Controllable synthesis Fe3O4@POHABA core-shell nanostructure as high-performance recyclable bifunctional magnetic antimicrobial agent

We demonstrated a method to form magnetic antimicrobial POHABA (poly-N,N′-[(4,5-dihydroxy-1,2-phenylene)bis(methylene)]bisacrylamide)-based core-shell nanostructure by free-radical polymerization of OHABA on the Fe₃O₄ core surface. The magnetic antimicrobial agent Fe₃O₄@POHABA can be used in domestic water treatment against bacterial pathogens. The thickness of POHABA shell could be controlled from 10.4 ± 1.2 to 56.3 ± 11.7 nm by the dosage of OHABA. The results of antimicrobial-activity test indicated that POHABA-based core-shell nanostructure had broad-spectrum inhibitory against Gram-negative, Gram-positive bacteria and fungi. The minimum inhibitory concentration (MIC) values of Fe₃O₄@POHABA nanostructure against Escherichia coli and Bacillus subtilis were both 0.4 mg/mL. Fe₃O₄@POHABA nanostructures responded to a permanent magnet and were easily recycled. Fe₃O₄@POHABA nanoparticles retained 100% antimicrobial efficiency for both Gram-negative and Gram-positive bacteria throughout eight recycle procedures.

     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

Toxicity of TiO2, ZrO2, Fe,Fe2O3, and Mn2O3 nanoparticles to the yeast, Saccharomyces cerevisiae

The growing application of engineered nanomaterials is leading to an increased occurrence of nanoparticles (NPs) in the environment. Thus, there is a need to better understand their potential impact on the environment. This study evaluated the toxicity of nanosized TiO₂, ZrO₂, Fe⁰, Fe₂O₃, and Mn₂O₃ towards the yeast Saccharomyces cerevisiae based on O₂ consumption and cell membrane integrity. In addition, the state of dispersion of the nanoparticles in the bioassay medium was characterized.     

Degradation of 2,4-D in soils by Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles combined with stimulating indigenous microbes

Purpose  

Degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in soils by Fe₃O₄ nanoparticles combined with soil indigenous microbes was investigated, and the effects of Fe₃O₄ nanoparticles on soil microbial populations and enzyme activities were also studied.     

Synthesis and characterization of magnetic Fe3O4@CaSiO3 composites and evaluation of their adsorption characteristics for heavy metal ions

A two-component material (Fe₃O₄@CaSiO₃) with an Fe₃O₄ magnetite core and layered porous CaSiO₃ shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe₃O₄@CaSiO₃ composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu²⁺, Ni²⁺, and Cr³⁺ adsorption were studied. The Fe₃O₄@CaSiO₃ composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m²/g, pore size of 16 nm, and pore volume of 0.25 cm³/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu²⁺, Ni²⁺, and Cr³⁺ by Fe₃O₄@CaSiO₃ fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe₃O₄@CaSiO₃ toward Cu²⁺, Ni²⁺, and Cr³⁺ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe₃O₄@CaSiO₃ exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Metal ferrite incorporated polysulfone thin-film nanocomposite membranes for wastewater treatment

Effluents from food, fermentation, and sugar industries contain a large quantity of glucose which has to be removed to limit the chemical oxygen demand (COD) of the water discharged. This work proposes novel thin-film nanocomposite (TFN) membranes incorporated with MgFe₂O₄ and ZnFe₂O₄ nanoparticles to address this concern. The nanoparticles synthesized by the sol–gel method was extensively characterized and then incorporated into the active polyamide layer of the thin-film composite polysulfone membranes. The change in membrane morphology, wettability, chemical structure, and mechanical strength with the incorporation of nanoparticles was studied in detail. Membranes with 0.005 wt.% MgFe₂O₄ nanoparticle exhibited highest glucose rejection (96.52?±?2.35%) at 10 bar, 25 °C, and sufficiently high pure water flux (50.54?±?1.92 L/m²h). This membrane also displayed 69.1?±?5.12% salt rejection when challenged with 2000 ppm synthetic NaCl solution.

