Synthesis and properties of iron oxide coated carbon nanotubes hybrid materials and their use in epoxy coatings

Multi‐walled carbon nanotubes (MWCNTs) were acidified with nitration mixture, and the Fe₂O₃‐MWCNTs (iron oxide coated multi‐walled carbon nanotubes) hybrid material via sol‐gel method then verified the results through scanning electron microscope, X‐ray diffraction, and thermal gravimetric analysis. We modified the hybrid material with silane coupling agent (KH560), Fe₂O₃‐MWCNTs/epoxy, MWCNTs/epoxy composites coating, and the pure epoxy coatings were respectively prepared. The properties of the composite coatings were tested through the electrochemical workstation (electrochemical impedance spectroscopy), shock experiments, and thermal gravimetric analysis. Finally, we used scanning electron microscope to observe the surface conditions of the coatings. The results show that Fe₂O₃‐MWCNTs have good dispersion in the epoxy resin, and the Fe₂O₃‐MWCNTs/epoxy composite coatings have enhanced mechanical properties and corrosion resistance. Copyright © 2015 John Wiley & Sons, Ltd.     

Functionalized boron carbide for enhancement of anticorrosion performance of epoxy resin

In this study, epoxy coatings were modified by adding various compositions of B₄C particles. In order to achieve proper dispersion of particles in the epoxy coating and increasing chemical interactions between particles and polymeric coating, the surface of the B₄C particles was treated with γ‐(2,3‐epoxypropoxy) propytrimethoxysilane (KH560). The surface modification and microstructure of B₄C were characterized by Fourier transform infrared, X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical impedance spectroscopy was also used to evaluate the impedance of coatings. The results revealed that the KH560 not only enhanced the interaction between B₄C particles and epoxy resin but also exhibited a remarkable ability to improve the anticorrosion performance of epoxy resin. The epoxy coating with the 3 wt% B₄C‐KH560 particles exhibited the best anticorrosion performance, which can be attributed to the best uniform dispersion of the B₄C‐KH560 particles, and the particles effectively block the aggressive species (Cl⁻, O₂, and H₂O) from the coating.     

Synthesis of a novel and reusable biological urea based acidic nanomagnetic catalyst: Application for the synthesis of 2‐amino‐3‐cyano pyridines via cooperative vinylogous anomeric based oxidation

In the current study, a novel and reusable biological urea based nano magnetic catalyst namely Fe₃O₄@SiO₂@(CH₂)₃‐urea‐benzimidazole sulfonic acid was designed and synthesized. The structure of the titled catalyst was fully characterized using several skills including Fourier transform infrared (FT‐IR) spectroscopy, energy dispersive X‐ray (EDX) analysis, X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermo gravimetric analysis/differential thermal analysis (TG/DTG) and vibrating sample magnetometer (VSM). Then, the catalytic performance of Fe₃O₄@SiO₂@(CH₂)₃‐urea‐benzimidazole sulfonic acid was successfully inspected towards the multicomponent synthesis of 2‐amino‐3‐cyano pyridine derivatives through a vinylogous anomeric based oxidation pathway.     

Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe3O4@polyaniline composites as a highly efficient,magnetically separable and atom‐economical catalyst for reduction of nitrobenzenes

The preparation of Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe₃O₄@polyaniline composites is reported. Fe₃O₄ nanoclusters were first synthesized through the solvothermal method and then the SiO₂ shell was coated on the Fe₃O₄ surface via a sol–gel process. To prepare Fe₃O₄@SiO₂@polyaniline composites, polyvinylpyrrolidone was first grafted on to the surface of Fe₃O₄@SiO₂ composites and subsequently polymerization of aniline was carried out via an ultrasound‐assisted in situ surface polymerization method. Selective etching of the middle SiO₂ layer was then accomplished to obtain the yolk–shell Fe₃O₄@polyaniline composites. The approach uses polyaniline (PANI) conductive polymer as a template for the synthesis of Ni@Pd core–shell nanoparticles. The catalytic activity of the synthesized yolk–shell Fe₃O₄@PANI/Ni@Pd composite was investigated in the reduction of o‐nitroaniline to benzenediamine by NaBH₄, which exhibited conversion of 99% in 3 min with a very low content of the catalyst. Transmission electron microscopy, X‐ray photoelectron spectroscopy, TGA, X‐ray diffraction, UV–visible, scanning electron microscopy, X‐ray energy dispersion spectroscopy and FT‐IR were employed to characterize the synthesized nanocatalyst. Copyright © 2014 John Wiley & Sons, Ltd.     

