Facet-dependent activation of oxalic acid over hematite nanocrystals under the irradiation of visible light for efficient degradation of pollutants.

Naturally occurring hematite has been widely studied in the Fenton-like system for water pollutant remediation due to its abundance and non-toxicity. However, its inadequate catalytic activity results in difficulty in effectively degrading pollutants in the catalytic degradation system that it constitutes. Thus, we constructed a photochemical system composed of hematite with {001} facet of high activity facet and low-cost and non-toxic oxalic acid (OA) for the removal of various types of pollutants. The removal rate for the degradation of metronidazole, tetracycline hydrochloride, Rhodamine B, and hexavalent chromium by hematite nanoplate with the exposed {001} facet activating OA under visible light irradiation was 4.75, 2.25, 2.33, and 2.74 times than that by the exposed {110} facet, respectively. Density functional theory (DFT) calculation proved that the OA molecule was more easily adsorbed on the {001} facet of hematite than that on the {110} facet, which would favor the formation of the more Fe(III)-OA complex and reactive species. In addition, the reactive site of metronidazole for the attraction of radicals was identified on the basis of the DFT calculation on the molecular occupied orbitals, and the possible degradation pathway for metronidazole included carbon chain fracture, hydroxyethyl-cleavage, denitrogenation, and hydroxylation. Thus, this finding may offer a valuable direction in designing an efficient iron-based catalyst based on facet engineering for the improved activity of Fenton-like systems such as OA activation.

Insight into CaO2-based Fenton and Fenton-like systems: strategy for CaO2-based oxidation of organic contaminants.

This study conducted a comparison of the CaO2-based Fenton (CaO2/Fe(II)) and Fenton-like (CaO2/Fe(III)) systems on their benzene degradation performance. The H2O2, Fe(II), Fe(III), and HO● variations were investigated during the benzene degradation. Although benzene has been totally removed in the two systems, the variation patterns of the investigated parameters were different, leading to the different benzene degradation patterns. In terms of the Fe(II)/Fe(III) conversion, the CaO2/Fe(II) and CaO2/Fe(III) systems were actually inseparable and had the inherent mechanism relationships. For the CaO2/Fe(III) system, the initial Fe(III) must be converted to Fe(II), and then the consequent Fenton reaction could be later developed with the regenerated Fe(II). Moreover, some benzene degradation intermediates could have the ability to facilitate the transformation of the Fe(III) to Fe(II) without the classic H2O2-associated propagation reactions. By varying the Fe(II) dosing method, an effective degradation strategy has been developed to take advantage of the two CaO2-based oxidation systems. The proposed strategy was further successfully tested in TCE degradation, therefore extending the potential for the application of this technique.

Protocatechuic acid enhanced the selective degradation of sulfonamide antibiotics in Fe(III)/peracetic acid process under actually neutral pH conditions.

The practical application of the Fe-catalyzed peracetic acid (PAA) processes is seriously restricted due to the need for narrow pH working range and poor anti-interference capacity. This study demonstrates that protocatechuic acid (PCA), a natural and eco-environmental phenolic acid, significantly enhanced the removal of sulfonamide antibiotics in Fe(III)/PAA process under actually neutral pH conditions (6.0-8.0) by complexing Fe(III). With sulfamethoxazole (SMX) as the model contaminant, the pseudo-first-order rate constant of SMX elimination in PCA/Fe(III)/PAA process was 63.5 times higher than that in Fe(III)/PAA process at pH 7.0, surpassing most of the previously reported strategies-enhanced Fe-catalyzed PAA processes (i.e., picolinic acid and hydroxylamine etc.). Excluding the primary contribution of reactive species commonly found in Fe-catalyzed PAA processes (e.g., •OH, R-O•, Fe(IV)/Fe(V) and 1O2) to SMX removal, the Fe(III)-peroxy complex intermediate (CH3C(O)OO-Fe(III)-PCA) was proposed as the primary reactive species in PCA/Fe(III)/PAA process. DFT theoretical calculations indicate that CH3C(O)OO-Fe(III)-PCA exhibited stronger oxidation potential than CH3C(O)OO-Fe(III), thereby enhancing SMX removal. Four potential removal pathways of SMX were proposed and the toxicity of reaction solution decreased with the removal of SMX. Furthermore, PCA/Fe(III)/PAA process exhibited strong anti-interference capacity to common natural anions (HCO3-, Cl-and NO3-) and humic acid. More importantly, the PCA/Fe(III)/PAA process demonstrated high efficiency for SMX elimination in actual samples, even at a trace Fe(III) dosage (i.e., 5 µM). Overall, this study provided a highly-efficient and eco-environmental strategy to remove sulfonamide antibiotics in Fe(III)/PAA process under actually neutral pH conditions and to strengthen its anti-interference capacity, underscoring its potential application in water treatment.

