Preparation and application of calix[4]arene-grafted magnetite nanoparticles for removal of dichromate anions

Magnetic Fe₃O₄ nanoparticles were prepared by the chemical co-precipitation of Fe(III) and Fe(II) ions. Then, the nanoparticles were modified directly by 3-aminopropyltrimethoxy silane (APTMS) to introduce reactive groups onto the particles' surface, and diester derivative of calix[4]arene was immobilized onto the surface of modified-Fe₃O₄ nanoparticles by aminolysis reaction. The prepared magnetite nanoparticles (Calix-GM) were characterized by a combination of IR, TGA and TEM analyses. The extraction properties of the new material toward dichromate anions were also studied. It was observed that the prepared magnetite nanoparticles were an effective extractant for the removal of dichromate anions at pH 2.5–4.5.     

Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants

In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe₃O₄) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core–shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g⁻¹ and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12–14 mg_La/g_MNP. The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet.     

Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants

Abstract

In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe₃O₄) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core–shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g^?1 and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12–14 mg_La/g_MNP. The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet.     

Strong adsorption of chlorotetracycline on magnetite nanoparticles

In this work, environmentally friendly magnetite nanoparticles (Fe₃O₄ MNPs) were used to adsorb chlorotetracycline (CTC) from aqueous media. Fe₃O₄ MNPs exhibit ultrahigh adsorption ability to this widely used antibiotic. The adsorption behavior of CTC on Fe₃O₄ MNPs fitted the pseudo-second-order kinetics model, and the adsorption equilibrium was achieved within 10 h. The maximum Langmuir adsorption capacity of CTC on Fe₃O₄ (476 mg g⁻¹) was obtained at pH 6.5. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was endothermic and spontaneous. Low concentration of NaCl and foreign divalent cations hardly affected the adsorption. Negative effect of coexisting humic acid (HA) on CTC adsorption was also observed when the concentration of HA was lower than 20 mg L⁻¹. But high concentration of HA (>20 mg L⁻¹) increased the CTC adsorption on Fe₃O₄ MNPs. The matrix effect of several environmental water samples on CTC adsorption was not evident. Fe₃O₄ MNPs were regenerated by treatment with H₂O₂ or calcination at 400 °C in N₂ atmosphere after separation from water solution by an external magnet. This research provided a high efficient and reusable adsorbent to remove CTC selectively from aqueous media.     

Study of Structural and Magnetic Properties of Superparamagnetic Fe3O4–ZnO Core–Shell Nanoparticles

In this work, Fe₃O₄–ZnO core–shell nanoparticles have been successfully synthesized using a simple two-step co-precipitation method. In this regard, Fe₃O₄ (magnetite) and ZnO (zincite) nanoparticles (NPs) were synthesized separately. Then, the surface of the Fe₃O₄ NPs was modified with trisodium citrate in order to improve the attachment of ZnO NPs to the surface of Fe₃O₄ NPs. Afterwards, the modified magnetite NPs were coated with ZnO NPs. Moreover, the influence of the core to shell molar ratio on the structural and magnetic properties of the core–shell NPs has been investigated. The prepared nanoparticles have been characterized utilizing transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and vibrating sample magnetometer (VSM). The results of XRD indicate that Fe₃O₄ NPs with inverse spinel phase were formed. The results of VSM imply that the Fe₃O₄–ZnO core–shell NPs are superparamagnetic. The saturation magnetization of prepared Fe₃O₄ NPs is 54.24 emu/g and it decreases intensively down to 29.88, 10.51 and 5.75 emu/g, after ZnO coating with various ratios of core to shell as 1:1, 1:10 and 1:20, respectively. This reduction is attributed to core–shell interface effects and shielding. TEM images and XRD results imply that ZnO-coated magnetite NPs are formed. According to the TEM images, the estimated average size for most of core–shell NPs is about 12 nm.     

