Well-Dispersed Fe3O4/SiO2 Nanoparticles Synthesized by a Mechanical Stirring and Ultrasonication Assisted St?ber Method

Core–shell structured Fe₃O₄/SiO₂ nanoparticles (NPs) sized 40–50 nm with a narrow size distribution have been synthesized by a mechanical stirring and ultrasonication assisted St?ber method at the room temperature. It is shown that the combination of the ultrasonication and mechanical stirring during the preparation process benefits the formation of the well-dispersed NPs. The Fe₃O₄/SiO₂ core–shell microstructure is identified with X-ray diffraction and transmission electron microscopy measurements and such NPs exhibit superparamagnetism.     

Hybrid Au nanoparticles on Fe3O4@polymer as efficient catalyst for reduction of 4-nitrophenol

In this paper, we attempted to synthesize a hybrid nanostructure by the incorporation of Au nanoparticles (NPs) with polymer-coated Fe₃O₄ microspheres. Also, Au NPs on 3-aminopropyl triethylsilane (APTS)-modified Fe₃O₄@SiO₂ and Fe₃O₄@polymer microspheres were synthesized to assess the catalytic activity of Au NPs on Fe₃O₄@polymer microspheres for the reduction of 4-nitrophenol. It was found that Au NPs on Fe₃O₄@polymer catalysts showed higher catalytic activity and recyclability than other APTS-modified catalysts.     

The synthesis and characterization of monodispersed chitosan-coated Fe3O4 nanoparticles via a facile one-step solvothermal process for adsorption of bovine serum albumin

Preparation of magnetic nanoparticles coated with chitosan (CS-coated Fe₃O₄ NPs) in one step by the solvothermal method in the presence of different amounts of added chitosan is reported here. The magnetic property of the obtained magnetic composite nanoparticles was confirmed by X-ray diffraction (XRD) and magnetic measurements (VSM). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) allowed the identification of spherical nanoparticles with about 150 nm in average diameter. Characterization of the products by Fourier transform infrared spectroscopy (FTIR) demonstrated that CS-coated Fe₃O₄ NPs were obtained. Chitosan content in the obtained nanocomposites was estimated by thermogravimetric analysis (TGA). The adsorption properties of the CS-coated Fe₃O₄ NPs for bovine serum albumin (BSA) were investigated under different concentrations of BSA. Compared with naked Fe₃O₄ nanoparticles, the CS-coated Fe₃O₄ NPs showed a higher BSA adsorption capacity (96.5 mg/g) and a fast adsorption rate (45 min) in aqueous solutions. This work demonstrates that the prepared magnetic nanoparticles have promising applications in enzyme and protein immobilization.     

Synthesis of pH-sensitive hollow polymer microspheres with movable magnetic core

The pH-sensitive hollow poly(N,N′-methylenebisacrylamide-co-methacrylic acid) (P(MBAAm-co-MAA)) microspheres with movable magnetic/silica (Fe₃O₄/SiO₂) cores were prepared by the selective removal of poly(methacrylic acid) (PMAA) layer in ethanol/water from the corresponding Fe₃O₄/SiO₂/PMAA/P(MBAAm-co-MAA) tetra-layer microspheres, which were synthesized by the distillation precipitation copolymerization of N,N′-methylenebisacrylamide (MBAAm) and methacrylic acid (MAA) in the presence of Fe₃O₄/SiO₂/PMAA tri-layer microspheres as seeds in acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The Fe₃O₄/SiO₂/PMAA tri-layer microspheres were afforded by the distillation precipitation polymerization of MAA with 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified Fe₃O₄/SiO₂ core-shell particles as the seeds. The functional multi-layer inorganic/polymer microspheres and the corresponding hollow polymer microspheres with movable magnetic cores were characterized with transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectra, dynamic light scattering (DLS), and vibrating sample magnetometer (VSM).     