Coupled effects of Fenton-like systems with different concentrations of H2O2/Biochar on diethyl phthalate removal: Dominant role of environmental persistent free radicals (EPFRs).

To investigate the impact of different H2O2 concentrations on the Fenton-like systems of H2O2/biochar, this study examined the mechanism of the physical structure and environmental persistent free radicals (EPFRs) of biochar during diethyl phthalate (DEP) removal by the Fenton-like system. The peak-splitting method was utilized to differentiate EPFRs types in cotton stalk biochar produced at different temperatures. High-temperature environments promote π-electron delocalization, which facilitates phenyl π free radicals and σ-π oxygen-containing free radicals. By analyzing relationships between the removal rate K1 and removal constant Kobs of DEP with the structural properties of biochar, it was discovered that EPFRs concentrations in biochar had a significant positive correlation with K1 (r = 0.92) and Kobs (r = 0.97). Different H2O2 concentrations added to the biochar removal system resulted in varied DEP removal efficiency. Among them, CS500, CS550, and CS600 exhibited superior DEP removal efficiency when H2O2 concentration was 5 mM.

Application of MXene-based materials in Fenton-like systems for organic wastewater treatment: A review.

Recently, Fenton-like systems have been widely explored and applied for the removal of organic matter from wastewater. Two-dimensional (2D) MXene-based materials exhibit excellent adsorption and catalysis capacity for organic pollutants removal, which has been reported widely. However, there is no summary on the application of MXene-based materials in Fenton-like systems for organic matter removal. In this review, four types of MXene-based materials were introduced, including 2D MXene, MXene/Metal complex, MXene/Metal oxide complex, and MXene/3D carbon material complex. In addition, the Fenton-like system usually consists of adsorption and degradation processes. The oxidation process might contain hydrogen peroxide (H2O2) or persulfate (PS) oxidants. This review summarizes the performance and mechanisms of organic pollutants adsorption and oxidants activation by MXene-based materials systematically. Finally, the existing problems and future research directions of MXene-based materials are proposed in Fenton-like wastewater treatment systems.

Vanadium as co-catalyst for exceptionally boosted Fenton and Fenton-like oxidation: Vanadium species mediated direct and indirect routes.

In this study, vanadium powder (V) was employed as a cocatalyst to enhance the Fenton-like system. The V-Fe(III)/H2O2 system can rapidly produce hydroxyl radicals and completely oxidize chloramphenicol with exceptionally high stability for long-term operation. The low-valent vanadium sites on the surface during the stepwise oxidation of vanadium from V0 to V(IV) can donate electrons for direct H2O2 activation and indirect Fenton reaction by reducing Fe(III) to produce hydroxyl radicals. Meanwhile, density functional theory (DFT) calculation unveils that low-valent vanadium sites of vanadium can lengthen Fe-O bonds of FeOH2+ to elevate the oxidation potential of Fe(III) and promote Fe(III) reduction induced by H2O2. The self-cleaning effect of vanadium under acidic conditions can maintain reactive sites for sustainable electron donation and long-lasting enhanced Fenton oxidation. This study provides a novel enhanced Fenton oxidation for water remediation and the first mechanistic insights into the origins of V-based advanced oxidation technologies, it may also be beneficial to treat vanadium-contained wastewater.

Unraveling the critical role of iron-enriched sludge hydrochar in mediating the Fenton-like oxidation of triclosan.