Simultaneous synthesis of polyaniline nanorods and magnetite nanoparticles via self-assembly method

In this work, polyaniline (PANI) nanorods and magnetite (Fe₃O₄) nanoparticles have been synthesised by using ammonium persulphate as oxidant via in-situ chemical oxidative polymerisation of aniline in presence of excess of organic sulphonic acid. The resulting PANI/Fe₃O₄ nanocomposites materials were characterised using X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, vibrating sampling magnetometer and thermogravimetric analysis. Spectroscopic results indicated the successful formation of PANI/Fe₃O₄ nanocomposites. As obtained, PANI/Fe₃O₄ nanocomposites have Fe₃O₄ particle size in the range of 3.2–7?nm. Morphologies of PANI/Fe₃O₄ nanocomposites were found to be dependent on the molar ratio of aniline to organic acid. Under certain polymerisation conditions, PANI rods like structures were obtained. PANI/Fe₃O₄ nanocomposites have superparamagnetism and higher thermal stability.     

Magnetic 99mTc- core-shell of polyethylene glycol/polyhydroxyethyl methacrylate based on Fe3O4 nanoparticles: Radiation synthesis,characterization and biodistribution study in tumor bearing mice

Magnetic nanoparticles (Fe₃O₄) coated with polyethylene glycol (PEG), (Fe₃O₄/PEG), were synthesized by chemical co-precipitation of Fe²⁺/Fe³⁺ salts by aqueous ammonia in PEG solution. Radiation polymerization of 2-hydroxyethyl methacrylate (HEMA) monomer solution onto Fe₃O₄/PEG was performed at different doses to synthesize (Fe₃O₄/PEG)-pHEMA, namely FPH, nanocomposites. Properties of FPH nanocomposites were characterized by FT-IR, XRD, SEM, TEM, DLS, ESR and TGA techniques. The XRD of FPH nanocomposites showed all the peaks of Fe₃O₄ nanoparticles. SEM was used to assess the surface morphology of FPH. TEM showed that the average diameter of FPH nanocomposites was in the range of 9–40 nm. The thermal stability of FPH nanocomposites was higher than that of Fe₃O₄ and Fe₃O₄/PEG. Radio-labeling of (Fe₃O₄/PEG)-pHEMA nanocomposite irradiated at 10 kGy (FPH10) with ^99mTc was performed using stannous chloride as reducing agent. Factors affecting the labeling yield (%) such as the substrate amount, the amount of reducing agent, the pH of reaction medium, the reaction time and the reaction temperature were investigated. The maximum labeling yield was 93% using 0.25 mg of FPH10 at pH 6 and 20 min reaction time. The biodistribution study of ^99mTc-FPH10 was examined on two groups of ascites and solid tumor bearing mice. The biodistribution results referred that ^99mTc-FPH10 was rapidly uptake in tumor sites ascites or solid tumors. The results indicated that FPH nanocomposites could be potentially used for tumor imaging and therapy.     

Synthesis of Poly(DL-Lactide-Co-Glycolide) Nanoparticles with Entrapped Magnetite by Emulsion Evaporation Method

The goal of this study was to synthesize Poly(DL-lactide-Co-glycolide) nanoparticles with entrapped magnetite, of under 100 nm in diameter, for future drug delivery applications. The emulsion evaporation method was selected to form poly(lactide-co-glycolide) (PLGA) nanoparticles with entrapped magnetite (Fe₃O₄) in the polymeric matrix, in the presence of sodium dodecyl sulfate (SDS) as a surfactant. Magnetite, a water-soluble compound, was surface functionalized with oleic acid to ensure its efficient entrapment in the PLGA matrix. The inclusion of magnetite with oleic acid (MOA) into the PLGA nanoparticles was accomplished in the organic phase. Synthesis was followed by dialysis, performed to eliminate the excess SDS, and lyophilization. The synthesized nanoparticles ranged in size from 38.6 to 67.1 nm for naked PLGA nanospheres and from 78.8 to 87.2 nm for MOA-entrapped PLGA nanospheres. The entrapment efficiency ranged from 57.36% to 77.3%.     