Enhanced photocatalytic degradation of tri-chlorophenol by Fe3O4@TiO2@Au photocatalyst under visible-light

Heterogeneous Fe₃O₄@TiO₂@Au core-shell microspheres, a facile and highly efficient catalyst have been fabricated by a simple surface modification. The fabrication process involved the coating of TiO₂ nanoshell onto the magnetic core using by sol-gel process, and then the anchoring of Au nanoparticles onto the surface of the Fe₃O₄@TiO₂ microspheres through the wet chemical reaction of 3-aminopropyltriethoxysilane (APTES). The as-synthesized Fe₃O₄@TiO₂ microspheres exhibited a narrow size distribution, with a typical size of 350 nm and shell thickness of 25 nm. The Fe₃O₄@TiO₂@Au microspheres can be easily collected by applying external magnetic field due to the magnetic property of core Fe₃O₄ particles. Compared to unmodified Fe₃O₄@TiO₂ microspheres, the Fe₃O₄@TiO₂@Au microspheres showed higher photocatalytic activity for 2, 4, 6-trichlorophenol (TCP). The photocatalytic efficiency of the Fe₃O₄@TiO₂ microspheres was 28% after 40 min irradiation while, the efficiency of Fe₃O₄@TiO₂@Au microspheres was 98% at the same condition.     

Synthesis and properties of magnetite nanoparticles with peroxide-containing polymer shell and nanocomposites based on them

Magnetite nanoparticles (Fe₃O₄ NPs) with peroxide-containing polymer shell have been synthesized using the method of coprecipitation from the mixture solutions of Fe (II) and Fe (III) salts in the presence of peroxide-containing copolymer (PCC). Polymer shell presence has been proved by elemental and complex thermal analysis. Synthesized Fe₃O₄ NPs possess superparamagnetic properties. Their specific saturation magnetization decreases gradually from 65 to 54 A·m²·kg⁻¹ with increasing PCC concentration owing to the surface spin pinning effect caused by a polymer shell. The average sizes of Fe₃O₄ NPs estimated from the data of XRD analysis and magnetic measurements are in the range of 9–12 nm. The NP sizes determined by the DLS method lie in the range of 150–270 nm; this result is significantly larger than the sizes estimated by the two aforementioned methods evidencing a tendency for Fe₃O₄ NPs toward self-association. Cross-linked composite films based on polyvinyl alcohol have been obtained via radical curing initiated by the PCC shell of nanoparticles. The resulting composite films are magnetically sensitive films with rather high physico-mechanical properties (tensile strength reaches 48–67 MPa and relative elongation – 4%–21% depending on cross-linking degree), a priori non-toxic and biocompatible, which makes them promising materials for various applications.     

Sonochemical synthesis of magnetic core–shell Fe3O4@ZrO2 nanoparticles and their application to the highly effective immobilization of myoglobin for direct electrochemistry

In this study, bifunctional Fe₃O₄@ZrO₂ magnetic core–shell nanoparticles (NPs), synthesized by a simple and effective sonochemical approach, were attached to the surface of a magnetic glassy carbon electrode (MGCE) and successfully applied to the immobilization/adsorption of myoglobin (Mb) for constructing a novel biosensor platform. With the advantages of the magnetism and the excellent biocompatibility of the Fe₃O₄@ZrO₂ NPs, Mb could be easily immobilized on the surface of the electrode in the present of external magnetic field and well retained its bioactivity, hence dramatically facilitated direct electron transfer of Mb was demonstrated. The proposed Mb/Fe₃O₄@ZrO₂ biofilm electrode exhibited excellent electrocatalytic behaviors towards the reduction of H₂O₂ with a linear range from 0.64 μM to 148 μM. This presented system avoids the complex synthesis for protecting Fe₃O₄ NPs, supplies a simple, effective and inexpensive way to immobilize protein, and is promising for construction of third-generation biosensors and other bio-magnetic induction devices.     