     

Modification of photocatalytic property of BaTiO3 perovskite structure by Fe2O3 nanoparticles for CO2 reduction in gas phase

In this work, perovskite structure of BaTiO₃ was coupled with Fe₂O₃ in different molar ratios achieving the best photocatalytic performance of CO₂ reduction in the presence of CH₄ as reducing agent; both of them are main greenhouse gases. The photocatalysts were synthesized by facile hydrothermal method. The samples were characterized by XRD, FTIR, FESEM, EDX, UV–Vis DRS, and photoluminescence (PL) analyses. The BaTiO₃ synthesized in this research showed a weak PL signal which is due to the intrinsic ferroelectric property as has been observed in previous reports. Compared to the pure BaTiO₃ and Fe₂O₃, the heterojunctions exhibited enhanced photocatalytic activity. The maximum CO₂ reduction under visible light irradiation was obtained to be 22% during 60 min process time. The enhanced photocatalytic activity could be attributed to the increased optical absorption, the good separation, and immigration of photogenerated charge carriers that decreased the recombination rate of charge carriers in the n–n heterojunction.

     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Synthesis of magnetic CoFe2O4/ordered mesoporous carbon nanocomposites and application in Fenton-like oxidation of rhodamine B

CoFe₂O₄/ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFe₂O₄ nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFe₂O₄/OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO₄ ⁻·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFe₂O₄ and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFe₂O₄/OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFe₂O₄/OMC nanocomposites compared to that of CoFe₂O₄ nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).

     

Efficient degradation of semi-coking wastewater in three-dimensional electro-Fenton by CuFe2O4 heterocatalyst

Semi-coking wastewater contains a rich source of toxic and refractory compounds. Three-dimensional electro-Fenton (3D/EF) process used CuFe₂O₄ as heterocatalyst and activated carbon (AC) as particle electrode was constructed for degrading semi-coking wastewater greenly and efficiently. CuFe₂O₄ nanoparticles were prepared by coprecipitation method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy disperse spectroscopy (EDS). Factors like dosage of CuFe₂O₄, applied voltage, dosage of AC and pH, which effect COD removal rate of semi-coking waste water were studied. The results showed that COD removal rate reached to 80.9% by 3D/EF process at the optimum condition: 4 V, 0.3 g of CuFe₂O₄, 1 g of AC and pH?=?3. Trapping experiment suggesting that hydroxyl radical (?OH) is the main active radical. The surface composition and chemical states of the fresh and used CuFe₂O₄ were analyzed by XPS indicating that Fe, Cu, and O species are involved into the 3D/EF process. Additionally, anode oxidation and the adsorption and catalysis of AC are also contributed to the bleaching of semi-coking waste water. The possible mechanisms of 3D/EF for degrading semi-coking waste water by CuFe₂O₄ heterocatalyst were proposed.

     

Activated carbon/Fe(3)O(4) nanoparticle composite: fabrication, methyl orange removal and regeneration by hydrogen peroxide

In the water treatment field, activated carbons (ACs) have wide applications in adsorptions. However, the applications are limited by difficulties encountered in separation and regeneration processes. Here, activated carbon/Fe₃O₄ nanoparticle composites, which combine the adsorption features of powdered activated carbon (PAC) with the magnetic and excellent catalytic properties of Fe₃O₄ nanoparticles, were fabricated by a modified impregnation method using HNO₃ as the carbon modifying agent. The obtained composites were characterized by X-ray diffraction, scanning and transmission electron microscopy, nitrogen adsorption isotherms and vibrating sample magnetometer. Their performance for methyl orange (MO) removal by adsorption was evaluated. The regeneration of the composite and PAC-HNO₃ (powdered activated carbon modified by HNO₃) adsorbed MO by hydrogen peroxide was investigated. The composites had a high specific surface area and porosity and a superparamagnetic property that shows they can be manipulated by an external magnetic field. Adsorption experiments showed that the MO sorption process on the composites followed pseudo-second order kinetic model and the adsorption isotherm date could be simulated with both the Freundlich and Langmuir models. The regeneration indicated that the presence of the Fe₃O₄ nanoparticles is important for a achieving high regeneration efficiency by hydrogen peroxide.     

Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions

Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2′,3,4,4′,5,5′,6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl₄Bz) is the predominant congener formed on the SiO₂/Fe₂O₃ surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl₄Bz molecules formed 2,2′,3,4,4′,5,5′,6-OCDE in the presence of Fe₂O_3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO₂/CuO surface without oxygen, although the 2,2′,3,4,4′,5,5′,6-OCDE was the dominant product on the SiO₂/CuO surface with oxygen. Therefore, the presence of Fe₂O₃ and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe₂O₃ can promote both the condensation and dechlorination reaction without oxygen_. On the contrary, with oxygen, Fe₂O₃ suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.     

