Synthesis of Magnetic Fe3O4 Modified Graphene Nanocomposite and its Application on the Adsorption of some Dyes from Aqueous Solution

A novel magnetic Fe₃O₄ modified reduced graphene oxide nanocomposite (Fe₃O₄@SiO₂-rGO) was prepared by a covalent bonding method. The morphology and properties of the Fe₃O₄@SiO₂-rGO were characterized by transmission electron microscopy and X-ray diffraction. The prepared Fe₃O₄@SiO₂-rGO was tested as an efficient adsorbent for the removal of some dyes from aqueous solution for the first time. The performance of Fe₃O₄@SiO₂-rGO was evaluated using methylene blue and neutral red as model compounds. Experiments were carried out to investigate the adsorption kinetics and adsorption capacity of the adsorbent and the effect of the adsorbent dosage and sample solution pH on the removal of the dyes. Kinetic data were well fitted by pseudo second-order model. The Langmuir model and the Freundlich model were used to study the adsorption isotherms. The Fe₃O₄@SiO₂-rGO nanocomposite showed to be a highly efficient adsorbent with the advantage of separation convenience. The thermodynamic parameters indicated that the adsorption of the dyes onto the Fe₃O₄@SiO₂-rGO was a spontaneous process.     

Functionalized magnetic core-shell Fe3O4@SiO2 nanoparticles as selectivity-enhanced chemosensor for Hg(II)

A colorimetric and ‘‘turn-on” fluorescent chemosensor Rho-Fe₃O₄@SiO₂ for Hg²⁺ in which N-(rhodamine-6G)lactam-ethylenediamine (Rho-en) is conjugated with the magnetic core-shell Fe₃O₄@SiO₂ NPs has been strategically designed and synthesized. The final product was characterized by X-ray power diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR) and UV-visible absorption and fluorescence emission. Fluorescence and UV-visible spectra results showed that the resultant multifunctional nanoparticles Rho-Fe₃O₄@SiO₂ exhibited selective ‘turn-on’ type fluorescent enhancements and distinct color changes with Hg²⁺. The selectivity of the Rho-Fe₃O₄@SiO₂ for Hg(II) ion is better than that of the Rho-en in the same conditions. In addition, the presence of magnetic Fe₃O₄ nanoparticles in the sensor Rho-Fe₃O₄@SiO₂ NPs would also facilitate the magnetic separation of the Hg(II)-Rho-Fe₃O₄@SiO₂ from the solution.     

Synthesis of sulfides via reaction of aryl/alkyl halides with S8 as a sulfur-transfer reagent catalyzed by Fe3O4-magnetic-nanoparticles-supported L-Histidine-Ni(II)

One-pot synthesis of symmetrical diaryl/alkyl sulfides in high yields from the reaction between aryl/alkyl halides and S₈ can be carried out in a short period, using Fe₃O₄@SiO₂@His@Ni(II) as a reusable catalyst. The present approach offers the advantages of a clean reaction, simple methodology and high efficiency, and avoids the use of a toxic catalyst.     

Nano-CuFe2O4@SO3H Catalyzed Efficient One-Pot Cyclo-Dehydration of Dimedone and Synthesis of Chromeno[4,3-b]chromenes

Chlorosulfonic acid immobilized on CuFe₂O₄ nanoparticles (nano-CuFe₂O₄@SO₃H) was evaluated as a recoverable catalyst for the one-pot cyclo-dehydration of dimedone and synthesis of chromeno[4,3-b]chromene derivatives by reaction of arylaldehydes, dimedone or 1,3-cyclohexanedione, with 3-hydroxycoumarine or 4-hydroxycoumarine in good to excellent yield. Also, 2,2′-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) was synthesized by the reaction of aromatic aldehyde and dimedone using nano-CuFe₂O₄ in ethanol at room temperature. The catalyst could be recycled several times without significant loss of its catalytic activity. Clean methodologies, easy work-up procedure, high yield and simple preparation of the catalyst are some advantages of this procedure.     

