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The extensive use of pharmaceuticals has increased their presence in the environment, posing significant ecological and public health concerns. The current study reports the magnetic nanocomposite (M-ABAC) synthesis using the algal-bacterial sludge as the precursor for activated carbon and evaluates its potential in fluoroquinolone antibiotics removal. The activated carbon from algal-bacterial sludge was composited with Fe3O4 nanoparticles using the co-precipitation method. The M-ABAC was characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), Brunauer-Emmett-Teller (BET) analysis, and vibrating sample magnetometry (VSM). M-ABAC was employed for antibiotic ciprofloxacin (CIP) removal by combined adsorption and heterogenous Fenton degradation. The adsorption studies reveal that the Langmuir isotherm best fits the experimental data, with a maximum adsorption capacity of 81.6 mg/g. Pseudo-second-order kinetic model well describes adsorption kinetics. Fenton catalytic degradation was performed using H2O2 as the activating agent. The optimal H2O2 dosage was observed to be 10 mM. A CIP adsorptive removal efficiency of 75% was observed at 2 g/L dosage of M-ABAC in a 200 ppm CIP solution. Simultaneous adsorption and Fenton catalytic degradation further enhanced the removal efficiency to 92%. Radical scavengers experiment revealed that the hydroxyl radical (•OH) was the dominant reactive oxidation species. The degradation products of the CIP were identified using liquid chromatography quadrupole time-of-flight mass spectroscopy (LC-QTOF-MS). The possible CIP degradation mechanisms include decarboxylation, piperazine moiety degradation, defluorination, and hydroxylation.

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Solar-driven interfacial water evaporation (SIWE) has emerged as a promising avenue for cost-effective freshwater production from seawater or wastewater. However, the simultaneous evaporation of volatile organic compounds (VOCs) presents a limitation for the widespread implementation of this technique. Thus, developing dual-functional evaporators capable of both desalining seawater and degrading VOCs is challenging. Herein, we fabricated an iron-based metal-organic framework MIL-88A/carbon nanotubes (CNTs) poly(vinyl alcohol) hydrogel (MCH) evaporator via the conventional freezing method for solar-driven seawater desalination and simultaneous photo-Fenton VOC degradation. Because of the superior photothermal conversion capability of CNTs, reduced thermal conductivity and water evaporation enthalpy within the hydrogel, and the photo-Fenton activity of rod-shaped MIL-88A, the MCH evaporator exhibits a higher evaporation rate of 2.26 kg m-2 h-1 under 1 sun illumination with simultaneous VOC degradation. The higher hydrophilicity and vertical channels in the MCH evaporator enable its self-salt cleaning ability, facilitating consistent seawater desalination, even in high salt concentrations up to 10 wt %. The synergistic effects of localized heating from CNTs and hydrogen peroxide activation through reactive sites of MIL-88A allow the MCH evaporator to degrade more than 93% of the added phenol during evaporation. This work presents a sustainable and efficient approach for solar-driven seawater desalination, offering simultaneous VOC degradation.

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The FeOCl-based photo-Fenton heterojunction catalyst holds great promise for effective water pollution treatment. A novel heterojunction FeOCl/MOF-In2S3 (F/M-I) was fabricated by coating hollow MOF-In2S3 nanoflowers onto the surface of FeOCl. Under the optimal conditions, the maximum photo-Fenton degradation rate constants of FeOCl/MOF-In2S3 for oxytetracycline (OTC) within 20 min is 0.88192 L mg-1·min-1, which are 3.2 and 2.5 times that of pure FeOCl (0.27357 L mg-1·min-1) and MOF-In2S3 (0.35222 L mg-1·min-1). Density functional theory (DFT) results confirm that the electron-rich nature of MOF-In2S3 accelerates the cycle between Fe (III)/Fe (II)of FeOCl, promoting H2O2 adsorption by FeOCl/MOF-In2S3 and generating more hydroxyl radicals (·OH) for pollutant degradation. Based on the results of DFT, combined with the results of the reactive oxidation species scavenger (ROSs), electron paramagnetic resonance (EPR) and Mott-Schottky curves, the separation and transfer behavior of photoexcited charges in FeOCl/MOF-In2S3 heterojunction and the possible photocatalytic degradation mechanism were investigated. Finally, a Z-scheme heterostructure is proposed to elucidate the catalytic mechanism. This study provides a new perspective on designing and synthesizing semiconductor materials for water treatment by photo-Fenton catalysis.

