the specific hollow cavity-porous structure. A possible mechanism for H₂O₂ activation over hollow CuFe₂O₄/C nanospheres was detailed and discussed. Full article

In this work, a classical linear control approach for the peroxide (H${}_2$O${}_2$) dosage in a photo-Fenton process is presented as a suitable solution for improving the efficiency in the treatment of recalcitrant organic compounds that cannot be degraded by classical wastewater treatment processes like anaerobic digestion. Experiments were carried out to degrade Lignin, Melanoidin, and Gallic acid, which are typical recalcitrant organic compounds present in some kinds of effluents such as vinasses from the Tequila and Cachaça industries. Experiments were carried in Open-Loop mode for obtaining the degradation model for the three compounds in the form of a Transfer Function, and in Closed-Loop mode for controlling the concentration of each compound. First-order Transfer Functions were obtained using the reaction curve method, and then, based on these models, the parameters of Proportional Integral controllers were calculated using the direct synthesis method. In the Closed-Loop experiments, the Total Organic Carbon removal was 39% for lignin, 7% for melanoidin, and 29% for Gallic acid, which were greater than those obtained in the Open-Loop experiments. Full article

In this study, the viability of South African ilmenite sands as a catalyst in the photo-Fenton-like degradation of methyl orange (MO) dye was investigated. The mineralogy and other properties of the material were characterized. Complete decolorization occurred under acidic conditions (pH < 4) in the presence of ilmenite and H₂O₂. Light irradiation accelerated the rate of reaction. Parameter optimization revealed that a pH of 2.5, UVB irradiation, 2 g/L catalyst loading, and a hydrogen peroxide concentration of 1.0 mM were required. Under these conditions, complete decolorization was observed after 45 min. Degradation kinetics were best described by the pseudo-first order (PFO) model. Rate constants of 0.095 and 0.034 min⁻¹ were obtained for 5 and 20 mg/L MO concentrations, respectively. A 37% total organic carbon removal was observed after 60 min. This suggests a stepwise MO degradation pathway with intermediate formation rather than complete mineralization. Although iron leaching was detected, the mineralogy of the catalyst recovered after the reaction was similar to the fresh catalyst. Full article

In this work, the photochemical treatment of a real municipal wastewater using a persulfate-driven photo-Fenton-like process was studied. The wastewater treatment efficiency was evaluated in terms of total carbon (TC), total organic carbon (TOC) and total nitrogen (TN) removal. Response surface methodology (RSM) in conjunction Box-Behnken design (BBD) and multilayer artificial neural network (ANN) have been utilized for the optimization of the treatment process. The effects of four independent factors such as reaction time, pH, K₂S₂O₈ concentration and K₂S₂O₈/Fe²⁺ molar ratio on the TC, TOC and TN removal have been investigated. The process significant factors have been determined implementing Analysis of Variance (ANOVA). Both RSM and ANN accurately found the optimum conditions for the maximum removal of TOC (100% and 98.7%, theoretically), which resulted in complete mineralization of TOC at the reaction time of 106.06 min, pH of 7.7, persulfate concentration of 30 mM and K₂S₂O₈/Fe²⁺ molar ratio of 7.5 for RSM and at the reaction time of 104.93 min, pH of 7.7, persulfate concentration of 30 mM and K₂S₂O₈/Fe²⁺ molar ratio of 9.57 for ANN. On the contrary, the attempts to find the optimal conditions for the maximum TC and TN removal using statistical, and neural network models were not successful. Full article