Amino Functionalized Nano Fe3O4@SiO2 as a Magnetically Green Catalyst for the One-Pot Synthesis of Spirooxindoles Under Mild Conditions

(3-Aminopropyl)-triethoxysilane attached to Fe₃O₄@SiO₂ nanoparticles has been characterized by powder X-ray diffraction, vibrating sample magnetometer, scanning electronic microscope, transmission electron microscope, energy dispersive X-ray, thermal gravimetric analysis, and Fourier transform infrared spectroscopy. The prepared nanoparticles employed as a heterogeneous catalyst in the synthesis of spirooxindoles derivatives in one-pot four-component reactions of isatin, methyl cyanoacetate or malononitrile, hydrazine hydrate, and ethyl acetoacetate. Amino-functionalized magnetic nanoparticles showed high catalytic activity in mild reaction conditions and excellent yields of products in short reaction times. Also, this nanocatalyst can be easily recovered by a magnet and reused for subsequent reactions for at least 5 times without noticeable loss in catalytic activity.     

CoFe2O4@SiO2/PrNH2 nanoparticles as highly efficient and magnetically recoverable catalyst for the synthesis of 1,3-thiazolidin-4-ones

An efficient three-component synthesis of 1,3-thiazolidin-4-ones is described by one-pot condensation of aldehydes, aromatic amine and thioglycolic acid with nano-CoFe₂O₄@SiO₂/PrNH₂ as a robust heterogeneous catalyst. The significant advantages of this protocol are the use of magnetically recoverable catalyst, high to excellent product yields, operational simplicity and the use of CoFe₂O₄@SiO₂/PrNH₂ nanoparticles as an environment-friendly catalyst.     

Facile Synthesis of FeCo/Fe3O4 Nanocomposite with High Wave-Absorbing Properties

The FeCo/Fe₃O₄ nanocomposite was synthesized using the hydrothermal approach, in which the FeCo alloy and Fe₃O₄ are formed by one step. The structure of the FeCo/Fe₃O₄ nanocomposite was characterized by means of Scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray energy-dispersive spectrometer spectroscopy (EDX). They show that the mass ratio of FeCo/Fe₃O₄ strongly depends on the reaction temperature. Such various architectures follow a stepwise growth mechanism of the composites prepared in various reaction temperatures were also discussed. It indicates that this strategy is facile, effective and controllable for the synthesis of FeCo/Fe₃O₄ by the one-step method. Furthermore, the magnetic and wave-absorbing properties of the nanocomposites with various structures were investigated in detail. The results show that the FeCo/Fe₃O₄ with higher mass ratio has higher magnetic properties. Moreover, the FeCo/Fe₃O₄ nanocomposite shows high wave-absorbing properties (e.g., −37.9 dB), which are expected to apply in microwave absorbing materials.     

Synthesis and application of nanocomposite Fe3O4@SiO2@CTAB–SiO2 as a novel adsorbent for removal of cyclophosphamide from water samples

ABSTRACT

We present a way of synthesizing nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ by employing simple sol–gel technique with selective etching for extreme selectivity adsorption of cyclophosphamide (CP). The transmission electron microscopy (TEM); scanning electron microscopy (SEM); X-ray diffraction (XRD); Fourier transform infrared (FT-IR); vibrating sample magnetometer (VSM); pH_PZC; and Brunauer, Emmett and Teller (BET) techniques were used for nanocomposite characterization. These nanoparticles have an S_BET of 157.8 m² g^?1 and a high saturation magnetization of 67.5 emu g^?1. First, the adsorption system was examined as a function of contact time under various initial CP contents, ionic strength, initial solution pH, adsorbent dose and temperature in batch test. The optimum dose, pH and contact time were obtained to be 0.01 g, 7.0 and 30 min, respectively. Ultimately, experimental isotherm and kinetics data of adsorption of CP onto nanocomposite Fe₃O₄@SiO₂@CTAB–SiO₂ were fitted to classical models. Additionally, it was found that the maximum adsorption process capacity of CP on adsorbent was 342.8 mg g^?1.     

Synthesis of magnetic Pb/Fe3O4/SiO2 and its catalytic activity for propylene carbonate synthesis via urea and 1,2-propylene glycol

To facilitate the recovery of Pb/SiO₂ catalyst, magnetic Pb/Fe₃O₄/SiO₂ samples were prepared separately by emulsification, sol-gel and incipient impregnation methods. The catalyst samples were characterized by means of X-ray diffraction and N₂ adsorption-desorption, and their catalytic activity was investigated in the reaction for synthesizing propylene carbonate from urea and 1,2-propylene glycol. When the gelatin was applied in the preparation of Fe₃O₄ at 60°C and the pH value was controlled at 4 in the preparation of Fe₃O₄/SiO₂, the Pb/Fe₃O₄/SiO₂ sample shows good catalytic activity and magnetism. Under the reaction conditions of a reaction temperature of 180°C, reaction time of 2 h, catalyst percentage of 1.7 wt-% and a molar ratio of urea to PG of 1:4, the yield of propylene carbonate attained was 87.7%.     