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Iron-containing MOFs have attracted extensive interest as promising Fenton-like catalysts. In this work, magnetic Fe3O4 nanofiber (FNS)/MOFs composites with stable structure, included FNS/MIL-88B, FNS/MIL-88A and FNS/MIL-100, were prepared via the in-situ solvothermal method. The surface of the obtained fibers was covered by a dense and continuous MOFs layer, which could effectively solve the agglomeration problem of MOFs powder and improved the catalytic performance. The adsorption and catalytic properties of FNS/MOFs composites were evaluated by removal of norfloxacin. FNS/MIL-88B showed the best performance with a maximum adsorption capacity up to 214.09 mg/g, and could degrade 99% of NRF in 60 min. Meanwhile, FNS/MIL-88B had a saturation magnetization of 20 emu/g, and could be rapidly separated by an applied magnetic field. The self-supported nanofibers allowed the adequate contact between MOFs and pollutants, and promoted the catalytic activity and high stability. We believe that this work provided a new idea for the design and preparation of Fenton-like catalysts especially MOFs composites.

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Tartary buckwheat (Fagopyrum tataricum (L.) Gaertn) leaf has abundant rhamnogalacturonan-I enriched pectic polysaccharides, which exert various health-promoting effects. Nevertheless, the potential relationship between the chemical structure and the biological function of pectic polysaccharides from Tartary buckwheat leaves (TBP) remains unclear. Therefore, to bridge the gap between the chemical structure and the biological function of TBP, the impacts of ultrasound-assisted Fenton degradation (UFD) and mild alkaline de-esterification (MAD) on structural properties and biological effects of TBP were systematically studied. Compared with the native TBP (molecular mass, 9.537 × 104 Da), the molecular masses of degraded TBPs (TBP-MMW, 4.811 × 104 Da; TBP-LMW, 2.101 × 104 Da) were significantly reduced by the UFD modification, while their primary chemical structures were overall stable. Besides, compared with the native TBP (esterification degree, 22.73 %), the esterification degrees of de-esterified TBPs (TBP-MDE, 14.27 %; TBP-LDE, 6.59 %) were notably reduced by the MAD modification, while their primary chemical structures were also overall stable. Furthermore, the results revealed that both UFD and MAD modifications could significantly improve the antioxidant, antiglycation, and immunostimulatory effects of TBP. Indeed, TBP's biological effects were negatively correlated to its molecular mass and esterification degree, while positively linked to its free uronic acids. The findings demonstrate that both UFD and MAD modifications are promising techniques for the structural modification of TBP, which can remarkedly promote its biological effects. Besides, the present results are conducive to better understanding TBP's structure-bioactivity relationship.

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Magnetite nanoparticles (Fe3O4 NPs) are among the most effective Fenton-Like heterogeneous catalysts for degrading environmental contaminants. However, Fe3O4 NPs aggregate easily and have poor dispersion stability because of their magnetic properties, which seriously decrease their catalytic efficiency. In this study, a novel environmentally friendly method for synthesising Fe3O4@CA was proposed. Fe3O4 NPs were immobilized on the 3D cellulose aerogels (CAs) in order to augment the degradation efficiency of p-nitrophenol (PNP) treatment and make the separation of the catalyst accessible by vacuum filtration method. Besides, CAs were fabricated from a cellulose source extracted from water hyacinth by using different cross-linking agents, such as kymene (KM) and polyvinyl alcohol-glutaraldehyde system (PVA-GA), and other drying methods, including vacuum thermal drying and freeze drying, were evaluated in the synthesis process. As-synthesized samples were analysed by various methods, including Powder X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray analysis and Brunauer-Emmett-Teller. Then, using ultraviolet-visible spectroscopy, the difference in the degradability of PNP of the obtained material samples was also investigated to determine their potential applications. Results highlighted that the Fe3O4-3@CA-KF catalyst with an Fe3O4 loading of 0.40 g/gCA used KM as a cross-linker and the freeze-drying method demonstrated the highest PNP removal efficiency (92.5 %) in all Fe3O4@CA samples with a H2O2 content of 5 g/L. The degradation kinetics and well-fitted pseudo-first-order model were investigated. Notably, after five successive PNP degradation experiments, this catalyst retained ∼80 % of the ability to degrade PNP, indicating its outstanding reusability. In environmental remediation, this study provides valuable insights into the development of simply separated and high-efficiency catalysts for heterogeneous catalytic reactions.