Three-dimensional magnetic graphene oxide foam/Fe3O4 nanocomposite as an efficient absorbent for Cr(VI) removal

We developed a novel three-dimensional (3D) graphene oxide foam/Fe₃O₄ nanocomposite (GOF/Fe₃O₄) and evaluated its adsorption performance for Cr(IV) removal. The 3D free-standing graphene foam was firstly synthesized on nickel foam and then oxidized and magnetically functionalized with Fe₃O₄ nanoparticles to form GOF/Fe₃O₄. The GOF/Fe₃O₄ exhibited a very large surface area of 574.2 m²/g, a high saturation magnetization of 40.2 emu/g, and a maximum absorption capacity of 258.6 mg/g for Cr(IV) removal, which significantly outperformed the reported 2D graphene-based adsorbents and other conventional adsorbents. The present work may offer a way to prepare a range of 3D magnetic graphene-based adsorbents for application in effective removal of heavy metal ions.     

Synthesis and application of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as novel adsorbent for removal of Cd(II), Hg(II) and Ni(II) ions from water samples

In the current study, SiO₂/Fe₃O₄ core–shell nanoparticles functionalized with TiO₂, using a simple method and application for removal of Cd(II), Hg(II) and Ni(II) ions from aqueous solution. The structure of the resulting product was confirmed by X-ray diffraction spectrometry, transmission electron microscopy (TEM), pH_pzc and Brunauer, Emmett and Teller methods. The average diameter of TiO₂/SiO₂/Fe₃O₄ nanoparticles according to TEM was obtained around 48 nm. In batch tests, the effects of pH, initial metal concentration, contact time and temperature were studied. Adsorption of metal ions was studied from both kinetics and equilibrium point of view. Maximum adsorption capacity of Cd(II), Hg(II) and Ni(II) on TiO₂/SiO₂/Fe₃O₄ nanoparticles was 670.9, 745.6 and 563.0 mg g^?1, respectively. Adsorption–desorption results showed that the reusability of nanoparticles was encouraging. This adsorbent was successfully applied to removal Cd(II), Hg(II) and Ni(II) ions in real samples including tap water, electronic wastewater and medical wastewater.     

Effect of the preparation route,PEG and annealing on the phase stability of Fe3O4 nanoparticles and their magnetic properties

Fe₃O₄ nanoparticles are synthesised via two different methods: (1) co-precipitation of Fe²⁺ and Fe³⁺ ions and (2) oxidative alkaline hydrolysis of Fe²⁺ ions under atmospheric pressure using different protective agents (PEG 200 and PEG 3000) and urea as a base. The preparation method and the polyethylene glycol (PEG) used are concurrently affecting the phase stability of the formation of the iron oxides: the co-precipitation method using PEG 200 (E4a) or PEG 3000 (E4b) leads to the formation of different ratios of Fe₂O₃ and Fe₃O₄, whereas the oxidative hydrolysis of Fe²⁺ using PEG 200 gives Fe₃O₄ (E2) powder as a major product. The average crystallites size of E4a and E4b is almost identical, i.e. around 19?nm but the saturation magnetisation of E4b is three times larger than that of E4a. The sample E2 shows the highest saturation magnetisation value 74?emu/g, with an average crystallites size of 71?nm. Transmission electron microscopy analysis confirmed that the E2 sample shows the presence of needles crystals with typical sizes around 10 and 50?nm and its selected area diffraction (SAD) shows a typical diffraction of the spinel structure of magnetite. On the other hand, E4b sample shows elongated nanoparticles with typical sizes around 24?nm and its SAD confirmed the presence of a mixture of Fe₂O₃ and Fe₃O₄ as many dispersed spots were obtained.     

