Search Results (395)

Although Ru-based catalysts have been investigated in various oxidation systems, their application in sulfate radical-based AOPs, particularly as heterogeneous activators for acidic wastewater treatment, remains limited. Herein, Ru was incorporated into α-MnO₂ via lattice doping and surface loading to construct Ru_latt/α-MnO₂ and Ru_surf/α-MnO₂, and their PMS activation performance toward carbamazepine (CBZ) degradation was evaluated. Ru_latt/α-MnO₂ exhibited superior activity, achieving near-complete CBZ removal within minutes under acidic conditions. PMS dosage, catalyst loading, and pH affected the degradation efficiency, with acidic environments significantly enhancing PMS activation. Cl⁻ slightly promoted CBZ degradation, whereas HCO₃⁻ and natural organic matter inhibited it. Mechanistic analysis revealed that Ru activated PMS through a nonradical pathway, continuously generating ¹O₂ via a reversible Ru (II)/Ru (III)/Ru (IV) cycle, while the Mn (III)/Mn (IV) redox couple acted as an electron buffer to sustain Ru cycling and improve durability. The catalyst maintained high activity in complex water matrices, demonstrating strong potential for practical remediation of CBZ-contaminated acidic wastewater. Full article

Iron-based catalysts for peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation represent a cornerstone of advanced oxidation processes (AOPs) in environmental remediation, prized for their cost-effectiveness, environmental compatibility, and high catalytic potential. These catalysts, including zero-valent iron, iron oxides, and iron-organic frameworks, activate PMS/PDS through heterogeneous and homogeneous pathways to generate reactive species such as sulfate radicals (SO₄•⁻) and hydroxyl radicals (•OH). However, their large-scale implementation is constrained by inefficient iron cycling, characterized by sluggish Fe³⁺/Fe²⁺ conversion and significant iron precipitation, leading to catalyst passivation and oxidant wastage. This comprehensive review systematically dissects innovative strategies to augment iron cycling efficiency, encompassing advanced material design through elemental doping, heterostructure construction, and defect engineering; system optimization via reductant incorporation, bimetallic synergy, and pH modulation; and external field assistance using light, electricity, or ultrasound. We present a mechanistic deep-dive into these approaches, emphasizing facilitated electron transfer, suppression of iron precipitation, and precise regulation of radical versus non-radical pathways. The performance in degrading persistent organic pollutants—including antibiotics, per- and polyfluoroalkyl substances (PFASs), and pesticides—in complex environmental matrices is critically evaluated. We further discuss practical challenges related to scalability, long-term stability, and secondary environmental risks. Finally, forward-looking directions are proposed, focusing on rational catalyst design, integration of sustainable processes, and scalable implementation, thereby providing a foundational framework for developing next-generation iron-persulfate catalytic systems. Full article

The non-oxidizing antimicrobial 2-Methyl-4-Isothiazolin-3-one (MIT) poses a significant environmental risk given its frequent detection in municipal wastewater. This study showed that the combination of Vacuum UV/UV (VUV/UV) and persulfate (PDS) efficiently achieved the rapid transformation and removal of 10 μM MIT within 90 s, which is much faster than UV, UV/PDS, and VUV/UV. Increasing the PDS dosage improved MIT degradation, whereas changes in pH between 4 and 10 had little effect. Radical quenching experiments showed that 93% of the MIT oxidation was attributable to the hydroxyl radical (•OH) and the sulfate radical (SO₄•⁻). SO₄•⁻ and •OH at concentrations of 8.6 × 10⁻¹² M and 1.5 × 10⁻¹² M accounted for 32% and 61% of the MIT degradation, respectively, and the greater contribution of •OH was attributed to its higher reaction rate constant with MIT compared to SO₄•⁻. Sulfate had a negligible impact on the radical concentrations. Chloride (1 mM) reduced the SO₄•⁻ and •OH concentrations by 61% and 27%, respectively. And the SO₄•⁻ contribution to MIT degradation fell to 19%. Nitrate (5 mM) readily quenched •OH but minimally affected SO₄•⁻. The •OH concentration decreased by 79%, reducing its contribution to 27%. Bicarbonate/carbonate (5 mM) simultaneously reduced the SO₄•⁻ and •OH by 26–30% and had little effect on their contributions. Because of the quenching effect of organic matter and inorganic anions on radicals, secondary effluent inhibited the degradation of MIT. After a 120 s treatment, the total organic carbon, UV₂₅₄, and fluorescence regional integration were reduced by 5%, 8%, and 17–24%, respectively. This study provides a quantitative analysis of how inorganic ions alter the concentrations and contributions of •OH and SO₄•⁻, elucidating the MIT removal mechanisms in VUV/UV/PDS for sustainable wastewater reclamation. Full article