The traditional Fenton system is subject to the low efficiency of the Fe(III)/Fe(II) conversion cycle, with significant attempts made to improve the oxidation efficiency by overcoming this hurdle. In support of this goal, iron-enriched sludge-derived hydrochar was prepared as a high-efficiency catalyst by one-step hydrothermal carbonization and its performance and mechanisms in mediating the oxidation of triclosan were explored in the present study. The hydrochar prepared at 240 °C for 4 h (HC240-4) had the highest removal of triclosan (97.0%). The removal of triclosan in the HC240-4/H2O2 system was greater than 90% in both acidic and near-neutral environments and remained as high as 83.5% after three cycles, indicating the broad pH applicability and great recycling stability of sludge-derived hydrochar in Fenton-like systems. H2O2 was activated by both persistent free radicals (PFRs; 19.7%) and iron (80.3%). The binding of Fe(III) to carboxyl decreased the electron transfer energy from H2O2 to Fe(III), making its degradation efficiency 2.6 times greater than that of the conventional Fenton reaction. The study provides a way for iron-enriched sludge utilization and reveals a role for hydrochar in promoting iron cycling and electron transfer in the Fenton reaction.

Treatment of sewage sludge hydrothermal carbonization aqueous phase by Fe(II)/CaO2 system: Oxidation behaviors and mechanism of organic compounds.

The Fe(II)/CaO2 system with a stable oxidant and a low-cost homogeneous activating agent has been considered as a prospective process for the disposal of wastewater. The system was constructed to treat sewage sludge hydrothermal carbonization aqueous phase (HTC-AP) in this study. As the hydrothermal temperature increased, the organics in the HTC-AP were first decomposed and then cyclized, while the Maillard reaction occurs throughout the stage. The oxidation efficiency of the Fe(II)/CaO2 system was related to the composition of organics in HTC-AP, and the removal of dissolved organic carbon (DOC) by the system was 38.56 % in the HTC-AP obtained by hydrothermal treatment at 220 °C. Redundancy analysis showed that the low molecular weight organics, hydrophobic acids, and hydrophobic neutral components were beneficial to DOC removal, while Maillard products and cyclization products were hard to be oxidized to CO2 and H2O. The CN functional group of the protein facilitated DOC removal, and some organics in HTC-AP were oxidized to acids and phenols. The energy input to remove DOC in Fe(II)/CaO2 system was 27.74 MJ per kg carbon. This study provides a low-energy consumption Fe(II)/CaO2 system for the post-treatment of HTC-APs and explores the applicability of the system.

Efficient removal of organic contaminants in CuS-mediated solid-liquid-interfacial fenton-like system: Role of bimetallic cycle and sulfur species.

The conventional Fenton-like system (Fe(III)/H2O2) is severely limited by the inferior activity of Fe(III) on H2O2 activation to produce highly active species and the sluggish regeneration rate of Fe(II). This work significantly enhanced the oxidative breakdown of the target organic contaminant bisphenol A (BPA) by Fe(III)/H2O2 by introducing cheap CuS at a low dose of 50 mg/L. The BPA removal (20 mg/L) in CuS/Fe(III)/H2O2 system reached 89.5 % within 30 min under the optimal conditions: CuS dosage 50 mg/L, Fe(III) concentration 0.05 mM, H2O2 concentration 0.5 mM and pH 5.6. Compared to CuS/H2O2 and Fe(III)/H2O2 systems, the reaction constants had a 47- and 12.3-fold enhancement, respectively. Even compared with the conventional Fe(II)/H2O2 system, the kinetic constant also increased more than twice, further confirming the distinctive superiority of constructed system. Element species change analyses showed that Fe(III) in solution was adsorbed onto the CuS surface, and then Fe(III) was rapidly reduced by Cu(I) in the CuS lattice. Combining CuS and Fe(III) (in-situ formed CuS-Fe(III) composite) created a robust co-effect on the activation of H2O2. Also, S(-II) and its derivatives, e.g., Sn2- and S0 (as an electron donor), could quickly reduce Cu(II) to Cu(I) and ultimately oxidize to the harmless product SO42-. Notably, a mere 50 µM of Fe(III) was sufficient to maintain enough regenerated Fe(II) to effectively activate H2O2 in CuS/Fe(III)/H2O2 system. In addition, such a system achieved a broad range of pH applications and was more suitable for real wastewater containing anions and natural organic matter. Scavenging tests, electron paramagnetic resonance (EPR), and probes further verified the critical role of •OH. This work provides a new approach to solving the problems of Fenton systems through a solid-liquid-interfacial system design and exhibits considerable application potential in wastewater decontamination.