聚乙二醇/聚乙烯吡咯烷酮修饰的纳米Fe3O4粒子的制备与表征

为了获得能够在水中稳定分散,具有广泛应用前景的磁性纳米粒子,以不同分子量的聚乙烯吡咯烷酮(PVP)作为修饰剂,在聚乙二醇(PEG)中高温热分解乙酰丙酮铁(Fe(acac)₃)制备了纳米Fe₃O₄粒子。采用X射线粉末衍射仪(XRD)、透射电镜(TEM)、高分辨透射电镜(HRTEM)、超导量子干涉仪(SQUID)、热重分析仪(TGA)、傅里叶变换红外光谱仪(FT-IR)、纳米粒度与zeta电位分析仪对样品进行了表征,并对样品在生理盐水和生理缓冲液中的稳定性进行了研究,结果表明:制备的纳米Fe₃O₄粒子具有高的结晶度以及单分散性,在300 K下,具有超顺磁性和较高的饱和磁化强度;PEG和PVP共同修饰于纳米Fe₃O₄粒子表面,为纳米Fe₃O₄粒子提供了良好的水分散性;制备的纳米Fe₃O₄粒子在生理盐水和多种生理缓冲液中能够高度溶解并稳定地分散。水中的纳米Fe₃O₄粒子表面呈电中性,表面修饰层的空间位阻效应是所制备的纳米粒子在水溶液中高分散的原因。     

Influence of Fe3O4 nanoparticles decoration on dye adsorption and magnetic separation properties of Fe3O4/rGO nanocomposites

Magnetite (Fe₃O₄) nanoparticles were prepared by solvothermal method and its composites with reduced graphene oxide namely FG1, FG2, and FG3 (changing magnetite precursor loading 0.1, 0.5, and 1 respectively) were used as adsorbents for the removal of methyl violet (MV) dye. The structural and morphological results confirm that rGO sheets were decorated with Fe₃O₄ and it ensures the variation of active sites toward dye removal property. The maximum adsorption capacity obtained for FG2 was 196 mg/g. The adsorption isotherms and kinetics better fit Langmuir and pseudo-second-order kinetic model for FG1 and FG2. Increasing of Fe₃O₄ loading on rGO reduces the dye adsorption sites and too low Fe₃O₄ loading affects the magnetic separation. The optimal loading of Fe₃O₄ on rGO is important parameter for the adsorption process and fast separation of adsorbent.     

A novel method for the synthesis of Fe3O4 nanoparticles/CdS nanowires heterostructure nanocomposite and uses in photodegradation of methylene blue

We report here a simple, efficient, practical, and novel method for the preparation of Fe₃O₄ nanoparticles (NPs)/CdS nanowires. The CdS nanowire/Fe₃O₄ NP reported here was characterized by transmission electron microscopy (TEM), X-ray Diffraction (XRD), vibrating sample magnetometer (VSM), and energy-dispersive X-ray. Cadmium diethyl dithiophosphate has been used as a 3 in 1 precursor (cadmium, sulfur, and ligand source) for the synthesis of high-quality one-dimensional Fe₃O₄ NPs/CdS nanowires using a simple hydrothermal method in the presence of Fe₃O₄ NPs in water. Photocatalytic activity studies show that the nanocomposite has good photocatalytic activity toward the photodegradation of methylene blue in an aqueous solution.     