Removing toxic formaldehyde (HCHO) from environmental water is crucial for human health and the ecosystem. Perovskite-type Lanthanum cobalt oxide (LaCoO₃) has achieved great success in a wide range of catalytic processes; however, this concept has been rarely applied to the degradation of HCHO. Here, we prepared perovskite-type catalysts with different La/Co molar ratios, and the time for HCHO oxidation degradation at room temperature was shortened by 12 times (10 min vs. 119 min) compared to other heterogeneous catalysts. LaCoO₃ exhibits superior catalytic activity for HCHO degradation at room temperature when the La/Co molar ratio is 1:1 compared to lanthanum cobalt oxides with other molar ratios. The X-ray photoelectron spectroscopy (XPS) test results show that increasing the La/Co molar ratio reduces the Co²⁺ content in the catalyst, while Co²⁺ plays the most important role in the catalyst. Quencher experiments indicated that sulfate radicals (SO₄·⁻) and hydroxyl radicals (·OH) were the primary reactive species for the removal of HCHO. This finding suggests that the catalytic oxidation reaction involving HCHO operates as a heterogeneous Fenton-like oxidation reaction. Full article

Sulfonated carbon catalysts, as a type of solid protonic acid, have been widely recommended for various applications. However, syntheses of them typically require strict conditions, posing challenges in efficiency and environmental impact. Herein, we report a rapid, acid-free method to introduce sulfonic and sulfate ester groups onto carbon nanotubes (CNTs) by simply stirring them in an aqueous sodium persulfate solution (Na₂S₂O₈) at room temperature. Within 45 min, the treated CNTs reached sulfur-containing acid densities up to 0.34 mmol g⁻¹ without thermal treatment and hazardous reagents. The resulting catalyst demonstrated effective performance in terms of cellulose hydrolysis, attaining 31.6% conversion and 23.2% glucose yield. The process requires only the energy input of magnetic stirring, underscoring its environmental and practical advantages. This simple approach provides a sustainable and cost-effective alternative for the preparation of carbon-based catalysts, offering significant potential for biomass conversion and other green-chemistry applications. Full article

Micro-nano bubbles (MNBs) have been widely used in water treatment due to their large specific surface area, long retention time, and high zeta potential. This study investigated the degradation of bisphenols by activating persulfate (PDS, an oxidizing agent) with air MNBs (MNBs/PDS). The removal rate of bisphenol A (BPA) in the MNBs/PDS process was 98.3% within 25 min, while there was almost no degradation observed by PDS or MNBs alone. This enhancement was attributed to the huge amount of energy released during the collapse of MNBs, sufficient to break the O–H bonds of water molecules or the O–O bond of PDS to induce the formation of reactive oxygen species (ROS, such as HO^• and SO₄^•−). To qualitatively analyze ROS generated in this system, electron paramagnetic resonance and quenching experiments were conducted, and the HO^• and SO₄^•− were detected in MNBs/PDS. Furthermore, the degradation percentages of bisphenols after 25 min of MNBs/PDS treatment followed the order of bisphenol B (100%) > BPA (98.3%) > bisphenol E (87.9%) > bisphenol F (86.5%) > bisphenol AF (84.9%) > bisphenol S (51%). Higher PDS dosage, higher gas flow rate, and lower pH values were preferred for the degradation. Moreover, the MNBs/PDS treatment reduced the TOC of secondary effluent containing BPA by 45.8% in one hour, indicating the application potential of MNBs/PDS in the advanced treatment of wastewater. Full article