Synthesis and magnetic characterization of magnetite obtained by monowavelength visible light irradiation

Magnetite (Fe₃O₄) nanoparticles were controllably synthesized by aerial oxidation Fe^IIEDTA solution under different monowavelength light-emitting diode (LED) lamps irradiation at room temperature. The results of the X-ray diffraction (XRD) spectra show the formation of magnetite nanoparticle further confirmed by Fourier transform infrared spectroscope (FTIR) and the difference in crystallinity of as-prepared samples. Fe₃O₄ particles are nearly spherical in shape based on transmission electron microscopy (TEM). Average crystallite sizes of magnetite can be controlled by different irradiation light wavelengths from XRD and TEM: 50.1, 41.2, and 20.3 nm for red, green, and blue light irradiation, respectively. The magnetic properties of Fe₃O₄ samples were investigated. Saturation magnetization values of magnetic nanoparticles were 70.1 (sample M-625), 65.3 (sample M-525), and 58.2 (sample M-460) emu/g, respectively.     

Effect of Carbon Shell on the Structural and Magnetic Properties of Fe3O4 Superparamagnetic Nanoparticles

Carbon-encapsulated iron oxides (Fe₃O₄/C) with a core/shell structure have been successfully synthesized by using a simple two-step hydrothermal method at 180 ^°C. Fe₃O₄ core nanoparticles were prepared by coprecipitation under two conditions. Synthesized nanoparticles were characterized by transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. TEM images and FTIR results prove that carbon coated iron oxide is formed and the estimated size for most of them is below 11 nm, which was consistent with the XRD result. The Williamson–Hall (W–H) method has been used to calculate crystallite sizes and lattice strain based on the peak broadening of the Fe₃O₄ and Fe₃O₄/C nanoparticles. The results of VSM imply that the Fe₃O₄ core and core–shell nanoparticles are superparamagnetic. The saturation magnetization of Fe₃O₄ and Fe₃O₄/C are 49 emu/gr and 40 emu/gr, respectively. The magnetic behaviors reveal that the amorphous carbon shell can decrease the saturation magnetization of Fe₃O₄ nanoparticles due to core–shell interface effects and shielding.     

Preparation and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Ag composite magnetic nanoparticles

Fe₃O₄ magnetic nanoparticles being used as seeding materials, Ag⁺ ions on the Fe₃O₄ magnetic nanoparticles reduced to the metal form by tartaric acid using heated treatment. Thus, Fe₃O₄/Ag composite core-shell magnetic nanoparticles were synthesized. The products were characterized by transmission electron microscope (TEM) and x-ray diffraction (XRD). Both TEM and XRD results showed that the Ag nanoparticles were well distributed on the surface of Fe₃O₄ magnetic nanoparticles. The size for Fe₃O₄/Ag composite magnetic nanoparticles which were spherical shape was ≃40 nm. Furthermore, the magnetic properties of samples were characterized on a vibrating sample magnetometer. Under optimal conditions, Fe₃O₄/Ag composite nanoparticles showed higher magnetism than pure Fe₃O₄ nanoparticles. The text was submitted by the authors in English.     

Magnetoresistance and electroresistance effects in Fe3O4 nanoparticle system

Nearly monodisperse spherical magnetite (Fe₃O₄) nanoparticles are prepared by colloidal chemistry route. Magnetic and electronic transport properties of the annealed pellets of these nanoparticles are reported. Effect of external magnetic and electric fields on the magnetic and transport properties of the material are studied as a function of temperature. We find that the highest resistance state of the ferromagnetic system occurs at a magnetic field which is approximately equal to its magnetic coercivity; this establishes the magnetoresistance (MR) in this system to be of the conventional tunnelling type MR as against the spin-valve type MR found more recently in some ferromagnetic oxide systems. The material also shows electroresistance (ER) property with its low-temperature resistance being strongly dependent on the excitation current that is used for the measurement. This ER effect is concluded to be intrinsic to the material and is attributed to the electric field-induced melting of the charge-order state in magnetite.     