Preparation and characterization of conductive and magnetic PPy/Fe3O4/Ag nanocomposites

In this article, conductive and magnetic nanocomposites composed of polypyrrole (PPy), magnetite (Fe₃O₄) nanoparticles (NPs), silver (Ag) NPs, have been successfully synthesized with a two step process. First, the PPy/Fe₃O₄ was prepared by the ultrasonic in situ polymerization. Next, the PPy/Fe₃O₄/Ag was synthesized through the electrostatic adsorption. The products were characterized by fourier‐transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), Thermogravimetric (TG), conductivity and magnetization analysis, and the results showed that the Ag NPs with the good conductivity coated uniformly on the surface of PPy/Fe₃O₄ and improved the conductivity of PPy/Fe₃O₄/Ag composites. In addition, as compared with PPy/Fe₃O₄, PPy/Fe₃O₄/Ag composites also have the excellent electro‐magnetic property and enhanced thermostability. POLYM. COMPOS., 35:450–455, 2014. © 2013 Society of Plastics Engineers     

Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

Synthesis and characterization of poly(styrene-co-fluorescein O-methacrylate)/poly(N-isopropylacrylamide)-Fe3O4 core/shell composite particles

We demonstrate the synthesis and characteristics of multifunctional poly(styrene-co-fluorescein O-methacrylate)/poly(N-isopropylacrylamide)-Fe₃O₄ [P(St/FMA)/PNIPAAm-Fe₃O₄] core/shell composite particles, in which the core consists of fluorescent materials and the shell consists of magnetic and thermo-responsive components. First, core/shell particles consisting of a fluorescent P(St/FMA) core and thermo-responsive PNIPAAm-rich shell were prepared by two-stage shot-growth emulsion polymerization. Next, Fe₃O₄ nanoparticles were immobilized via electrostatic interactions and then covalently linked to the shell via surface coordinated Aphen by a coupling reaction in order to obtain magnetic properties. The morphology of P(St/FMA)/PNIPAAm-Fe₃O₄ composite particles, confirmed by transmission electron microscopy (TEM), reveals that Fe₃O₄ nanoparticles are located in the PNIPAAm shell. The thermo-sensitivity of composite particles to hydrodynamic diameter was confirmed by using dynamic light scattering (DLS). Photoluminescence (PL) spectra indicate that the fluorescence emission intensity of core/shell particles is highly sensitive to the pH of an aqueous medium. The core/shell composite particles exhibited a combination of fluorescent, magnetic, pH and thermo-responsive behavior.     

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.     

Bimagnetic hard/soft and soft/hard ferrite nanocomposites: Structural,magnetic and hyperthermia properties

Recent studies show that the chemical composition and shape of magnetic nanoparticles (NPs) play an important role in their properties. In particular, the bimagnetic NPs display useful and in many cases, more interesting properties than single-phase NPs. In this work, we prepared Fe₃O₄ and CoFe₂O₄ cube-like NPs and bimagnetic hard/soft (CoFe₂O₄/Fe₃O₄) and soft/hard (Fe₃O₄/CoFe₂O₄) nanocomposites (core/coating) using a facile and eco-friendly co-precipitation method that allows the synthesis of the cube-like NPs at temperatures near room temperature. The phase purity and the crystallinity of the NPs with a spinel structure were confirmed by the X-ray diffraction and infrared spectra techniques. Transmission electron microscopy (TEM) images revealed that the NPs have a cubic-like shape with an average dimension of 20 nm. Energy dispersive X-ray analysis, Mössbauer spectroscopy and SQUID magnetic measurements indicated the co-existence of Fe₃O₄ and CoFe₂O₄ phases in nanocomposites. In addition, the hysteresis loops exhibited a single-phase behavior in the nanocomposites that indicates there is a good exchange-coupling interaction between the hard and soft magnetic phases. The CoFe₂O₄/Fe₃O₄ nanocomposites presented a larger saturation magnetization than the CoFe₂O₄ NPs that is effective for their use in magnetic hyperthermia. Finally, we studied the hyperthermia properties of samples in an alternating magnetic field with a frequency of 276 kHz and field amplitude of 13.9 kA/m. Our results showed that magnetic hyperthermia efficiency simultaneously depends on the composition of samples along with magnetic anisotropy and saturation magnetization.     