Degradation of refractory organic matter in MBR effluent from treating landfill leachate by the UV-nZVI-H2O2 system.

In this study, nano zero-valent iron (nZVI) was used as the Fe2+ source in the Fenton reaction, and a UV-nZVI-H2O2 system was constructed to efficiently degrade and mineralize refractory organic matter in landfill leachate. The results showed that under the optimal conditions (initial pH = 3, UV = 14 W, nZVI = 0.5 g/L, and [H2O2] = 30 mM), the removal efficiencies of total organic carbon, absorbance at 254 nm, and color number were 61.38%, 83.89%, and 85.79%, respectively. Control experiments show that the UV-nZVI-H2O2 system has the highest removal rate and mineralization rate of refractory organic matter. The excellent performance of the UV-nZVI-H2O2 system is related to a higher H2O2 utilization rate. The H2O2 residue in the UV-nZVI-H2O2 system was the lowest, and the effective utilization rate of H2O2 was as high as 98.80%. Alcohol quenching experiments and hydroxyl radical quantitative experiments showed that the dominant reactive oxygen species in the UV-nZVI-H2O2 system was HO• and the yield of HO• was as high as 2007.80 µM, which was much higher than that in other systems. The results of spectra analysis showed that the low molecular weight, high fluorescence frequency organic matter, and relatively stable aromatic organic matter were significantly degraded after treatment with the UV-nZVI-H2O2 system and the aromatic degree, humification degree, molecular weight, and molecular polymerization degree of refractory organic matter were also significantly decreased. The mechanism of the UV-nZVI-H2O2 reaction includes homogeneous and heterogeneous Fenton reactions and adsorption and precipitation of organic matter by iron-based colloids. This study can provide theoretical and technical support for the advanced treatment of refractory organic matter in landfill leachate.

Hydroxylamine facilitated catalytic degradation of methylene blue in a Fenton-like system for heat-treatment modified drinking water treatment residues.

Rational treatment of drinking water treatment residues (WTR) has become an environmental and social issue due to the risk of secondary contamination. WTR has been commonly used to prepare adsorbents because of its clay-like pore structure, but then requires further treatment. In this study, a Fenton-like system of H-WTR/HA/H2O2 was constructed to degrade organic pollutants in water. Specifically, WTR was modified by heat treatment to increase its adsorption active site, and to accelerate Fe(III)/Fe(II) cycling on the catalyst surface by the addition of hydroxylamine (HA). Moreover, the effects of pH, HA and H2O2 dosage on the degradation were discussed with methylene blue (MB) as the target pollutant. The mechanism of the action of HA was analyzed and the reactive oxygen species in the reaction system were determined. Combined with the reusability and stability experiments, the removal efficiency of MB remained 65.36% after 5 cycles. Consequently, this study may provide new insights into the resource utilization of WTR.

Enhanced photocatalytic activity of magnetically recyclable spherical Fe3O4/Cu2O S-scheme heterojunction.

In this study, magnetically recyclable spherical Fe3O4/Cu2O particles comprising S-scheme heterojunctions were prepared by a simple hydrothermal approach using n-type semiconductor Fe3O4 as precursor and p-type semiconductor Cu2O. A Fenton-like system was thus constructed via the addition to Fe3O4/Cu2O of hydrogen peroxide. A rhodamine B (RhB) solution was used to simulate polluted wastewater, and photocatalytic RhB removal experiments were conducted under visible light irradiation. Powder X-ray diffractometry, vibrating-sample magnetometry, nitrogen adsorption-desorption, transmission electron microscopy, and X-ray photoelectron spectroscopy experiments were conducted to characterise Fe3O4 and Fe3O4/Cu2O composite. The band gap of Fe3O4/Cu2O was 1.76 eV, narrower than that of Fe3O4 (2.14 eV). The effects of the pH, sample dosage, hydrogen peroxide concentration, and RhB initial concentration on RhB removal were investigated. According to evidence, under the optimum reaction conditions, the RhB removal rate was 99.4%. The Fe3O4/Cu2O composite exhibited good photocatalytic efficacy even after four cycles of testing. Based on the results of free radical capture experiments, hydroxyl radicals and holes cooperated as main reactive species in the photocatalytic system. The Fe3O4/Cu2O photocatalyst can be easily removed based on magnetism, and it has been proven to be very effective for the degradation of RhB under both UV and visible light irradiation.