The ability of ultrasound/peracetic acid (US/PAA) to degrade the azo dye Sunset Yellow FCF (SSY) was evaluated considering the impacts of power, pH, inorganic carbon, common salts, radical scavengers, and real water matrices. Pseudo-first-order rate constants revealed synergy indices of 2.90, 3.28, 2.22, and 2.03 at electrical powers of 40, 60, 80, and 100 W, respectively. Selective scavenger assays revealed a mixed radical regime. ^•OH radical involvement was confirmed by inhibition with alcohols (tert-butanol, 2-propanol), benzoic acid, nitrobenzene, sodium azide, and phenol, while suppression by TEMPO highlighted the key role of PAA-derived acyl and peroxyl radicals. Nitrobenzene caused pronounced inhibition at elevated doses, while nitrite acted as a decisive quencher by converting ^•OH and other oxidants into less reactive species. Carbonate alkalinity exerted dual effects: at acidic pH (3.7–4.4) it diverted ^•OH radicals to carbonate radicals and reduced cavitation through dissolved CO₂, whereas at near-neutral pH it buffered conditions toward the optimum (pH 9) and enhanced degradation. Common anions (chloride, sulfate, nitrate) at ≤10 mM produced minor effects. Tests in environmental waters revealed the following reactivity order: seawater > ultrapure water > tap water ≈ Zamzam water > tertiary effluent. Enhanced performance in seawater was attributed to halide-mediated formation of reactive chlorine and bromine species, while inhibition in effluent was linked to organic matter scavenging. Overall, US/PAA emerges as a robust and adaptable advanced oxidation process for azo dye abatement across diverse water matrices. Full article

The effectiveness of periodate-assisted photocatalysis in removing the cationic dye Safranin O (SO) was evaluated using a UV/TiO₂/IO₄⁻ process operated at room temperature under near-neutral pH conditions. Under base conditions ([IO₄⁻] = 0.15 mM, [TiO₂] = 0.4 g/L, [SO] = 10 mg/L), the ternary system achieved a pseudo-first-order rate constant of 0.6212 min⁻¹, outperforming the UV/TiO₂ and UV/IO₄⁻ processes by approximately 21- and 29-fold, respectively. This yielded a synergy ratio of about 12 compared to the sum of the binary processes. Targeted quenching experiments revealed the operative pathways. Strong inhibition by ascorbic acid and phenol indicates that interfacial holes and ^•OH are key oxidants. Methanol caused a moderate slowdown, consistent with ^•OH and hole scavenging. Benzoquinone and oxalate suppressed removal by intercepting the electron and O₂^•− pathways, respectively. Dichromate markedly inhibited the process via optical screening and competition for electrons. Azide had little effect, suggesting a minor role for singlet oxygen. Matrix studies showed progressively slower kinetics from deionized water to mineral water to seawater. This was due to halides, sulfate, alkalinity, and TiO₂ aggregation driven by ionic strength. Additional tests confirmed that the dominant modulators of performance were humic acid (site fouling and light screening), chloride and sulfate (radical speciation and surface effects), nitrite (near-diffusion radical quenching), and bicarbonate at pH 8.3 (conversion of ^•OH to CO₃^•−). Nonionic surfactants (Tween 80, Triton X-100) also depressed SO removal through micellar sequestration and competitive adsorption on TiO₂. The study confirms the potential of UV/TiO₂/IO₄⁻ as a tunable AOP capable of delivering rapid and reliable dye degradation under a wide range of water quality conditions. The mechanistic mapping unifies two roles for IO₄⁻, an electron acceptor that inhibits recombination and a photochemical precursor of iodine centered and ^•OH radicals and connect these roles to the observed synergy and to the trend across deionized water, mineral water, and seawater. The scavenger outcomes assign the main oxidant flux to holes and ^•OH radicals with a contributory electron or O₂^•− branch from IO₄⁻ reduction. Full article

As an eco-friendly flame-retardant additive, magnesium hydroxide (MH) is widely employed in low-smoking, halogen-free polymer materials due to its environmentally benign nature. In order to enhance flame retardancy performance, the modified MH was modified with tetrakis(hydroxymethyl)phosphonium sulfate (THPS) by a one-pot hydrothermal method. The resulting morphology was characterized using scanning electron microscopy (SEM), and it shows the dispersion of nanometer particles and almost no aggregation. The X-ray photoelectron spectroscopy (XPS) along with Raman spectroscopy show that the THPS is connected with the Mg(OH)₂ by chemical bond. The sample was incorporated into ethylene–vinyl acetate (EVA) to evaluate the flame retardancy was assessed via limiting oxygen index (LOI) and vertical burning tests (UL-94). The results show that THPS modified MH effectively enhanced the flame retardancy, achieving a V-0 rating and an LOI value of 31.3%. In addition, the composites retain good mechanical integrity. The thermal analysis with TGA and DTG shows the formation of the MgO decomposition product, along with water vapor and phosphorus-containing radicals released by modified MH in the combustion process, forming a strong flame-retardant protective layer. In addition, the maximum smoke density of EVA/MHP-3 composite was 155.4, lower than 411.3 for EVA/MH, with a 62.2% reduction in total smoke production. The result shows that THPS is effective for improving the flame-retardant efficiency of inorganic metal hydroxide in polymer composites. Full article

