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.     

浸渍-碱性微波法载磁活性炭粉对壬基酚的吸附

利用浸渍-碱性微波法制备载磁粉末活性炭,通过等温吸附实验和动力学吸附实验,研究对比了其与原料活性炭、浸渍载铁活性炭对壬基酚的吸附性能。采用氮气吸附仪、FTIR、XRD、国标(GB/T12496.19-1999)邻菲啰啉分光度法及VSM,分别对3种样品进行了物相结构、表面官能团、铁含量及磁性能的分析,并探讨了吸附机理。结果表明,浸渍-碱性微波法载磁活性炭的总孔容及孔隙率均有较大提高;其吸附等温线符合Freundich方程,吸附动力学过程符合准二级动力学方程与孔道内扩散模型,相关系数R2均大于0.900。原活性炭经一定浓度的铁盐溶液浸渍后,铁含量由2%提高到8%。在碱性、N2气氛条件下微波后,铁系物主要存在形式为零价铁和Fe3O4,制得的载磁活性炭饱和磁化强度为1.12 emu/g。     

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。     

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.

     

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.     

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.     

海绵铁还原耦合活性炭吸附-微波再生技术降解甲基橙

采用海绵铁(s-Fe0)还原耦合活性炭(GAC)吸附-微波(MW)再生技术降解甲基橙(MO)溶液,重点考察了s-Fe0投加量、粒径、微波功率等因素对MO去除效果的影响。结果表明,s-Fe0投加剂量为15.0 g/L、粒径为3～5 mm、超声波功率为200 W,反应1 h,MO的去除率为94.2%。其次,采用GAC吸附-MW再生技术(800 W,照射1 min)循环处理上述脱色后的MO废水。结果表明,GAC吸附可有效降低废水的生物毒性及残留的染料、TOC和总铁离子浓度,且MW辐射可有效再生吸附饱和的GAC颗粒。因此,s-Fe0还原耦合GAC吸附-MW再生技术可以有效降解MO染料,具有处理效果好、实现资源循环利用等优点。     

CuFe2O4/activated carbon composite: a novel magnetic adsorbent for the removal of acid orange II and catalytic regeneration

CuFe2O4/activated carbon magnetic adsorbents, which combined the adsorption features of activated carbon with the magnetic and the excellent catalytic properties of powdered CuFe2O4, were developed using a simple chemical coprecipitation procedure. The prepared magnetic composites can be used to adsorb acid orange II (AO7) in water and subsequently, easily be separated from the medium by a magnetic technique. CuFe2O4/activated carbon magnetic adsorbents with mass ratio of 1:1, 1:1.5 and 1:2 were prepared. Magnetization measurements, BET surface area measurements, powder XRD and SEM were used to characterize the prepared adsorbents. The results indicate that the magnetic phase present is spinel copper ferrite and the presence of CuFe2O4 did not significantly affect the surface area and pore structure of the activated carbon. The adsorption kinetics and adsorption isotherm of acid orange II (AO7) onto the composites at pH 5.2 also showed that the presence of CuFe2O4 did not affect the adsorption capacity of the activated carbon. The thermal decomposition of AO7 adsorbed on the activated carbon and the composite was investigated by in situ FTIR, respectively. The results suggest that the composite has much higher catalytic activity than that of activated carbon, attributed to the presence of CuFe2O4. The variation of the adsorption capacity of the composites after several adsorption-regeneration cycles has also been studied.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.     

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.

     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

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.

     

The effect of γ-Fe2O3 nanoparticles on Escherichia coli genome

Extensive production and application of γ-Fe₂O₃ magnetic nanoparticles (MNPs) has increased their potential risk on environment and human health. This report illustrates a genetic impact of γ-Fe₂O₃ magnetic nanoparticles (MNPs) on Escherichia coli (E. coli). After 3000-generation incubation with MNPs addition, obvious genomic variations were revealed by using repetitive extragenic palindromic PCR (rep-PCR) DNA fingerprint technique. The physicochemical interactions between MNPs and bacteria could be responsible for such genomic responses. It was revealed that Fe³⁺ concentration increased in the medium. Transmission electronic microscopy (TEM) and flow cytometry (FCM) analysis consistently demonstrated the occurrences of adsorption and membranes-internalization of MNPs outside and inside cells. Both increased Fe³⁺ ion and the uptake of MNPs facilitated Fe binding with proteins and DNA strands, resulting in enhancing the mutation frequency of E. coli. Our results would be of great help to assessing the potential impact of MNPs on human and environment.     

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O₃) and in liquid phase using nitric acid (HNO₃). The activated carbon samples were characterized using N₂ adsorption–desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m²/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich–Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO₃), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.     

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.     

Hemoglobin (Hb) immobilized on amino-modified magnetic nanoparticles for the catalytic removal of bisphenol A

Catalytic removal of bisphenol A from aqueous solution with hemoglobin immobilized on amino-modified magnetic nanoparticles as an enzyme catalyst was reported. The amino-modified magnetite nanoparticles were firstly prepared by the coprecipitation of Fe²⁺ and Fe³⁺ with NH₃·H₂O and then modified by 3-aminopropyltriethoxysilane. The immobilization process was optimized by examining enzyme concentration, glutaraldehyde concentration, cross-link time, and immobilization time. The optimum conditions for the removal of bisphenol A with immobilized hemoglobin were also investigated. Under the optimality conditions, the removal efficiency of bisphenol A was about 80.3%. The immobilization had a beneficial effect on the stability of hemoglobin and conversions of bisphenol A. According to the proposed breakdown pathway and the intermediates, the enzyme-catalytic removal of bisphenol A by the immobilized hemoglobin is considered to be an effective method.     

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.     

改性活性炭对石煤提钒废水中低浓度NH3-N和V等的吸附

为研究石煤提钒离交尾水的深度处理技术,利用质量分数为1%、5%和10%的过氧化氢溶液对ZWY15型活性炭进行改性,得到3种改性活性炭即1%AC、5%AC和10%AC;探讨其对该废水中低浓度的NH3-N、V等的吸附效果。实验结果表明:AC或改性AC的加入可使废水的碱度升高,随着吸附时间及吸附剂投加量的增加,升高幅度增大,且不同改性AC对废水碱度提高的幅度不同;相较于未改性活性炭,过氧化氢改性活性炭对V的吸附效果明显提高,去除率最大可提高30%,对NH3-N的去除率提升约11%;当投加量为60 g/L时,10%AC可使废水中V的浓度降低至1.88 mg/L,此时废水中Cr、Cd和Zn的浓度分别降低至0.006、0.010和0.036 mg/L,均低于《钒工业污染物排放标准》(GB26452-2011)所规定的排放限值。     

沼液中臭味物质的去除方法及其对营养物质的影响

采用臭氧曝气法、粉末活性炭吸附法、颗粒活性炭过滤法、臭氧曝气-粉末活性炭吸附联用法、空气曝气-粉末活性炭吸附联用法对沼液中的氨气、硫化氢、吲哚、挥发酚类等主要致嗅物质的去除情况进行了研究,同时分析了不同方法对沼液中营养物质TN、DN、TP、DP等的影响。结果表明,采用粉末活性炭吸附法处理沼液,臭味物质的去除情况以及营养物质的保留效果最好,当粉末活性炭投加量为15 000 mg/L时,沼液中的硫化氢、吲哚、挥发酚已经完全去除,氨氮、氨气的去除率分别为11.42%、13.98%;DN、DP含量分别减少了10.46%、19.53%,但是TN、TP含量分别增加了6.26%、9.63%。