Search Results (59)

Fenton oxidation is effective for degrading refractory organic contaminants, but slow Fe³⁺-to-Fe²⁺ regeneration under acidic conditions limits continuous H₂O₂ activation. Here, Acid Orange 7 (AO7) was used as a model pollutant to evaluate a coupled Mn⁰/Fe/H₂O₂ system designed to promote iron redox cycling and enhance H₂O₂ activation. AO7 degradation was examined under different operating conditions, and reactive species and mechanisms were identified using electron spin resonance spectroscopy, chemical probes, and quenching experiments. Under optimized conditions (pH 3.0, 10 μM AO7, 2 mM H₂O₂, 9 μM Fe²⁺, and 0.05 g/L Mn⁰), 88% of AO7 was degraded within 30 min. Hydroxyl radicals (•OH) and FeO²⁺ were identified as the main reactive species, accounting for 88.6% and 11.4% of AO7 degradation, respectively. Mn⁰ promoted AO7 degradation by directly activating H₂O₂ to form •OH and by reducing Fe³⁺ to Fe²⁺, thereby sustaining Fe²⁺/Fe³⁺ cycling and facilitating •OH and FeO²⁺ generation. Sulfate and carbonate had negligible effects, whereas fulvic acid, nitrate, and chloride inhibited degradation. AO7 degradation decreased to 40% in lake water and 60% in river water. These results demonstrate that Mn⁰ addition can enhance Fenton-like oxidation by accelerating iron redox cycling, suggesting its potential in treating dye-contaminated wastewater under controlled operational conditions. Full article

MgCr₂O₄ nanospinel samples were synthesized using a modified Pechini method, followed by controlled calcination. The resulting materials were evaluated in terms of crystal structure, particle morphology, and optical and electronic properties. Their oxidative activity towards the degradation of organic dyes was investigated via photocatalysis, Fenton-like, and photon-Fenton-like processes. Various analytical techniques were employed to characterize the samples, including X-ray diffraction (XRD) with Rietveld refinements, infrared (IR) spectroscopy, UV–Vis spectroscopy, colorimetry, and transmission and high-resolution transmission electron microscopy (TEM/HRTEM). Structural characterization revealed that MgCr₂O₄ crystallized after calcination at 600 °C, and Rietveld refinements confirmed cubic Fd-3m symmetry. IR spectra confirmed the short-range order through the presence of vibrational modes assigned to CrO₆^2- octahedra. UV–Vis spectroscopy indicated mixed Cr valences (Cr³+/Cr⁶+) for samples calcined at temperatures below 900 °C, with Cr⁶+ eliminated at higher temperatures, confirmed by electron paramagnetic resonance (EPR) spectroscopy. This suggests that an oxidation reaction occurred due to oxygen vacancies in the lattice. Optical bandgap (Eg) increased with temperature. Samples calcined at low temperatures were dark green and became more saturated at temperatures above 900 °C, suggesting photoresponse to visible light, as indicated by the Eg values. The oxidative activity of the nanospinels in degrading the dyes methylene blue (MB) and rhodamine B (RhB) under visible light depended on the nature of the dye, the catalyst concentration, and the use of H₂O₂ in the process to improve the formation of hydroxyl radicals (•OH), as confirmed by photohydroxylation of terephthalic acid (TA). The highest degradation rate was observed in the photo-Fenton-like process, with 96% and 97% degradation of RhB and MB dyes in 60 min, reaching a kinetic rate constant (${\mathit{K}}_{app}$) of 0.055 min⁻¹ and 0.051 min⁻¹, respectively. This study highlights the importance of controlling various parameters to promote the formation of reactive oxygen species (ROS) required for oxidative degradation by nanospinels. Full article