不同纳米修复剂对污染土壤中胡萝卜吸收、转运Cd的影响

通过盆栽实验研究不同纳米修复剂(羟基磷灰石HAP、赤泥RM、Fe3O4、胡敏酸-Fe3O4)对2种不同污染土壤Cd吸收、转运的影响。结果表明,上述纳米修复剂均可显著增加胡萝卜植株生物量,显著提高植株Cd胁迫的耐受指数;不同土壤施用不同纳米修复剂均显著降低胡萝卜植株Cd的含量,并且随着修复剂施加浓度的增加而显著降低;与对照相比,植株茎叶Cd含量最大降低达78.8%,根中Cd的含量最大降低67.8%;添加不同修复剂能不同程度地降低了土壤中Cd的转运系数和富集系数,这可能与施用不同纳米修复剂促进了土壤中非残留态Cd向残留态Cd的转化有关,总体而言,不同纳米型修复剂对降低Cd的有效性顺序为:RM～HAP>胡敏酸-Fe3O4>Fe3O4。     

Synthesis, properties and application research of atrazine Fe3O4@SiO2 magnetic molecularly imprinted polymer

Introduction

Magnetic Fe₃O₄ nanoparticles were prepared by coprecipitation and then were coated with SiO₂ on the surface.

Materials and methods

Fe₃O₄@SiO₂ composite microspheres were modified by KH570. Using molecular imprinting technology, atrazine magnetic molecularly imprinted polymer was prepared by using atrazine as template molecule, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linkers. The morphology, composition and magnetic properties of magnetic nanoparticles were characterized. The recognition selectivity of polymer was studied for template molecule and simulation by UV spectrophotometry. The adsorption properties and selectivity ability were analyzed by Scatchard analysis.

Results

Scatchard linear regression analysis indicated that there are two binding sites of the target molecules. The magnetic molecularly imprinted polymer has been applied to the analysis of atrazine in real samples.

Conclusion

The results show that: the recovery rates and the relative standard deviation were 94.0??98.7% and 2.1??4.0% in corn, the recovery rates and the relative standard deviation were 88.7??93.5% and 2.8??7.2% in water.     

Adsorption and photocatalytic conversion of ethyl mercaptan to diethyl disulfide on Fe2O3-loaded HNbMoO6 nanosheet

Ethyl mercaptans which commonly exist in natural gas need to be removed due to their toxic, odorous, and corrosive properties. Herein, a novel Fe₂O₃-modified HNbMoO₆ nanosheet catalyst (Fe₂O₃@e-HNbMoO₆) was prepared by an exfoliation-impregnation method for the ethyl mercaptans removal. In the heterojunction catalyst, e-HNbMoO₆ can be excited by visible light to generate the photogenic charge and has certain adsorption property for ethyl mercaptan with hydrogen bonding (Nb-OH or Mo-OH as the hydrogen bonding donor); Fe₂O₃ plays the role of accelerating photogenerated electrons and holes, and enhancing the adsorption of ethyl mercaptan with another hydrogen bonding (Fe-OH as the hydrogen bonding donor and receptor). Results showed that the adsorption capacity of Fe₂O₃@e-HNbMoO₆ is 69.9 μmol/g for ethyl mercaptan. In addition, the photocatalytic conversion efficiency of ethyl mercaptan to diethyl disulfide is nearly 100% and it is higher than that of the other Nb-Mo based photocatalysts, such as LiNbMoO₆, Fe_1/3NbMoO₆, Ce_1/3NbMoO₆, TiO₂-HNbMoO₆, e-HNbMoO₆, CeO₂@e-HNbMoO₆, and Ag₂O@e-HNbMoO₆. Under the experimental conditions, the photocatalytic conversion efficiency is greater than the adsorption efficiency over Fe₂O₃@e-HNbMoO₆, and there is no ethyl mercaptan output in the process of adsorption and photocatalytic conversion. Fe₂O₃@e-HNbMoO₆ heterojunction catalyst has practical value and reference significance for purifying methane gas and enhancing photocatalytic conversion of ethyl mercaptan.