Forging Fenton-like system to functionalize electron/hole enrichment regions for ATZ photocatalytic degradation.

Independent functional regions for electrons and holes enrichment are usually driven by the construction of multiple heterostructures, which is difficult to achieve fine-controlling, resulting in the limited photocatalytic activity. TiO2-based photocatalysts with suitable forbidden band widths are promising for wide application prospects, where the construction of Schottky heterojunctions is the trick to achieve directional migration of electrons and holes. Here, a regionalized surface modification method of H-TiO2 with oxygen vacancy (Ov) and defects for efficient carrier separation was reported, in which interspersed Ag nanoparticles and SiO2 layers serve as electron/hole enrichment regions, respectively. Meanwhile, SiO2 can be served as adsorption sites for photocatalytic oxidation of small-molecule pollutants, while Ag nanoparticles with H+ adsorption capacity and reasonable guide band position can be used as an engine of Fenton-like reactions to cyclically generate the active substance H2O2 to participate in the reduction reaction. The degradation efficiency of Ag-SiO2-H-TiO2 (ASHT) can be increased by 159% for pesticide atrazine (ATZ). The superoxide radicals generated by electrons and oxygen in ASHT also generate H2O2, which promotes the centralized generation of hydroxyl radicals to improve photocatalytic performance. The structural design strategy of ASHT provides a new concept for the process of ring-opening reactions of benzene-containing contaminants in water and conversion to small molecules which will eventually be rapidly mineralized.

An assessment of the UV/nFe0 /H2 O2 system for the removal of refractory organics in the effluent produced by the biological treatment of landfill leachate.

The removal efficiency and mechanism of the ultraviolet/nanoscale Fe0 /H2 O2 (UV/nFe0 /H2 O2 ) system for refractory organics in membrane bioreactor effluent were investigated. The most effective removal of organics was achieved at initial pH = 3.0, H2 O2 dosage = 50 mM, nFe0 dosage = 1.0 g/L, and UV power = 15 W, with a reaction time of 60 min. Under these conditions, the absorbance at 254 nm, chromaticity, and total organic carbon removal efficiencies were 65.13%, 79.67%, and 61.51%, respectively, and the aromaticity, humification, molecular weight, and polymerization of organics were all significantly reduced. The surface morphology and elemental valence analysis of nano zero-valent iron (nFe0 ) before and after the reaction revealed the formation of iron-based (hydrated) oxides, such as Fe2 O3 , Fe3 O4 , FeOOH, and Fe (OH)3 , on the surface of the nFe0 . Refractory organics were removed by Fenton-like reactions in the homogeneous and heterogeneous adsorption-precipitation of iron-based colloids. At the same time, UV radiation accelerated the formation of Fe2+ on the nFe0 surface and promoted the Fe3+ /Fe2+ redox cycle to a certain extent, enhancing the removal of refractory organics. The results provide a theoretical basis for the application of the UV/nFe0 /H2 O2 system to remove refractory organics in the effluent produced by the biological treatment of landfill leachate. PRACTITIONER POINTS: The UV/nFe0 /H2 O2 process is effective in refractory organics removal in leachate treatment. Humus in leachate was largely destroyed and mineralized by the UV/nFe0 /H2 O2 process. Active nFe0 material participated in the Fenton-like process and was promoted by UV. The effects of nFe0 material and UV introduction were investigated.

Effects of CaO2 based Fenton - like reaction on heavy metals and microbial community during co-composting of straw and sediment.