Core-shell structured iron-containing ceramic nanoparticles: Facile fabrication and excellent electromagnetic absorption properties

In this work, novel core-shell structured Fe₃Si@C/SiC/Fe₃O₄/SiO₂ nanoparticles were fabricated via a polymer-derived ceramic approach, starting from sol-like polycarbosilane-encapsulated polynuclear carbonyl iron nanoparticles and with pitch as an isolator to avoid aggregation during polymer-to-ceramic transformation. Elemental analysis, X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscope, vibrating sample magnetometer and vector network analyzer were employed to investigate the composition, nano/microstructure, morphology, and dielectric/magnetic properties. The results show that the size of obtained Fe₃Si@C/SiC/Fe₃O₄/SiO₂ nanoparticles is in the range of 2-200 nm. And the unique core-shell structure with the hetero-interface combined with simultaneous dielectric and magnetic loss endow Fe₃Si@C/SiC/Fe₃O₄/SiO₂ nanoparticles outstanding electromagnetic (EM) wave absorbing performance. With a sample thickness of 4.5 mm, the minimum reflection coefficient (RC) of the composites Fe₃Si@C/SiC/Fe₃O₄/SiO₂ mixed with paraffin wax reaches −44.7 dB, indicating that more than 99.99% EM waves can be attenuated by the composites. By adjusting the sample thicknesses, the effective bandwidth (the bandwidth of RC values lower than −10 dB) amounts 9.5 GHz (from 2.5 to 12.0 GHz), covering the whole C and X bands.     

Controlled preparation of Fe3O4/P (St-MA) magnetic composite microspheres by DPE method

In this work, controlled radical polymerization based on 1, 1-diphenylethylene (DPE method) was used to prepare magnetic composite microspheres. By this method, Fe₃O₄/P (St-MA) magnetic composite microspheres were prepared via copolymerization of styrene (St) and maleic anhydride (MA) using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres obtained were characterized by IR, ¹H-NMR, SEC-MALLS, TEM, TGA, VSM, DLS and other instruments. It was found that the DPE method allows the controlled preparation of magnetic composite microspheres, and Fe₃O₄/ P(St-MA) microspheres possess perfect sphere-shaped morphology, homogeneous particle size, carboxylic surface, superparamagnetism with a saturation magnetization of 14.704 emu/g, and magnetic content with a value of 25%.     

One-pot method fabrication of superparamagnetic sulfonated polystyrene/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/graphene oxide micro-nano composites

In this work, using monodispersed sulfonated polystyrene (SPS) microspheres as carriers, FeCl₃·6H₂O and FeSO₄·7H₂O as precursors, NaOH as precipitant in the presence of graphene oxide (GO), SPS/Fe₃O₄/GO micro-nano composites were fabricated by a simple one-pot method employing an inverse coprecipitation in-situ compound technology. The SPS/Fe₃O₄/GO micro-nano composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffractometer, Fourier transform infrared spectroscopy, nitrogen adsorption/desorption isotherms and vibrating sample magnetometer. The results show that the SPS/Fe₃O₄/GO micro-nano composites were fabricated with SPS as core, GO and Fe₃O₄ nanoparticles as shell. The SPS/Fe₃O₄/GO micro-nano composites had larger BET specific surface area, average pore width and micropore volume than the pure SPS microspheres. Meanwhile, the SPS/Fe₃O₄/GO micro-nano composites had superparamagnetism and hydrophilic property. The saturation magnetization (M_s) of the SPS/Fe₃O₄/GO micro-nano composites was 10.86 emu/g, which was enough to ensure the convenient magnetic separation of solid and liquid phase.     

Fe3O4@mesoporouspolyaniline: A Highly Efficient and Magnetically Separable Catalyst for Cross‐Coupling of Aryl Chlorides and Phenols

A high surface, magnetic Fe₃O₄@mesoporouspolyaniline core‐shell nanocomposite was synthesized from magnetic iron oxide (Fe₃O₄) nanoparticles and mesoporouspolyaniline (mPANI). The novel porous magnetic Fe₃O₄ was obtained by solvothermal method under sealed pressure reactor at high temperature to achieve high surface area. The mesoporouspolyaniline shell was synthesized by in situ surface polymerization onto porous magnetic Fe₃O₄ in the presence of polyvinylpyrrolidone (PVP) and sodium dodecylbenzenesulfonate (SDBS), as a linker and structure‐directing agent, through ‘blackberry nanostructures’ assembly. The material composition, stoichiometric ratio and reaction conditions play vital roles in the synthesis of these nanostructures as confirmed by variety of characterization techniques. The role of the mesoporouspolyaniline shell is to stabilize the porous magnetic Fe₃O₄ nanoparticles, and provide direct access to the core Fe₃O₄ nanoparticles. The catalytic activity of magnetic Fe₃O₄@mesoporousPANI nanocomposite was evaluated in the cross‐coupling of aryl chlorides and phenols.     