The present study investigates the solar-assisted photo-Fenton-like degradation of a reactive azo dye (Red SPR) using an iron-based metal–organic framework, MIL-100(Fe), as a heterogeneous catalyst. The synthesized MIL-100(Fe) was successfully characterized by XRD, SEM, EDX, and FTIR analyses, confirming the formation of a crystalline, porous structure with well-dispersed Fe active sites. The catalytic performance was systematically evaluated under various operational parameters, including hydrogen peroxide dosage, catalyst loading, pH, circulation flow rate, initial dye concentration, and temperature. The results demonstrated that optimal degradation efficiency was achieved at pH 3.0, H₂O₂ concentration of 400 mg L⁻¹, and catalyst dosage of 40 mg L⁻¹, while a circulation flow rate of 400 mL min⁻¹ ensured optimal hydrodynamic conditions. The system exhibited rapid degradation kinetics, achieving nearly complete dye removal within 60 min under solar irradiation. Kinetic analysis revealed that the degradation process follows pseudo-first-order behavior, with rate constants increasing from 0.1040 to 0.1589 min⁻¹ as temperature increased from 25 to 55 °C. Thermodynamic analysis indicated that the process is endothermic (ΔH` = 8.72 kJ mol⁻¹) and kinetically favorable with a low activation energy (Ea = 11.32 kJ mol⁻¹), while negative entropy values suggested the formation of an ordered transition state. Radical scavenger experiments confirmed that hydroxyl radicals (•OH) are the dominant reactive species, with secondary contributions from superoxide radicals (O₂•⁻). The enhanced performance is attributed to the synergistic effect of solar irradiation and Fe³⁺/Fe²⁺ redox cycling within the MIL-100(Fe) framework. Hence, the study demonstrates that MIL-100(Fe) is a highly efficient and sustainable catalyst for solar-driven wastewater treatment applications. Full article

Manganese dioxide (MnO₂) modified biochar catalysts derived from biomass and waste polymer feedstocks were synthesized and evaluated as heterogeneous Fenton-like catalysts for solar-driven degradation of Rhodamine B (RhB) in aqueous systems. Biochars produced from maple wood and plastic waste (high-density polyethylene) provided porous carbon matrices with oxygen-rich surface functionalities that enabled effective MnO₂ loading and catalytic activity. Photocatalytic experiments conducted under real sunlight using a solar-collector reactor demonstrated faster RhB degradation compared to a conventional ultraviolet (UV) system, confirming the advantage of solar-driven operation. Complete RhB removal was achieved at initial concentrations of 100–300 ppm, whereas higher dye concentrations (500 ppm) exceeded the catalytic capacity within the tested reaction time. Kinetic analysis revealed catalyst-dependent reaction behaviors, indicating that degradation pathways were strongly influenced by the biopolymer-derived carbon structure and MnO₂ dispersion. Degradation efficiency was correlated with solar irradiance and reactor temperature, with higher UV index conditions enhancing catalytic performance. Reusability tests showed that the catalysts remained active over multiple cycles, although gradual decreases in reaction rates and catalyst recovery were observed. These results demonstrate the potential of biopolymer-derived carbon materials as effective solar-driven catalysts for wastewater treatment applications. Full article

The development of efficient, sustainable, and low-cost catalysts for wastewater treatment remains a major environmental challenge. In this work, Zn-doped CuO nanostructures were successfully synthesized via a green route using Aloysia citrodora leaf extract as a natural reducing and stabilizing agent. The structural and morphological properties of the prepared catalysts were systematically characterized by XRD, Raman spectroscopy, FTIR, SEM, and EDX analyses. The results revealed the formation of highly crystalline monoclinic CuO nanoparticles, whose defect density and surface properties were significantly modified by Zn incorporation. The catalytic performance of the synthesized materials was evaluated through the heterogeneous Fenton-like degradation of Rhodamine B in aqueous solution under dark conditions. The Zn-doped CuO catalyst exhibited outstanding degradation efficiency (~99.97%) within only 30 min, using a low catalyst dosage of 15 mg and a minimal H₂O₂ amount of 25 μL. The enhanced catalytic activity is attributed to the synergistic interaction between Zn-induced lattice defects and the Cu²⁺/Cu⁺ redox cycle, which promotes efficient H₂O₂ activation and •OH radical generation. Radical scavenging experiments confirmed the dominant role of hydroxyl radicals in the degradation process. Compared with previously reported CuO-based catalysts, the present system demonstrates superior performance in terms of reaction rate, oxidant consumption, and energy efficiency. These findings highlight the potential of Zn-doped CuO synthesized via green chemistry as a promising and sustainable catalyst for advanced wastewater treatment applications. Full article