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Construction of S-scheme heterojunction is an efficient strategy to enhance photocatalytic efficiency. Besides the retained redox ability, the wide work function gap and intimate interface contact are essential for efficient degradation. Nontoxic magnesium oxide (MgO) with two dimensional (2D) structures and high work function is a potential material for S-scheme photocatalysts. Herein, MgO was used to in-situ grown on graphitic carbon nitride (g-C3N4) for constructing the strongly connected MgO/g-C3N4 S-scheme photocatalyst with tight Mg-N bonds. Meanwhile, the presence of Mg-N bonds induces the formation of oxygen vacancy in MgO, which enhances the Fenton-like degradation. Furthermore, the Mg-N bond promotes the charge migration between MgO and g-C3N4. Consisting of the enhanced Fenton-like process and photocatalysis, the MgO/g-C3N4 shows a higher photo-Fenton degradation activity (80.01%) for degradation of organic pollutants (Rhodamine B, 100 mg L-1) in water, than g-C3N4 (28.46%) and MgO (55.64%). Therefore, the interfacial chemical bonds in heterojunction photocatalysts provide an efficient strategy for further enhancing the photocatalysis of S-scheme photocatalysts.

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A Fe-pillared montmorillonite (Fe-MMT) functionalized bio-based foam (Fe-MMT@CS/G) was developed by using chitosan (CS) and gelatin (G) as the matrix for high-efficiency elimination of organic pollutants through the integration of adsorption and Fenton degradation. The results showed that the mechanical properties of as-obtained foam were strengthened by the addition of certain amounts of Fe-MMT. Interestingly, Fe-MMT@CS/G displayed efficient adsorption ability for charged pollutants under a wide range of pH. The adsorption processes of methyl blue (MB), methylene blue (MEB) and tetracycline hydrochloride (TCH) on Fe-MMT@CS/G were well described by the Freundlich isotherm model and pseudo-second-order kinetic model. The maximum adsorption capacities were 2208.24 mg/g for MB, 1167.52 mg/g for MEB, and 806.31 mg/g for TCH. Electrostatic interactions, hydrogen bonding and van der Waals forces probably involved the adsorption process. As expected, this foam could exhibit better removal properties toward both charged and uncharged organic pollutants through the addition of H2O2 to trigger the Fenton degradation reaction. For non-adsorbable and uncharged bisphenol A (BPA), the removal efficiency was dramatically increased from 1.20 % to 92.77 % after Fenton degradation. Additionally, it presented outstanding recyclability. These results suggest that Fe-MMT@CS/G foam is a sustainable and efficient green material for the alleviation of water pollution.

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Micro/nanomotors that can promote mass transport have attracted more and more research concern in the photocatalysis field. Here we first report a newly-designed hierarchical α-Fe2O3/ZnFe2O4/Mn2O3 magnetic micromotor as a heterogeneous photocatalyst for the degradation of cationic dye methylene blue (MB) from wastewater. The resulting three-dimensional (3D) flower-like hollow Janus micromotors are fabricated through a green and scalable strategy, in which each component has different functions. ZnFe2O4 microspheres serve as a magnetic scaffold for the nucleation and growth of α-Fe2O3 nanosheets and for the recycling of the micromachine. α-Fe2O3 nanosheets have shown great potential as an ideal semiconductor material for the photocatalytic decontamination of pollutants. Mn2O3 nanoparticles are mainly utilized as a catalyst to produce O2 bubbles to propel the autonomic movement of the micromotors in the presence of H2O2 fuel and also as a Fenton-like catalyst to decompose H2O2 to generate reactive oxygen species. Furthermore, the resultant micromotors exhibited linear-like motion form with an average speed of 189.1 µm s-1 in 5 wt% H2O2 solution. Moreover, the self-driven micromotors exhibited a superior catalytic degradation property toward MB, which was attributed to the synergistic effect of heterogeneous photocatalyst and the boosted micro-mixing and mass transfer caused by the vigorous motion of the micro-actuator. The possible degradation intermediates and passways of MB by α-Fe2O3/ZnFe2O4/Mn2O3 micromotor were identified with time of flight mass spectroscopy (TOF-MS). The 3D Janus micromotors have the potential to be used as a high-efficiency and active heterogeneous photocatalyst for the degradation of organic pollutants.