The degradation of Brilliant Coomassie Blue G-250 (BCB) was investigated using the thermally activated persulfate (TAP) process in deionized water. A kinetic model incorporating both hydroxyl (^●OH) and sulfate (SO₄^●–) radicals was developed to predict pseudo-first-order rate constants (kₒ) for the interaction of BCB with these radicals. Experimental results demonstrated efficient BCB degradation under TAP treatment. A parametric study examining the effects of initial conditions such as solution pH, persulfate concentration, initial BCB concentration, and temperature revealed that higher persulfate dosages, lower BCB concentrations, and alkaline pH enhanced degradation performance. Complete removal of BCB was achieved within 20 min under optimal conditions ([BCB]₀ = 10 mg/L, [PS]₀ = 2 mg/L, neutral pH). The kinetic model showed strong agreement with experimental data across a broad range of pH and persulfate concentrations. The rate constants for BCB reactions with ^●OH and SO₄^●– were determined through simulation to be 4.731 × 10⁹ M⁻¹s⁻¹ and 1.07 × 10⁹ M⁻¹s⁻¹, respectively. The selectivity analysis results revealed that SO₄^●– radicals played a dominant role in the degradation process across the various initial persulfate concentration scenarios. The remaining degradation was attributed to the contribution of ^●OH radicals. These findings are linked to the higher reactivity of BCB with SO₄^●– compared to ^●OH. Overall, the results demonstrate that TAP process is an effective method for the removal of emerging contaminants such as BCB from water. Full article

The widespread presence of bisphenol A (BPA), a persistent endocrine-disrupting pollutant, in aquatic environments poses significant ecological and health risks, necessitating its effective removal. However, conventional remediation technologies are often hampered by catalysts with narrow pH adaptability and poor stability. In this study, a novel catalyst, Zeolite-supported Cu₃Mn-layered double hydroxide (LDH), was fabricated using the co-precipitation method. The synthesized catalyst was applied to activate peroxymonosulfate (PMS), effectively enabling decomposition of BPA by advanced oxidation processes. The composite material was characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM), which confirmed the successful synthesis of the zeolite-supported Cu₃Mn-LDH. The catalyst exhibited high activity in both neutral and strongly alkaline environments, achieving complete degradation of 10 mg⋅L⁻¹ bisphenol A (BPA) within 40 min and a 98% total organic carbon (TOC) removal rate when both the PMS and catalyst were dosed at 0.15 g⋅L⁻¹. Singlet oxygen was detected as the primary reactive species responsible for BPA degradation, as verified by quenching experiments and EPR analysis, which also identified the presence of sulfate (SO₄^•−), hydroxyl (•OH), and superoxide (•O₂⁻) radicals. The catalyst exhibited excellent reusability, maintaining high catalytic efficiency over two consecutive cycles with minimal performance loss. Gas chromatography-mass spectrometry (GC-MS) analysis revealed five intermediate products, enabling the proposal of potential BPA degradation pathways. This work not only presents a novel synthetic approach for zeolite-supported LDH composites, but also offers a promising strategy for the efficient removal of BPA from aqueous systems through AOPs. Full article

In this study, we investigated the performance of iron-loaded biochar (Fe-BC) derived from mulberry branches in activating persulfate (PS) for the efficient degradation of sulfamethoxazole (SMX). The Fe-BC/PS system exhibited superior catalytic activity towards SMX degradation, achieving 97% removal within 60 min. The degradation efficiency was found to be highly dependent on preparation conditions, including calcination temperature, the type of iron salt, and biomass feedstock. Reactive species such as hydroxyl radicals (^•OH), sulfate radicals (SO₄^•−), and iron (IV) (Fe(IV)) were identified as key contributors to SMX degradation, with Fe(IV) playing a dominant role. The influence of water quality parameters, such as inorganic ions, pH, and natural organic matter (NOM), on the degradation of SMX was also examined. Proposed degradation pathways revealed the stepwise oxidation of SMX into smaller intermediates, ultimately leading to mineralization. Our findings highlight the potential of Fe-BC/PS systems as a sustainable and effective approach for the remediation of sulfonamide antibiotics in aquatic environments. Full article