A one-pot green combustion route was developed for the synthesis of ashy single-crystalline NiO nanoparticles using date molasses as a biogenic fuel and complexing medium. The obtained DM–NiO showed phase-pure cubic NiO with an average crystallite size of about 18 nm, a mesoporous texture with a BET surface area of 68.9 m² g⁻¹, a pore volume of 0.59 cm³ g⁻¹, an average pore diameter of 17.6 nm, and a mean particle size of 43.6 ± 8.13 nm. Optical characterization revealed defect-mediated light absorption with an energy gap of 3.11 eV, supporting solar-light-driven activity. In the photocatalytic degradation of pyronin Y, the catalyst exhibited strong pH dependence, reaching its best H₂O₂-free performance at pH 11 with a pseudo-first-order rate constant of 0.0072 min⁻¹, nearly six times higher than that at pH 3. The introduction of H₂O₂ markedly intensified the process, and at 9 mM H₂O₂, the rate constant increased to 0.048 min⁻¹, representing more than a sixfold enhancement over photocatalysis alone, while complete disappearance of the main visible absorption band was achieved within 38 min under solar illumination. Radical trapping experiments identified photogenerated holes and hydroxyl radicals as the dominant oxidative species. The catalyst also retained high activity over four successive cycles, with degradation efficiencies decreasing only slightly from 91.8% to 85.7%. These results demonstrate that date-molasses-assisted combustion synthesis provides a sustainable route to defect-active mesoporous NiO with highly enhanced solar photo-Fenton-like performance for dye-contaminated wastewater treatment. Full article

Hetero-multicomponent metal oxide catalysts are attracting increasing attention for wastewater remediation due to their tunable band structures, synergistic redox activity, and enhanced stability. This review thoroughly evaluates recent progress in the synthesis and application of such catalysts, highlighting Ti–Cu–Zn nanostructures as a representative case study. We examine synthesis approaches—including hydrothermal, biosynthesis, precipitation, and spray-based methods, with additional insight into sol–gel and other less commonly applied techniques—with emphasis on their suitability for constructing layered and multicomponent heterostructures. Mechanistic aspects of photocatalysis, Fenton and Fenton-like processes, adsorption, and electrochemical routes are discussed, with particular focus on charge separation, reactive oxygen species (ROS) generation, and pollutant-specific degradation pathways. Comparative performance metrics against antibiotics, pesticides, dyes, and fertilizers are analyzed, alongside considerations of leaching, reusability, and scale-up potential. Importantly, while significant progress has been made for organic micropollutants, applications in heavy metal remediation remain scarce, highlighting an urgent research gap. By situating Ti–Cu–Zn systems within the broader class of multicomponent catalysts, this review not only synthesizes current advances but also identifies opportunities to expand their role in sustainable wastewater management, including field deployment, regulatory compliance, and integration into decentralized treatment systems. Full article

To address the issues of hydrophobicity, easy fouling, and limited application of polyvinylidene fluoride (PVDF) membranes in water treatment processes, this study prepared Cu-MnO₂/GO/PVDF catalytic membranes via the immersion precipitation phase inversion method. Graphene oxide (GO) was incorporated to facilitate the construction of good water channels, while copper-doped manganese dioxide (Cu-MnO₂) was added to enhance catalytic activity. The structure, morphology, and performance of the membranes were characterized comprehensively. Results showed that Cu-MnO₂ was well interspersed between GO sheets, thereby increasing membrane surface roughness, effective filtration area, and hydrophilicity. The best catalytic membrane CM-5 exhibited the highest pure water flux (1391.20 L·m⁻²·h⁻¹) and methyl blue (MBE) rejection rate (98.06%), and it also displayed excellent reusability and stability. EPR tests confirmed the generation of HO· and HOO· in the Fenton-like system, which mediated dye degradation. The Cu-MnO₂/GO/PVDF catalytic membrane demonstrated excellent hydrophilicity, antifouling properties, and catalytic efficiency, thus providing a viable solution for dye wastewater treatment. Full article

This study systematically investigates the catalytic degradation performance and reaction mechanism of Fe₈₀P₁₃C₇ Metal Glass (MG) in a Fenton-like system for the removal of Methylene Blue (MB). Kinetic experiments on degradation reveal that under acidic conditions (pH = 3), Fe₈₀P₁₃C₇ MG exhibits exceptional catalytic activity, achieving complete degradation of a 50 mg/L MB solution within 12 min. Its degradation rate significantly surpasses that of Fe₇₈Si₉B₁₃ MG and commercially available ZVI powder. Key parameters such as catalyst dosage, H₂O₂ concentration, solution pH, and initial dye concentration were systematically examined to determine the optimal reaction conditions. The characterization results indicate that Fe₈₀P₁₃C₇ MG maintains high activity even after multiple cycles of use, attributed to surface selective corrosion and crack formation during the reaction process. This “self-renewal” mechanism continuously exposes fresh active sites. Mechanistic studies confirm that the degradation process is driven by an efficient redox cycle between Fe²⁺/Fe³⁺ within the material, ensuring sustained and stable generation of •OH, which ultimately leads to the complete mineralization of MB molecules. This research provides solid experimental and theoretical foundations for the application of Fe₈₀P₁₃C₇ MG in dye wastewater treatment. Full article