Ultrafine palladium nanoparticle-bonded to polyetheylenimine grafted reduced graphene oxide nanosheets: Highly active and recyclable catalyst for degradation of dyes and pigments

Much attention has been increasingly focused on the applications of noble metal nanoparticles (NPs) for the catalytic degradation of various dyes and pigments in industrial wastewater. We have demonstrated that Pd NPs/Fe₃O₄-PEI-RGO nanohybrids exhibit high catalytic activity and excellent durability in reductive degradation of MO, R6G, RB. Specific surface area was successfully prepared by simultaneous reduction of Pd(OAc)₂ chelating to PEI grafted graphene oxide nanosheets modified with Fe₃O₄. The as-prepared Pd NPs/Fe₃O₄-PEI-RGO nanohybrids were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution TEM and energy dispersive X-ray spectroscopy, and UV-lambda 800 spectrophotometer, respectively. The catalytic activity of Pd NPs/Fe₃O₄-PEI-RGO nanohybrids to the degradation of MO, R6G, RB with NaBH4 was tracked by UV-visible spectroscopy. It was clearly demonstrated that Pd NPs/Fe₃O₄-PEI-RGO nanohybrids exhibited high catalytic activity toward the degradation of dyes and pigments, which could be relevant to the high surface areas of Pd NPs and synergistic effect on transfer of electrons between reduced graphene oxide (RGO), PEI and Pd NPs. Notably, Pd NPs/Fe₃O₄-PEI-RGO nanohybrids were easily separated and recycled thirteen times without obvious decrease in system. Convincingly, Pd NPs/Fe₃O₄-PEI-RGO nanohybrids would be a promising catalyst for treating industrial wastewater.     

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。     

Immobilization of serum albumin on the synthesized three layers core–shell structures of super-paramagnetic iron oxide nanoparticles

In this study, the synthesis of four layer structures coated on magnetite nanoparticles such that Fe₃O₄/SiO₂/APTES/PEG/BSA was investigated. Magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution with the average size of 25 nm. To fabricate Fe₃O₄/SiO₂ core–shells, the magnetite nanoparticles coated by silica with Stöber method. The fabricated nanoparticles were treated by 3-aminopropyl-triethoxysilane to achieve Fe₃O₄/SiO₂/APTES nanostructures. Moreover, the nanoparticles were also attached to reactive polyethylene glycol chains. Eventually, the nanoparticles activated with bovine serum albumin for bio-application. X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, UV–vis spectroscopy and vibrating sample magnetometer were used to support the characterization.     

Functional acrylic acid as stabilizer for synthesis of smart hydrogel particles containing a magnetic Fe3O4 core

This paper reports a novel method to synthesize magnetic, stimuli-sensitive latex nanoparticles made with magnetite/poly(N-isopropylacrylamide-co-acrylic acid) (Fe₃O₄/P(NIPAAm-co-AAc)). To form a stabilized suspended core, iron oxide (Fe₃O₄) was functionalized with AAc such that further polymerization with NIPAAm and AAc monomers could occur. The P(NIPAAm-co-AAc) shell layer exhibited thermosensitive properties. The inclusion of Fe₃O₄ into the latex nanoparticles was confirmed using transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction spectroscopy, thermogravimetric analyzer (TGA), and superconducting quantum interference device magnetometer. The NIP–(AAc2.6–Fe) latex nanoparticles contained 2.25% Fe₃O₄ (by weight), as determined by TGA analysis. The particle diameters measured approximately 160–240 nm with a lower critical solution temperature of 35 °C. These novel magnetic stimuli-responsive latex nanoparticles have potential applications in numerous fields, such as catalyst supports, protein immobilization, cancer therapy, target drug delivery systems, and other biomedical applications.