The development of efficient and sustainable advanced oxidation processes (AOPs) for organic pollutant removal is of great significance for water purification. In this study, a CoFeNi-layered double hydroxide (CoFeNi-LDH) catalyst was synthesized and applied for the simultaneous activation of peroxymonosulfate (PMS) and ozone to degrade rhodamine B (RhB) in aqueous solution. The CoFeNi-LDH/PMS/ozone system achieved a remarkable RhB removal efficiency of 95.2 ± 1.2% within 8 min under neutral pH conditions. Systematic parametric studies revealed that synergistic interactions among CoFeNi-LDH, PMS, and ozone contributed to the generation of reactive oxygen species (ROS), primarily sulfate radicals (SO₄^•−) and singlet oxygen (¹O₂), as confirmed by EPR and quenching experiments. Density functional theory (DFT) calculations demonstrated that ozone enhanced PMS adsorption and activation at CoFeNi catalytic sites. The catalyst exhibited robust magnetic recyclability and structural stability after repeated use. This work highlights a synergistic catalytic strategy for PMS/ozone activation, offering an effective and environmentally friendly platform for dye wastewater remediation. Full article

Fucoidan B (FucB) is a sulfated polysaccharide with recognized biological activity. In this study, FucB was chemically modified through redox conjugation with gallic acid (GA) to obtain FucB-GA, aiming to enhance its antioxidant properties. Structural characterization using FTIR, NMR, and electrophoresis confirmed the successful covalent binding of GA to FucB without major structural degradation. The conjugation increased the phenolic content and reduced crystallinity, as shown by XRD and SEM, indicating greater amorphous character, which can favor biological applications. Thermogravimetric analysis demonstrated enhanced thermal stability in FucB-GA. Antioxidant activity was evaluated through various in vitro assays. FucB-GA showed superoxide radical scavenging activity of 91.96%, copper chelating capacity of 43.2%, antioxidant capacity of 37 mg AEE/g, and reducing power of 94.22%, significantly higher results than FucB, while no sample chelated iron. Under the conditions analyzed, gallic acid alone showed minimal or no activity in most assays. These results suggest that conjugation with GA increases the antioxidant potential of FucB, while also improving the activity and bioavailability of GA, likely due to the increase in electron-donating and metal-binding groups. Overall, the study supports the development of FucB-GA as a promising antioxidant compound for pharmaceutical or nutraceutical applications. Full article

Per- and polyfluoroalkyl substances (PFAS) are a diverse group of synthetic fluorinated compounds widely used in industrial and consumer products due to their exceptional thermal stability and hydrophobicity. However, these same properties contribute to their environmental persistence, bioaccumulation, and potential adverse health effects, including hepatotoxicity, immunotoxicity, endocrine disruption, and increased cancer risk. Traditional water treatment technologies, such as coagulation, sedimentation, biological degradation, and even advanced membrane processes, have demonstrated limited efficacy in removing PFAS, as they primarily separate or concentrate these compounds rather than degrade them. In response to these limitations, photoassisted processes have emerged as promising alternatives capable of degrading PFAS into less harmful products. These strategies include direct photolysis using UV or VUV irradiation, heterogeneous photocatalysis with materials such as TiO₂ and novel semiconductors, light-activated persulfate oxidation generating sulfate radicals, and photo-Fenton reactions producing highly reactive hydroxyl radicals. Such approaches leverage the generation of reactive species under irradiation to cleave the strong carbon–fluorine bonds characteristic of PFAS. This review provides a comprehensive overview of emerging photoassisted technologies for PFAS removal from water, detailing their fundamental principles, degradation pathways, recent advancements in material development, and integration with hybrid treatment processes. Moreover, it discusses current challenges related to energy efficiency, catalyst deactivation, incomplete mineralization, and scalability, outlining future perspectives for their practical application in sustainable water treatment systems to mitigate PFAS pollution effectively. Full article