The photo-Fenton process is an advanced oxidation method widely employed in environmental remediation. Herein, we developed a novel metal–organic framework@hydrogen-bonded organic framework (MOF/HOF) composite with excellent photo-Fenton-like activity for the efficient degradation of organic dye methylene blue (MB). Cu-based MOF (CuBTC) was firstly prepared via the solvothermal method, then melamine (MA) and trimesic acid (TMA)-based HOF (MA-TMA) was grown in situ on CuBTC with hydrogen bonding interactions to produce the MOF/HOF composite CuBTC-MA. The CuBTC-MA composite could catalyze H₂O₂ to produce active substances for efficient MB degradation. The degradation rate constant of the CuBTC-MA composite was 4.4 times and 16.7 times higher than that of CuBTC and MA-TMA. The remarkably enhanced performance was attributed to the synergistic effect between the efficient separation of electron–holes supported by the type-II heterojunction structure of the CuBTC-MA composite and the Cu(I)/Cu(II) inter-conversion. The CuBTC-MA composite demonstrated exceptional repeatability and maintained a stable performance across a broad pH range. This study provided a novel paradigm for engineering heterogeneous MOF/HOF heterostructures, demonstrating significant potential in advancing photo-Fenton-like catalytic systems for the efficient environmental remediation of organic pollutants through synergistic charge separation and radical generation mechanisms. Full article

Water pollution caused by synthetic dyes is a major environmental concern due to their stability, toxicity, and resistance to conventional wastewater treatments. This study presents a sustainable approach for synthesizing zinc oxide (ZnO) nanoparticles using artichoke biomass (waste) as a green precursor and enhancing their visible light photocatalytic activity through phosphorus doping. ZnO nanoparticles were successfully synthesized via a simple green route and doped with 3–6% phosphorus using NH₄H₂PO₄. The structural, morphological, and optical properties of the resulting P-ZnO were characterized by XRD, SEM/EDX, TEM, FTIR, and UV-Vis spectroscopy. (6 wt%) Phosphorus doping effectively reduced the band gap from 3.06 eV to 2.95 eV, extended light absorption into the visible range, and improved electron–hole separation, resulting in enhanced photocatalytic performance. The P-ZnO nanoparticles were evaluated for methylene blue (MB) degradation under visible light in a photo-Fenton-like process, with H₂O₂ as an oxidant. The degradation efficiency reached 87.05% with 6% P-ZnO and further increased to 92.35% upon addition of H₂O₂. Durability and reusability tests demonstrated that the 6% P-ZnO catalyst maintained its activity and structural integrity over four consecutive cycles, indicating negligible loss of efficiency and excellent resistance to surface poisoning. The photocatalytic activity was strongly impacted by the quantity of catalyst, solution pH, and initial dye levels, with optimal performance at 0.3 g/L catalyst loading, pH 3, and lower MB concentrations. Full article

The removal of synthetic dyes from industrial effluents remains challenging due to their chemical stability and poor biodegradability. Here we engineer metal-doped carbon dots (CDs) as heterogeneous Fenton-like catalysts and elucidate how dopant identity governs structure–activity relationships and reactive oxygen species (ROS) pathways. Fe-, Cu-, Zn- and Mg-doped CDs were prepared via a one-pot hydrothermal route and comprehensively characterised by TEM, FTIR, XPS and zeta-potential analysis. The resulting nanoparticles displayed narrow size distributions (10.2–15.2 nm) and dopant-dependent surface chemistries and charges. Catalytic tests with methylene blue (MB) and rhodamine B (RB) show that Fe-doped CDs deliver the highest activity toward MB degradation (k = 0.0218 min⁻¹), attributable to efficient Fe²⁺/Fe³⁺ redox cycling coupled with hydroxyl-rich surfaces that promote H₂O₂ activation. Zn-doped CDs achieve complete RB decolourisation under Fenton-like conditions, which we ascribe to their higher surface charge and abundant oxygenated sites that enhance pollutant adsorption and ROS generation. Cu- and Mg-doped CDs exhibit intermediate and dopant-specific performances consistent with their respective redox and adsorption characteristics. Collectively, these results establish clear correlations between dopant chemistry, surface functionality, and ROS formation routes, providing mechanistic guidance for the rational design of carbon-based Fenton catalysts for sustainable water remediation. Full article