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Plant polysaccharides exhibit many biological activities that are remarkably affected by molecular size and structures. This study aimed to investigate the degradation effect of ultrasonic-assisted Fenton reaction on the Panax notoginseng polysaccharide (PP). PP and its three degradation products (PP3, PP5, and PP7) were obtained from optimized hot water extraction and different Fenton reaction treatments, respectively. The results showed that the molecular weight (Mw) of the degraded fractions significantly decreased after treatment with the Fenton reaction. But the backbone characteristics and conformational structure were similar between PP and PP-degraded products, which was estimated by comparing monosaccharides composition, functional group signals in FT-IR spectra, X-ray differential patterns, and proton signals in 1H NMR. In addition, PP7, with an Mw of 5.89 kDa, exhibited stronger antioxidant activities in both the chemiluminescence-based and HHL5 cell-based methods. The results indicated that ultrasonic-assisted Fenton degradation might be used to improve the biological activities of natural polysaccharides by adjusting the molecular size.

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All remediation pathways in aqueous solutions come down to three dominant ones - physical, chemical, and combinations thereof. Materials proposed for adsorption and oxidative degradation can induce positive or negative effects on cells compared to the pollutants themselves. Present research deals with the effects different methods for pesticide remediation have and how they impact cytotoxicity. With this particular intention, Fe-modified zeolites (obtained via citrate/oxalate complexes) of three zeotypes (MFI, BEA and FAU) were prepared and tested as adsorbents and Fenton catalysts for the removal of the acetamiprid pesticide. The materials are characterized by AFM, FTIR spectroscopy and ICP-OES. A different effect of the zeolite framework and modification route was found among the samples, which leads to pronounced adsorption (FAU), efficient Fenton degradation (MFI) or synergistic effect of both mechanisms (BEA). The cytotoxic effects of acetamiprid in the presence of zeolites, in pristine and modified forms, were tested on the MRC-5 human fibroblast cell line. A complete survey of the toxicity effect behind different pesticide removal methods is presented. Since neither adsorption nor catalytic degradation is the best option for pesticide removal, the focus is shifted to a combination of these methods, which proved to be optimal for pesticide toxicity reduction.

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Nature presents the collective behavior of living organisms aiming to accomplish complex tasks, inspiring the development of cooperative micro/nanorobots. Herein, the spontaneous assembly of hematite-based microrobots with different shapes is presented. Autonomous motile light-driven hematite/Pt microrobots with cubic and walnut-like shapes are prepared by hydrothermal synthesis, followed by the deposition of a Pt layer to design Janus structures. Both microrobots show a fuel-free motion ability under light irradiation. Because of the asymmetric orientation of the magnetic dipole moment in the crystal, cubic hematite/Pt microrobots can self-assemble into ordered microchains, contrary to the random aggregation observed for walnut-like microrobots. The microchains exhibit different synchronized motions under light irradiation depending on the mutual orientation of the individual microrobots during the assembly, which allows them to accomplish multiple tasks, including capturing, picking up, and transporting microscale objects, such as yeast cells and suspended matter in water extracted from personal care products, as well as degrading polymeric materials. Such light-powered self-assembled microchains demonstrate an innovative cooperative behavior for small-scale multitasking artificial robotic systems, holding great potential toward cargo capture, transport, and delivery, and wastewater remediation.

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Taking inspirations from nature, we endeavor to develop catalytically self-propelled nanojets from a type of tubular clay minerals, halloysite nanotubes (HNTs), and utilize them as catalysts targeted for catalysis where the traditional means of mechanical agitation cannot be implemented. Nanojets of Fe3O4@HNTs/Pt were prepared by impregnating platinum nanoparticles (Pt NPs) in lumens of HNTs and selective grafting of magnetite (Fe3O4) particles on the external surface. The HNT-based nanojets were validated to be highly suitable both in free bulk solution and in microfluidic flow. An example of Fenton degradation catalyzed by these jets was demonstrated. The powerful movement of Fe3O4@HNTs/Pt (368 ± 50 µm·s-1) fueled by 5.0% wt. H2O2 was found to follow a bubble propulsion mechanism, and the motion exhibits collective behavior as swarms. The clay tubes were for the first time observed to self-assemble into fish-like aggregates during swimming, reflecting natural occurrence of motion-evolution philosophy. Guided motion was realized by employing magnetic manipulation which makes jets feasible for reactors with complex microchannels/reactors.