Gallic acid grafted to amine‐functionalized magnetic nanoparticles as a proficient catalyst for environmentally friendly synthesis of α‐aminonitriles

An effective approach of one‐pot catalytic Strecker reaction between aromatic aldehydes, aniline or toluidine and trimethylsilyl cyanide in the presence of amine‐functionalized Fe₃O₄@SiO₂ nanoparticles grafted with gallic acid (GA) as a powerful catalyst was developed. The fabricated reusable catalyst demonstrated high efficiency in the synthesis of α‐aminonitriles along with facile work‐up procedure. Fe₃O₄@SiO₂‐NH₂‐GA was characterized by Fourier transform‐infrared spectroscopy, scanning electron microscopy image, vibrating‐sample magnetometer curve, energy‐dispersive X‐ray analysis and thermogravimetric analysis.     

Direct Electrochemistry of Hemoglobin Based on Fe3O4@SiO2 Nanoparticles Modified Electrode

A biosensor based on hemoglobin‐Fe₃O₄@SiO₂ nanoparticle bioconjunctions modified indium‐tin‐oxide (Hb/Fe₃O₄@SiO₂/ITO) electrode was fabricated to determine the concentration of H₂O₂. UV‐vis absorption spectra, fourier transform infrared (FT‐IR) spectroscopy, cyclic voltammetry (CV) and high‐resolution transmission electron microscopy (HRTEM) were used to characterize the bioconjunction of Fe₃O₄@SiO₂ with Hb. Experimental results demonstrate that the immobilized Hb on the Fe₃O₄@SiO₂ matrix retained its native structure well. In addition, Fe₃O₄@SiO₂ nanoparticles (NPs) are very effective in facilitating electron transfer of the immobilized enzyme, which can be attributed to the unique nanostructure and larger surface area of the Fe₃O₄@SiO₂ NPs. The biosensor displayed good performance for the detection of H₂O₂ with a wide linear range from 2.03×10^?6 to 4.05×10^?3 mol/L and a detection limit of 0.32 µmol/L. The resulting biosensor exhibited fast amperometric response, good stability, reproducibility, and selectivity to H₂O₂.     

Characterization and anticorrosive properties of poly(2,3‐dimethylaniline)/nano‐Al2O3 composite synthesized by emulsion polymerization

Poly(2,3‐dimethylaniline)/nano‐Al₂O₃ composite (PAC) was synthesized by emulsion polymerization using dodecyl benzene sulfonic acid as emulsifier and dopant. The structure of PAC was characterized by Fourier fransformation infrared spectroscopy, UV–visible adsorption spectroscopy, and field emission scanning electron microscopy. The thermal stability was studied by thermogravimetric analysis, and the electrochemical performances were studied by cyclic voltammetry measurements. Epoxy coatings containing PAC and poly(2,3‐dimethylaniline) (P(2,3‐DMA)), respectively, were painted on steel, and accelerated immersion tests were performed to evaluate the anticorrosion property of the coatings in 3.5% NaCl solution. The results showed that the addition of PAC and P(2,3‐DMA) could improve the anticorrosion performance of epoxy coating significantly and the PAC coating had higher corrosion resistance than that of P(2,3‐DMA). Copyright © 2013 John Wiley & Sons, Ltd.     

Latent Fingerprints Enhancement Using a Functional Composite of Fe3O4@SiO2-Au

A functional composite of Fe₃O₄@SiO₂-Au was prepared and used for latent fingerprint detection. Material characterization results confirmed the successful fabrication of the Fe₃O₄@SiO₂-Au composite. In latent fingerprint detection, the Fe₃O₄@SiO₂-Au composite provides a better performance than commercial copper powder and also gold nanoparticles. More importantly, the Fe₃O₄@SiO₂-Au composite can be used in both powder and suspension forms, and also for common surfaces including glass, polyethylene bags, and paper. The favorable pH range (2.0–5.0) for the compositein finger marks detection is much wider than that of the traditional multi-metal deposition method (pH ranging from 2.0 to 3.0). The mechanism for the Fe₃O₄@SiO₂-Au composite in fingerprint detection was explored and discussed. This study provides a favorable choice for a one-step deposition method for latent fingerprint detection.     