A novel platform of hemoglobin on core–shell structurally Fe3O4@Au nanoparticles and its direct electrochemistry

A novel platform, which hemoglobin (Hb) was immobilized on core–shell structurally Fe₃O₄/Au nanoparticles (simplified as Fe₃O₄@Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe₃O₄@Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope (SEM) and energy dispersive spectra (EDS), were coated onto GCE mediated by chitosan so as to provide larger surface area for anchoring Hb. The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe₃O₄@Au NPs were discussed by UV–visible spectrum (UV–vis), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance technique (EQCM) and cyclic voltammetry (CV). The electrochemical parameters of Hb on Fe₃O₄@Au NPs modified GCE were further carefully calculated with the results of the effective working area as 3.61 cm², the surface coverage concentration (Γ) as 1.07 × 10⁻¹² mol cm⁻², the electron-transfer rate constant (K_s) as 1.03 s⁻¹, the number of electron transferred (n) as 1.20 and the standard entropy of the immobilized Hb (ΔS⁰′) as calculated to be −104.1 J mol⁻¹ K⁻¹. The electrocatalytic behaviors of the immobilized Hb on Fe₃O₄@Au NPs were applied for the determination of hydrogen peroxide (H₂O₂), oxygen (O₂) and trichloroacetic acid (TCA). The possible functions of Fe₃O₄ core and Au shell as a novel platform for achieving Hb direct electrochemistry were discussed, respectively.     

磁性Fe3O4纳米粒子用作靶向药物载体的制备及分析

Fe3O4 magnetic nanoparticles were prepared by the aqueous co-precipitation of FeCl3-6H2O and FeCl2-4H2O with addition of ammonium hydroxide. The conditions for the preparation of Fe3O4 magnetic nanoparticles were optimized, and Fe3O4 magnetic nanoparticles obtained were characterized systematically by means of transmission electron microscope （TEM）, dynamic laser scattering analyzer （DLS） and X-ray diffraction （XRD）. The results revealed that the magnetic nanoparticles were cubic shaped and dispersive, with narrow size distribution and average diameter of 11.4 nm. It was found that the homogeneous variation of pH value in the solution via the control on the dropping rate of aqueous ammonia played a critical role in size distribution. The magnetic response of the product in the magnetic field was also analyzed and evaluated carefully. A 32.6 mT magnetic field which is produced by four ferromagnets was found to be sufficient to excite the dipole moments of 0.05 g Fe3O4 powder 2 cm far away from the ferromagnets. In conclusion, the Fe3O4 magnetic nanoparticles with excellent properties were competent for the magnetic carders of targeted-drug in future application.     

Enhanced cycling performance of Fe3O4-graphene nanocomposite as an anode material for lithium-ion batteries

Fe₃O₄-graphene nanocomposite was prepared by a gas/liquid interface reaction. The structure and morphology of the Fe₃O₄-graphene nanocomposite were characterized by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The electrochemical performances were evaluated in coin-type cells. Electrochemical tests show that the Fe₃O₄-22.7 wt.% graphene nanocomposite exhibits much higher capacity retention with a large reversible specific capacity of 1048 mAh g⁻¹ (99% of the initial reversible specific capacity) at the 90th cycle in comparison with that of the bare Fe₃O₄ nanoparticles (only 226 mAh g⁻¹ at the 34th cycle). The enhanced cycling performance can be attributed to the facts that the graphene sheets distributed between the Fe₃O₄ nanoparticles can prevent the aggregation of the Fe₃O₄ nanoparticles, and the Fe₃O₄-graphene nanocomposite can provide buffering spaces against the volume changes of Fe₃O₄ nanoparticles during electrochemical cycling.     

Suzuki–Miyaura cross-coupling reactions catalyzed by efficient and recyclable Fe3O4@SiO2@mSiO2–Pd(II) catalyst

In this study, a novel Pd(II) complex functionalized core–shell magnetic mesoporous catalyst (Fe₃O₄@SiO₂@mSiO₂–Pd(II)) was synthesized by a simple cost effective procedure. It was characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometer, and nitrogen physical adsorption. The Fe₃O₄@SiO₂@mSiO₂–Pd(II) catalyst offered high surface area and exhibited excellent activity towards Suzuki–Miyaura cross-coupling reaction of halides with aryl boronic acids in ethanol in air. The Fe₃O₄@SiO₂@mSiO₂–Pd(II) catalyst was stable, reusable, and conveniently recovered by applying an external magnetic field. Moreover, it provided 91% conversion after the sixth catalytic run. The Fe₃O₄@SiO₂@mSiO₂–Pd(II) catalyst examined in this study combined both the efficiency of a homogeneous catalyst and the durability of a heterogeneous catalyst. The results revealed that the Fe₃O₄@SiO₂@mSiO₂–Pd(II) catalyst is promising as a candidate for various Pd-based catalytic applications.     