     

Magnetite/mesocellular carbon foam as a magnetically recoverable fenton catalyst for removal of phenol and arsenic

A magnetite-loaded mesocellular carbonaceous material, Fe₃O₄/MSU-F-C, exhibited superior activity as both a Fenton catalyst and an adsorbent for removal of phenol and arsenic, and strong magnetic property rendering it separable by simply applying magnetic field. In the presence of hydrogen peroxide, the catalytic process by Fe₃O₄/MSU-F-C completely oxidized phenol and As(III) under the conditions where commercial iron oxides showed negligible effects. Notably, the decomposition of H₂O₂ by Fe₃O₄/MSU-F-C was not faster than those by commercial iron oxides, indicating that hydroxyl radical produced via the catalytic process by Fe₃O₄/MSU-F-C was used more efficiently for the oxidation of target contaminants compared to the other iron oxides. The homogeneous Fenton reaction by the dissolved iron species eluted from Fe₃O₄/MSU-F-C was insignificant. At relatively high doses of Fe₃O₄/MSU-F-C, total concentration of arsenic decreased to a significant extent due to the adsorption of arsenic on the catalyst surface. The removal of arsenic by adsorption was found to proceed via preoxidation of As(III) into As(V) and the subsequent adsorption of As(V) onto the catalyst.     

Recycling of iron and silicon from drinking water treatment sludge for synthesis of magnetic iron oxide@SiO<Subscript>2</Subscript> composites

More attention has been paid to the deterioration of water bodies polluted by drinking water treatment sludge (DWTS) in recent years. It is important to develop methods to effectively treat DWTS by avoiding secondary pollution. We report herein a novel investigation for recovery of Si and Fe from DWTS, which are used for the synthesis of two iron oxide@SiO₂ composites for adsorption of reactive red X-3B (RRX-3B) and NaNO₂. The results show that Fe³⁺ (acid-leaching) and Si⁴⁺ (basic-leaching) can be successfully recovered from roasted DWTS. Whether to dissolve Fe(OH)₃ precipitation is the key point for obtaining Fe₃O₄ or γ-Fe₂O₃ particles using the solvothermal method. The magnetic characteristics of Fe₃O₄@SiO₂ (390.0 m² g^?1) or Fe₂O₃@SiO₂ (220.9 m² g^?1) are slightly influenced by the coated porous SiO₂ layer. Peaks of Fe–O stretching vibration (580 cm^?1) and asymmetric Si–O–Si stretching vibrations (1080 cm^?1) of Fe₃O₄@SiO₂ indicate the successful coating of a thin silica layer (20–150 nm). The adsorption capacity of RRX-3B and NaNO₂ by Fe₃O₄@SiO₂ is better than that of Fe₂O₃@SiO₂, and both composites can be recycled through an external magnetic field. This method is an efficient and environmentally friendly method for recycling DWTS.     

Removal of algal blooms from freshwater by the coagulation–magnetic separation method

This research investigated the feasibility of changing waste into useful materials for water treatment and proposed a coagulation–magnetic separation technique. This technique was rapid and highly effective for clearing up harmful algal blooms in freshwater and mitigating lake eutrophication. A magnetic coagulant was synthesized by compounding acid-modified fly ash with magnetite (Fe₃O₄). Its removal effects on algal cells and dissolved organics in water were studied. After mixing, coagulation, and magnetic separation, the flocs obtained from the magnet surface were examined by SEM. Treated samples were withdrawn for the content determination of chlorophyll-a, turbidity, chemical oxygen demand (COD), total nitrogen, and total phosphorus. More than 99 % of algal cells were removed within 5 min after the addition of magnetic coagulant at optimal loadings (200 mg L^?1). The removal efficiencies of COD, total nitrogen, and phosphorus were 93, 91, and 94 %, respectively. The mechanism of algal removal explored preliminarily showed that the magnetic coagulant played multiple roles in mesoporous adsorption, netting and bridging, as well as high magnetic responsiveness to a magnetic field. The magnetic–coagulation separation method can rapidly and effectively remove algae from water bodies and greatly mitigate eutrophication of freshwater using a new magnetic coagulant. The method has good performance, is low cost, can turn waste into something valuable, and provides reference and directions for future pilot and production scale-ups.