MgBr2 supported on Fe3O4@SiO2 ~ urea nanoparticle: An efficient catalyst for ortho‐formylation of phenols and oxidation of benzylic alcohols

Urea was successfully immobilized on the surface of chloropropyl‐modified Fe₃O₄@SiO₂ core–shell magnetic nanoparticles, then supported by MgBr₂ and acts as a unique catalyst for oxidation of benzylic alcohols to aldehydes and ketones, and ortho‐formylation of phenols to salicylaldehydes. The prepared catalyst was characterized by FT‐IR, transmission electron microscopy, scanning electron microscopy, X‐ray powder diffraction, dispersive X‐ray spectroscopy, CHN and TGA. It was found that Fe₃O₄@SiO₂ ~ urea/MgBr₂ showed higher catalytic activity than homogenous MgBr₂, and could be reused several times without significant loss of activity.     

Synthesis and characterization of polyvinylpyrrolidone immobilized on magnetic nanoparticles modified by ionic liquid as a novel and recyclable catalyst for the three‐component synthesis of amidoalkyl naphthols

In this study, an efficient and green procedure is explained for the preparation of 1‐amidoalkyl‐2‐naphthols applying one‐pot condensation reaction of 2‐naphthol, amide and aromatic nanoparticles (Fe₃O₄@SiO₂@IL‐PVP) as a novel solid acid catalyst under solvent‐free conditions. The remarkable features of this method are short reaction time, high conversions, and high yield of product, easy workup procedures and solvent‐free conditions. The Fe₃O₄@SiO₂@IL‐PVP catalyst was characterized via Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction patterns (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), vibrating sample magnetometer (VSM), and energy‐dispersive X‐ray spectroscopy (EDS). Also, nanocatalysts could be easily recovered by a simple magnet and reused for the next reactions without significant loss of its catalytic activity.     

Improvement on physical properties of polyethersulfone membranes modified by poly(1‐vinylpyrrolidone) grafted magnetic Fe3O4@SiO2 nanoparticles

Polyethersulfone (PES) and poly(1‐vinylpyrrolidone) (PVP) were used to prepare ultrafiltration membranes with grafted Fe₃O₄ magnetic nanoparticles (PVP‐g‐Fe₃O₄@SiO₂). The structure of synthesized PVP‐g‐Fe₃O₄@SiO₂ was confirmed by FT‐IR and SEM analysis. Physical properties of blend membranes such as thermal resistance, Tensile strength, water uptake, and hydrophilicity were also investigated. Blended membranes of PES/PVP‐g‐Fe₃O₄@SiO₂ have exhibited higher thermal resistance due to increasing the modified nanoparticle content. The hydrophilicity of the synthesized PES/PVP‐g‐Fe₃O₄@SiO₂ membranes also improved by increasing the PVP‐g‐Fe₃O₄@SiO₂ content. As expected, increasing the hydrophilicity of blended membrane, caused enhancement of fouling resistance in membranes. Results showed that the content of PVP‐g‐Fe₃O₄@SiO₂ has different effects on the properties of synthesized composite membranes. Despite increasing the content of PVP‐g‐Fe₃O₄@SiO₂ has a negative effect on elongation, positive effects on maximum stress was observed. Moreover, the water uptake of synthesized membranes was significantly enhanced in comparison to other similar studies.     

Magnetically recoverable copper nanorods and their catalytic activity in Ullmann cross‐coupling reaction

A novel polydentate ligand supported on Fe₃O₄@SiO₂ was designed and demonstrated for the synthesis of Cu nanorods. The Fe₃O₄@SiO₂/EP.EN.EG@Cu was characterized using X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy and vibrating sample magnetometry. The Fe₃O₄@SiO₂/EP.EN.EG@Cu showed excellent catalytic efficiency for the cross‐coupling reaction of nitrogen‐containing heterocycles with aryl halides. The catalyst could be effectively separated from the reaction mixture by simply applying an external magnetic field and reused at least five times without loss of activity.     