In this study, a Fenton-like system was constructed by CaO2 and nano-Fe3O4 in the co-composting system of straw and sediment. Its effect on the passivation of heavy metals and the evolution of microbial community were investigated. The results showed that the establishment of CaO2-Fenton-like system increased the residual Cu and residual Zn by 27.62% and 16.80%, respectively. In addition, the CaO2-Fenton-like system facilitated the formation of humic acid (HA) up to 20.84 g·kg-1. Redundancy analysis (RDA) showed that the CaO2-Fenton-like system accelerated bacterial community succession and promoted the passivation of Cu and Zn. Structural equation models (SEMs) indicated that Fenton reaction affected Cu and Zn passivation by affecting pH, bacterial communities, and HA. This study shows that the CaO2-Fenton-like system could promote the application of composting in the remediation of heavy metals contamination in sediment.

Fast preparation of Fe3O4@polydopamine/Au for highly efficient degradation of tetracycline.

This work reported the fast synthesis of magnetic polydopamine Au-Fenton catalyst (Fe3O4@PDA/Au) under UV irradiation at 365 nm. The microstructure of prepared nanocomposites was characterized by various techniques. The effects of several key factors (pH values, H2O2 content and TC concentration) of tetracycline (TC) degradation were evaluated. The results revealed that the TC and total organic carbon (TOC) removal rate reached up to 98.16% and 93.14% within 300 min under optimal conditions (pH 3, H2O2 80 µL, TC concentration 20 mg/L). Besides, HO radicals were generated during the Fenton-like degradation process and the plausible degradation mechanism was discussed. Moreover, Fe3O4@PDA/Au catalyst retained excellent catalytic capacity (TC removal rate 96.94% and TOC removal rate 87.69%) and exhibited fantastic stability after six cycles. Moreover, metal ions leaching was evaluated (0.023 mg/L). Altogether, the novel Fe3O4@PDA/Au Fenton-like catalyst is highly promising for wastewater management.

Oxygen functionalized g-C3N4 strengthen Fe(III)/H2O2 system by accelerating Fe(III)/Fe(II) cycles under natural solar light: A mutual-promoting configuration.

In response to the inherent restriction of low Fe(II) regeneration in the Fenton process, this study demonstrated a mutual-promoting configuration, where oxygen functionalized g-C3N4 (OCN) was applied in Fe(III)/H2O2 system to utilize mild natural solar light (SL) for persistent Fe(II) generation. The constructed OCN/Fe(III)/H2O2/SL system exhibited strong adaptability to various pollutants, and it well outperformed the g-C3N4 (GCN) modified system and the traditional Fenton system in pollutants degradation efficiency. Compared with GCN, OCN could significantly promote the Fe(II) generation under solar light (SL), leading to more efficient H2O2 activation. The characterization analyses revealed the larger surface area and enhanced charge separation of OCN, which were considered to take main responsibility for its enhanced photoactivity. The complexation of Fe(III) with the carboxyl groups of OCN also benefited the Fe(II) generation. ·OH was detected as the dominant radical responsible for metronidazole (MNZ) degradation, and its production in the OCN modified system was about twice that in the GCN modified system and the Fenton system. Moreover, the precipitation of FeOx on the OCN surface benefited the charge separation of the OCN, so that the improved OCN enabled a slight enhancement of MNZ degradation in the reuse experiments. The intermediates of MNZ degradation were analyzed based on the results of LC-MS, which provided insight into MNZ degradation pathways. This work highlighted the concept of self-improving photocatalyst, the ingenious combination of photocatalysis and Fenton-like system formed a mutual-promoting situation where the OCN and the Fenton-like system could both be improved, which endowed the configuration great potential for green and economical oxidation in environmental remediation.

Hydroxylamine driven advanced oxidation processes for water treatment: A review.