We studied the impact of some magnetic nanoparticles on two wastewater models of Rhodamine B dye, with 5 µM and 10 µM concentrations. The magnetite nanoparticles, synthesized by the co-precipitation technique, having less than 20 nm diameter and typical crystallinity features, were used to treat the Rhodamine B solutions and the results were analyzed using spectral measurements. The biological efficacy of the photo-Fenton-like reactions underlying this wastewater treatment was assessed using the V79-4 fibroblast cell line of Chinese hamster. The MTT test (colorimetric method with 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) was applied for the toxicity testing of Rhodamine B 10 µM and 5 µM, initially, and degraded with 8 g/L MNP and 10 mM hydrogen peroxide for 120 min of UV exposure, the cell viability decreasing to 57–59% and 69–74%, respectively, for the dose of 80 µL/mL. Morphological changes were identified by microscopy analysis, such as membrane disruption, cell content extravasation, apoptotic bodies, and also colored spherical inclusions suggesting non-metabolized dye solution aliquots. The simpler molecules consisting of Rhodamine B degradation products, i.e., benzoic acid, benzyloxyamine, and phthalic acid were analyzed for their theoretical reactivity through quantum chemical computational modeling, which revealed a significant chemical potential compared to Rhodamine B. Full article

Metallic glass, as an emerging catalytic material, possesses an atomic structure characterized by long-range disorder and short-range order, which creates abundant and accessible active sites that enhance the adsorption and reactivity toward pollutant molecules, particularly dye compounds. In treating highly colored and recalcitrant Reactive Black 5 (RB5) dye wastewater, Mo₅₁Fe₃₄B₁₅ metallic glass wire demonstrate outstanding catalytic degradation performance within a conventional Fenton-like system. Under acidic conditions (pH = 2), the material exhibits a degradation rate constant of 0.698 min⁻¹ for a 20 ppm RB5 dye solution, achieving a degradation efficiency of 98.8% within 10 min. After 10 consecutive cycles, the efficiency remains at 95%, and throughout 15 cycles, it consistently maintains a performance level above 90%. As the reaction proceeds, the degradation rate gradually decreases, primarily due to the accumulation of corrosion products on the catalyst surface, which are predominantly composed of MoO₃ and Fe₂O₃. During the degradation process, metallic Mo⁰ and Fe⁰ serve as electron donors that facilitate the decomposition of H₂O₂, generating highly reactive hydroxyl radicals (•OH). These radicals attack the chromophoric structure of the dye, leading to its structural disruption and enabling rapid decolorization. Full article

This study reports the hydrothermal synthesis, characterization, and Fenton-like catalytic performance of CeO₂–CoFe₂O₄ nanocomposites for degrading Congo Red (CR) dye and the oxytetracycline (OTC) antibiotic. A series of Ce-doped cobalt ferrite samples was prepared using a hydrothermal reaction. Additionally, the 50Ce-CFO sample was further activated with H₂O₂ treatment. XRD, FTIR, and SEM analyses confirmed the formation of a spinel phase alongside segregated CeO₂, which acts as a grain-growth inhibitor. The increased Ce content promotes particle amorphization. FTIR showed changes in the intensity of the M–O stretching band, indicating Ce-induced bond polarization in the spinel lattice. In H₂O₂ decomposition tests, the 50Ce-CFO catalyst fully decomposes H₂O₂ in 160 min, while the activated sample completes it in 125 min. Fenton-like degradation of CR and OTC by untreated and activated 50Ce-CFO sample followed pseudo-first-order kinetics. Catalyst stability was confirmed using post-reaction XRD, FTIR, and SEM analyses. Incorporation of CeO₂ into CoFe₂O₄ refines the crystallite size, increases the BET surface area, and enhances adsorption capacity, while the Ce⁴⁺/Ce³⁺ redox couple promotes reactive oxygen species generation. Owing to this dual structural and catalytic role, the CeO₂-CoFe₂O₄ composites exhibit significantly improved Fenton-like catalytic activity, enabling the efficient degradation of organic pollutants. Full article