Preparation and characterization of rapid magnetic recyclable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript>–Sn photocatalyst

Effective procedure to synthesize Fe₃O₄@SiO₂@TiO₂–Sn magnetically separable photocatalyst by a combination of co-precipitation, sol–gel and photodeposition methods was introduced. Products were characterized by XRD, SEM, VSM, EDS, DRS, TEM, ICP-OES and IR techniques. The dimensions of catalyst particle size were evaluated by scanning electron microscopy, and results approved nanoscale size for product. In addition, studying the magnetic nature by VSM analysis showed superparamagnetic properties for all samples. XRD pattern indicates that TiO₂ coated on Fe₃O₄@SiO₂ core well crystallized at 400 °C in anatase phase. Synthesized photocatalyst shows good photocatalytic performance in decolorization of rhodamine B aqueous solution. The composite nanoparticles showed high recycling efficiency and stability over five separation cycles.     

Fe3O4@SiO2@l‐arginine@Pd(0): a new magnetically retrievable heterogeneous nanocatalyst with high efficiency for C–C bond formation

The surface of Fe₃O₄@SiO₂ nanoparticles was modified using l ‐arginine as a green and available amino acid to trap palladium nanoparticles through a strong interaction between the metal nanoparticles and functional groups of the amino acid. The proposed green synthetic method takes advantage of nontoxic reagents through a simple procedure. Characterization of Fe₃O₄@SiO₂@l ‐arginine@Pd(0) was done using Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, vibrating sample magnetometry and inductively coupled plasma analysis. The catalytic activity of Fe₃O₄@SiO₂@l ‐arginine@Pd(0) as a new nanocatalyst was investigated in C – C coupling reactions. Waste‐free, use of green medium, efficient synthesis leading to high yield of products, eco‐friendly and economic catalyst, excellent reusability of the nanocatalyst and short reaction time are the main advantages of the method presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Functionalization of superparamagnetic Fe3O4@SiO2 nanoparticles with a Cu(II) binuclear Schiff base complex as an efficient and reusable nanomagnetic catalyst for N‐arylation of α‐amino acids and nitrogen‐containing heterocycles with aryl halides

Fe₃O₄@SiO₂ nanoparticles was functionalized with a binuclear Schiff base Cu(II)‐complex (Fe₃O₄@SiO₂/Schiff base‐Cu(II) NPs) and used as an effective magnetic hetereogeneous nanocatalyst for the N‐arylation of α‐amino acids and nitrogen‐containig heterocycles. The catalyst, Fe₃O₄@SiO₂/Schiff base‐Cu(II) NPs, was characterized by Fourier transform infrared (FTIR) and ultraviolet‐visible (UV‐vis) analyses step by step. Size, morphology, and size distribution of the nanocatalyst were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and dynamic light scatterings (DLS) analyses, respectively. The structure of Fe₃O₄ nanoparticles was checked by X‐ray diffraction (XRD) technique. Furthermore, the magnetic properties of the nanocatalyst were investigated by vibrating sample magnetometer (VSM) analysis. Loading content as well as leaching amounts of copper supported by the catalyst was measured by inductive coupled plasma (ICP) analysis. Also, thermal studies of the nanocatalyst was studied by thermal gravimetric analysis (TGA) instrument. X‐ray photoelectron spectroscopy (XPS) analysis of the catalyst revealed that the copper sites are in +2 oxidation state. The Fe₃O₄@SiO₂/Schiff base‐Cu(II) complex was found to be an effective catalyst for C–N cross‐coupling reactions, which high to excellent yields were achieved for α‐amino acids as well as N‐hetereocyclic compounds. Easy recoverability of the catalyst by an external magnet, reusability up to eight runs without significant loss of activity, and its well stability during the reaction are among the other highlights of this catalyst.     

Voltammetric determination of vitamin B<Subscript>6</Subscript> (pyridoxine) at a graphite screen-printed electrode modified with graphene oxide/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> nanocomposite

The preparation and study of electrochemical properties of a graphite screen-printed electrode (SPE) modified with the GO/Fe₃O₄@SiO₂ (GO is graphene oxide) nanocomposites are described. The morphologies of the GO/Fe₃O₄@SiO₂ nanocomposites were examined by scanning electron microscopy. The electrochemical oxidation of vitamin B₆ (pyridoxine) on SPE modified with the GO/Fe₃O₄@SiO₂ nanocomposite was investigated by cyclic voltammetry, differential pulse voltammetry, and chronoamperometry. Under optimum conditions (pH 7.0), the vitamin B₆ oxidation at the surface of the modified SPE occurs at a potential about 190 mV less positive than that at the unmodified SPE. A linear voltammetric response for vitamin B₆ was obtained in the concentration range 1.0?10 ⁶—9.0?10 ⁴ mol L^–1 with a detection limit of 5.2?10 ⁷ mol L^–1 using differential pulse voltammetry. The developed sensor was also successfully applied for determination of trace level of vitamin B₆ in both the standard vitamin B₆ sample and biological samples (urine).     