Studies on Properties of Rice Straw/Polymer Nanocomposites Based on Polycaprolactone and Fe3O4 Nanoparticles and Evaluation of Antibacterial Activity

Modified rice straw/Fe₃O₄/polycaprolactone nanocomposites (ORS/Fe₃O₄/PCL-NCs) have been prepared for the first time using a solution casting method. The RS/Fe₃O₄-NCs were modified with octadecylamine (ODA) as an organic modifier. The prepared NCs were characterized by using X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The XRD results showed that as the intensity of the peaks decreased with the increase of ORS/Fe₃O₄-NCs content in comparison with PCL peaks, the Fe₃O₄-NPs peaks increased from 1.0 to 60.0 wt. %. The TEM and SEM results showed a good dispersion of ORS/Fe₃O₄-NCs in the PCL matrix and the spherical shape of the NPs. The TGA analysis indicated thermal stability of ORS/Fe₃O₄-NCs increased after incorporation with PCL but the thermal stability of ORS/Fe₃O₄/PCL-NCs decreased with the increase of ORS/Fe₃O₄-NCs content. Tensile strength was improved with the addition of 5.0 wt. % of ORS/Fe₃O₄-NCs. The antibacterial activities of the ORS/Fe₃O₄/PCL-NC films were examined against Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus) by diffusion method using nutrient agar. The results indicated that ORS/Fe₃O₄/PCL-NC films possessed a strong antibacterial activity with the increase in the percentage of ORS/Fe₃O₄-NCs in the PCL.     

Microwave-hydrothermal synthesis of Fe-based materials for lithium-ion batteries and supercapacitors

Fe-based materials, Fe₂O₃, Fe₃O₄, and FeOOH, were synthesized by the microwave–hydrothermal process in the temperature range of 100–200 °C and under very short reaction times of 15 min to 2 h. Under microwave-controlled hydrolysis and redox reactions, cube-like Fe₂O₃ was crystallized using FeCl₃, Fe₃O₄ particles were crystallized from FeCl₂ and FeOOH nanorods were crystallized using FeCl₃. The Fe-based materials were fabricated to make anodes and cathodes of lithium-ion battery and supercapacitor electrode materials to study their potential electrochemical applications. The electrochemical results showed that FeOOH had better anode capacity as lithium-ion batteries than those of Fe₂O₃ and Fe₃O₄. The present results suggest that the microwave–hydrothermally synthesized Fe-based materials are promising lithium-ion battery anode materials.     

Efficiency and Mechanism of Ciprofloxacin Hydrochloride Degradation in Wastewater by Fe3o4/Na2S2O8

ABSTRACT

The nanosized Fe₃O₄ catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe₃O₄ in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L^?1, a sodium persulfate concentration of 1.0 g·L^?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min^?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe₃O₄/sodium persulfate catalytic system were mainly composed of SO₄^– and supplemented by OH· and HO₂· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.     

Degradation Effect and Mechanism of Dinitrotoluene Wastewater by Magnetic Nano-Fe3O4/H2O2 Fenton-like

The characteristics and influencing factors for dinitrotoluene degradation by nano-Fe₃O₄-H₂O₂ were studied, and the nano-scale Fe₃O₄ catalyst was prepared by the coprecipitation method, with dinitrotoluene wastewater as the degradation object. The results showed that the catalytic reaction system within the pH value range of 1 to 9 could effectively degrade dinitrotoluene, and the optimal pH value was 3; with the increase of catalyst dosage, the degradation efficiency and the catalytic reaction rate of dinitrotoluene grew as well. The optimal catalyst dosage was 1.0 g/L when the H₂O₂ dosage was within the range of 0 to 0.8 mL/L; the degradation efficiency and reaction rate grew with the increase of H₂O₂ dosage. With further increase of H₂O₂ dosage, degradation efficiency and reaction rate decreased; under the best conditions with the H₂O₂ dosage of 0.8 mL/L, the catalyst concentration of 1 g/L and the pH value of 3 at room temperature (25 °C), the degradation rate of the 100-mg/L dinitrotoluene in 120 min reached 97.6%. Through the use of the probe compounds n-butyl alcohol and benzoquinone, it was proved that the oxidation activity species in the nano-Fe₃O₄-H₂O₂ catalytic system were mainly hydroxyl radical (?OH) and superoxide radicals (HO2 ?), based on which, the reaction mechanism was hypothesized.