Hydroxylamine (HA) driven advanced oxidation processes (HAOPs) for water treatment have attracted extensive attention due to the acceleration of reactive intermediates generation and the improvement on the elimination effectiveness of target contaminants. In this review, HAOPs were categorized into three parts: (1) direct reaction of HA with oxidants (e.g., hydrogen peroxide (H2O2), peroxymonosulfate (PMS), ozone (O3), ferrate (Fe(VI)), periodate (IO4-)); (2) HA driven homogeneous Fenton/Fenton-like system (Fe(II)/peroxide/HA system, Cu(II)/O2/HA system, Cu(II)/peroxide/HA system, Ce(IV)/H2O2/HA system); (3) HA driven heterogeneous Fe/Cu-Fenton/Fenton-like system (iron-bearing material/peroxide/HA system, copper-bearing material/peroxide/HA system, bimetallic composite/peroxide/HA system). Degradation efficiency of the target pollutant, reactive intermediates, and effective pH range of various HAOPs were summarized. Further, corresponding reaction mechanism was elaborated. For the direct reaction of HA with oxidants, improvement of pollutants degradation was achieved through the generation of secondary reactive intermediates which had higher reactivity compared with the parent oxidant. For HA driven homogeneous and heterogeneous Fe/Cu-Fenton/Fenton-like system, improvement of pollutants degradation was achieved mainly via the acceleration of redox cycle of Fe(III)/Fe(II) or Cu(II)/Cu(I) and subsequent generation of reactive intermediates, which avoided the drawbacks of classical Fenton/Fenton-like system. In addition, HA driven homogeneous Fe/Cu-Fenton/Fenton-like system with heterogeneous counterpart were compared. Further, formation of oxidation products from HA in various HAOPs was summarized. Finally, the challenges and prospects in this field were discussed.

High selectivity and effectiveness for removal of tetracycline and its related drug resistance in food wastewater through schwertmannite/graphene oxide catalyzed photo-Fenton-like oxidation.

Selectively and effectively for removal of tetracycline (TC) and its related antibiotic resistance gene from food wastewater matrix with high-salt and high COD characteristics is highly desirable. In this work, novel schwertmannite/graphene oxide (SCH/GO) nanocomposites were synthesized through a facile oxidation-coprecipitation method. The SCH/GO nanocomposites were characterized by TEM, XRD, BET, PL, DRS, XPS and FTIR. In the presence of 1 mM H2O2, the SCH/GO catalyzed Fenton-like oxidation can thoroughly degrade TC under visible light irradiation, even under nature sunlight, whose second-order kinetic rate constant was about 15 times higher than that of pure SCH. SCH/GO was capable of highly selectively capturing and effectively degrading TC in the presence of similar concentration of Cl-, NO3-, SO42- and PO43- with that of food wastewater, even at organic matters concentration of 12.5 times than that of TC. At the same time, the removal of total organic carbon (TOC) and chemical oxygen demand (COD) in aforementioned food wastewater in SCH/GO+H2O2+Vis system reached 27.3 % and 34.5 % after 60 min, respectively. The inhibition zone experiments authenticated that the removal of drug resistance of bacteria by TC degradation intermediates can be achieved very well without producing secondary contamination in this system.

Simultaneous removal of methylene blue and total dissolved copper in zero-valent iron/H2O2 Fenton system: Kinetics, mechanism and degradation pathway.

This study aimed to investigate the simultaneous removal of methylene blue (MB) and total dissolved copper (TCu) by heterogeneous zero-valent iron (ZVI) Fenton-like system (ZVI/H2O2) and elucidate the mechanism of synergistic effect for co-contaminants removal. Hydroxyl radical (OH) formation was hypothesized to be the dominant pathway for the oxidation of MB, confirmed by the quenching experiments and ESR analysis. And the synergistic effect of TCu and ZVI greatly promoted the release of Fe2+, further accelerating the generation of hydroxyl radical (OH) via Fenton reaction. The generation process of OH was unveiled by quenching experiments and electron spin resonance (ESR) analysis, while the processes of ZVI corrosion and TCu reduction were revealed through several characterization approaches including SEM, XRD, FTIR and XPS. The degradation pathway of MB was also investigated by LC-MS analysis. The MB initial concentration, TCu initial concentration, H2O2 dosage, ZVI dosage and initial solution pH could play crucial roles in the removal of MB and TCu. The influence of water matrix including inorganic anions (Cl-, NO3-, HCO3-) and actual water was finally conducted to elucidate the role of natural organic matter (NOM) in the environmental systems.