Synthesis,characterization, and properties of monodispersed magnetite coated multi‐walled carbon nanotube/polypyrrole nanocomposites synthesized by in‐situ chemical oxidative polymerization

This study describes the preparation of a nanocomposites fabricated from monodispersed 4‐nm iron oxide (Fe₃O₄) coated on the surface of carboxylic acid containing multi‐walled carbon nanotube (c‐MWCNT) and polypyrrole (PPy) by in situ chemical oxidative polymerization. High‐resolution transmission electron microscopy images and X‐ray diffraction (XRD) data indicate that the resulting Fe₃O₄ nanoparticles synthesized using the thermal decomposition are close to spherical dots with a particle size about 4 ± 0.2 nm. The resulting nanoparticles were further mixed with c‐MWCNT in an aqueous solution containing with anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate to form one‐dimensional Fe₃O₄ coated c‐MWCNT template for further preparation of nanocomposite. Structural and morphological analysis using field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, and XRD showed that the fabricated Fe₃O₄ coated c‐MWCNT/PPy nanocomposites are one‐dimensional core (Fe₃O₄ coated c‐MWCNT)‐shell (PPy) structures. The conductivities of these Fe₃O₄ coated c‐MWCNT/PPy nanocomposites are about four times higher than those of pure PPy matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 727–733, 2008     

Removal of Chromium Ions by Fe3O4‐containing Polypyrrole Matrix and Environmental Applications

In this work, the PPy/Fe₃O₄@TiO₂ composite was synthesized and characterized by X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and magnetic measurements (using a vibrating sample magnetometer). The adsorption performance of PPy/Fe₃O₄@TiO₂ composite for Cr(VI) ions was evaluated by UV irradiation. The effects of pH, adsorbent dose, contact time, and the initial concentration on the adsorption performance of Cr(VI) onto PPy/Fe₃O₄@TiO₂ were investigated. The maximum adsorption capacity of Cr(VI) upon doped PPy/Fe₃O₄@TiO₂ is 85.30 mg/g at room temperature. The total adsorption process likely follows the Langmuir model and pseudo‐second‐order kinetics. Our study suggests that the PPy/Fe₃O₄@TiO₂ composite can be efficiently used for the adsorption of Cr(VI) ions.     

A highly reactive and magnetic recyclable catalyst based on silver nanoparticles supported on ferrite for N‐monoalkylation of amines with alcohols

Fe₃O₄@SiO₂‐Ag catalyst was found to be highly active and selective in the N ‐alkylation of amines with a variety of aromatic and linear alcohols. The heterogeneous nature of the Fe₃O₄@SiO₂‐Ag catalyst allows easy recovery and regeneration by applying an external magnet for six subsequent reaction cycles. The prepared catalyst was characterized using electron microscopy techniques, X‐ray diffraction, vibrating sample magnetometry and atomic absorption spectroscopy.     

Uniformly dispersed copper nanoparticles onto the modified magnetically recoverable nanocatalyst for aqueous synthesis of primary amides

Magnetically recoverable and environmentally friendly Cu‐based heterogeneous catalyst has been synthesized for the one‐pot conversion of aldehydes to their corresponding primary amides. The Fe₃O₄@SiO₂ nanocomposites were prepared by synthesis of Fe₃O₄ magnetic nanoparticles (MNPs) which was then coated with a silica shell via Stöber method. Bi‐functional cysteine amino acid was covalently bonded onto the siliceous shell of nanocatalyst. The Cu^II ions were then loaded onto the modified surface of nanocatalyst. Finally, uniformly dispersed copper nanoparticles were achieved by reduction of Cu^II ions with NaBH₄. Amidation reaction of aryl halides with electron‐withdrawing or electron‐donating groups and hydroxylamine hydrochloride catalyzed with Fe₃O₄@SiO₂@Cysteine‐copper (FSC‐Cu) MNPs in aqueous condition gave an excellent yield of products. The FSC‐Cu MNPs could be easily isolated from the reaction mixture with an external magnet and reused at least 8 times without significant loss in activity.