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Water is a supreme requirement for the existence of life, the contamination from the point and non-point sources are creating a great threat to the water ecosystem. Advance tools and techniques are required to restore the water quality and metal-organic framework (MOFs) with a tunable porous structure, striking physical and chemical properties are an excellent candidate for it. Fe-based MOFs, which developed rapidly in recent years, are foreseen as most promising to overcome the disadvantages of traditional water depolluting practices. Fe-MOFs with low toxicity and preferable stability possess excellent performance potential for almost all water remedying techniques in contrast to other MOF structures, especially visible light photocatalysis, Fenton, and Fenton-like heterogeneous catalysis. Fe-MOFs become essential tool for water treatment due to their high catalytic activity, abundant active site and pollutant-specific adsorption. However, the structural degradation under external chemical, photolytic, mechanical, and thermal stimuli is impeding Fe-MOFs from further improvement in activity and their commercialization. Understanding the shortcomings of structural integrity is crucial for large-scale synthesis and commercial implementation of Fe-MOFs-based water treatment techniques. Herein we summarize the synthesis, structure and recent advancements in water remediation methods using Fe-MOFs in particular more attention is paid for adsorption, heterogeneous catalysis and photocatalysis with clear insight into the mechanisms involved. For ease of analysis, the pollutants have been classified into two major classes; inorganic pollutants and organic pollutants. In this review, we present for the first time a detailed insight into the challenges in employing Fe-MOFs for water remediation due to structural instability.

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Iron-clay-cyclodextrin composites were designed as sorbent catalysts to adsorb and oxidize pollutants from water. The clay-iron backbone served as a mechanical support and as a heterogeneous Fenton catalyst, and the cyclodextrin monomers or polymers cross-linked with polyfluorinated aromatic molecules were used to accommodate adsorption of the pollutants. The composite based on iron-clay-cyclodextrin-polymers (Fe-MMT-ßCD-DFB) exhibited superior adsorption and degradation of the model pollutants, bisphenol A (BPA), carbamazepine (CBZ), and perfluorooctanoic acid (PFOA), compared to the monomer-based composite and the native iron clay. The variety of adsorption sites, such as the polyfluorinated aromatic cross-linker, cyclodextrin toroid, and iron-clay surface, resulted in high adsorption affinity toward all pollutants; BPA was primarily adsorbed to the cyclodextrin functional groups, CBZ showed high affinity toward the Fe-MMT surface and the Fe-MMT-ßCD-DFB composite, whereas PFOA was adsorbed mainly to the ßCD-DFB polymer. Degradation, using H2O2, was highly efficient, reaching over 90% degradation in 1 h for BPA and CBZ and ∼80% for PFOA. The composite also showed excellent degradation efficiency in a multicomponent system with all three model pollutants. Furthermore, the composite's activity remained steady for five consecutive cycles of adsorption and degradation. The ability to remediate a broad range of pollutants, and the high overall removal exhibited by this novel material, demonstrates the potential for future application in water remediation technologies.

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The morphology-dependent property of crystal materials has aroused extensive attention and raised high requirements for subtly tailoring the morphology of micro-/nanocrystals. Herein, we develop an in situ etching method for preparation of Prussian blue (PB) microcrystals with morphology evolution by progressively increasing the concentration of chloroplatinic acid in the reaction system. These PB microcrystals with controllable morphologies are employed as photo-Fenton reagents to degrade organic pollutants. PB hexapods (PB-hpds) and PB hexapod stars present superior catalytic performance to pristine PB microcubes and other PB intermediates with truncated corners or edges because of their high specific surface areas and adequate exposure of FeIII-NC coordination active sites. In the reusability test, the reused PB-hpds present more efficient catalytic performance for rhodamine B decomposition compared with the pristine catalyst. According to more investigations, the reasonable mechanism is proposed that FeIII-NC exhibits higher catalytic activity than FeII-CN in the specific coordination environment. The increased content of surface FeIII-NC coordination active sites is the key factor in accelerating the decomposition of H2O2 and enhancing the photo-Fenton performance of PB-hpds. Several operating parameters including catalyst dosage, H2O2 concentration, pH value, and reaction temperature are evaluated in detail. Classical quenching experiments and electron paramagnetic resonance measurements further reveal that HO• should be responsible for high performance of catalysts. This work will be significant for tailoring the morphology of the materials and arousing more attention to enhance the stability and reusability of catalysts.

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Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe3O4 nanoparticles (AG/Fe3O4) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe3O4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe3O4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70-120min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50-80min using AG/Fe3O4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe3O4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe3O4 NPs. Furthermore, the remarkable reusability of the AG/Fe3O4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.