Surface engineered magnetic nanoparticles for removal of toxic metal ions and bacterial pathogens

Surface engineered magnetic nanoparticles (Fe₃O₄) were synthesized by facile soft-chemical approaches. XRD and TEM analyses reveal the formation of single-phase Fe₃O₄ inverse spinel nanostructures. The functionalization of Fe₃O₄ nanoparticles with carboxyl (succinic acid), amine (ethylenediamine) and thiol (2,3-dimercaptosuccinic acid) were evident from FTIR spectra, elemental analysis and zeta-potential measurements. From TEM micrographs, it has been observed that nanoparticles of average sizes about 10 and 6 nm are formed in carboxyl and thiol functionalized Fe₃O₄, respectively. However, each amine functionalized Fe₃O₄ is of size ∼40 nm comprising numerous nanoparticles of average diameter 6 nm. These nanoparticles show superparamagnetic behavior at room temperature with strong field dependent magnetic responsivity. We have explored the efficiency of these nanoparticles for removal of toxic metal ions (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Pb²⁺ and As³⁺) and bacterial pathogens (Escherichia coli) from water. Depending upon the surface functionality (COOH, NH₂ or SH), magnetic nanoadsorbents capture metal ions either by forming chelate complexes or ion exchange process or electrostatic interaction. It has been observed that the capture efficiency of bacteria is strongly dependent on the concentration of nanoadsorbents and their inoculation time. Furthermore, these nanoadsorbents can be used as highly efficient separable and reusable materials for removal of toxic metal ions.     

Electromagnetic and microwave absorbing properties of magnetite nanoparticles decorated carbon nanotubes/polyaniline multiphase heterostructures

Magnetite nanoparticles decorated CNTs/PANI multiphase heterostructures were prepared by polymerization of aniline monomer and an additional process of the coprecipitation of Fe²⁺ and Fe³⁺. Scanning electron microscopy and transmission electron microscopy observation indicated that the monodispersed magnetite nanoparticles were uniformly decorated on the surface of CNTs/PANI. The formation of magnetite nanoparticles on CNTs/PANI was mainly through a preferentially position-selective precipitation process. More interestingly, a portion of Fe₃O₄ nanoparticles was found to form core–shell structures with PANI. The effects of different additional amounts of NH₂Fe(SO₄)₂·6H₂O reactant on the magnetic properties and microwave absorbing performances of CNTs/PANI/Fe₃O₄ heterostructures were investigated. The CNTs/PANI/Fe₃O₄ multiphase heterostructures were proved to be superparamagnetic. The microwave absorption measurement showed that the CNTs/PANI/Fe₃O₄ samples under 1.5 g of NH₂Fe(SO₄)₂·6H₂O condition exhibited much more effective absorption performance. These results suggested the novel CNTs/PANI/Fe₃O₄ multiphase heterostructures with PANI as the second phase may be potential candidate for microwave absorption systems.     

Characterisation of binary (Fe3O4/SiO2) biocompatible nanocomposites as magnetic fluid

This article describes coating of magnetite nanoparticles (NPs) with amorphous silica shells. Controlled co-precipitation technique under N₂ gas was used to prevent undesirable critical oxidation of Fe²⁺. The synthesised Fe₃O₄ NPs were first coated with trisodium citrate to achieve solution stability and then covered by SiO₂ layer using Stober method. For uncoated Fe₃O₄ NPs, the results showed an octahedral geometry with saturation magnetisation range of 82–96?emu/g and coercivity of 85–120?Oe for particles between 35 and 96?nm, respectively. The best value of specific surface area (41?m²/g) for Fe₃O₄ alone was obtained at 0.9?M NaOH at 750?rpm and it increased to about 81?m²/g for Fe₃O₄/SiO₂ combination. The total thickness and the structure of core–shell was measured and studied by transmission electron microscopy. The average particles size was about 50?nm, indicating the presence of about 15?nm SiO₂ layer. Finally, the stable magnetic fluid contained well-dispersed magnetite-silica nanocomposites which showed monodispersity and fast magnetic response.     

The effect of polyethylenimine on the microwave absorbing properties of a hybrid microwave absorber of Fe3O4/MWNTs

The hybrid microwave absorber of Fe₃O₄/multi-walled carbon nanotubes (MWNTs)modified with polyethylenimine (PEI) polymers was fabricated by chemical co-precipitation. The structure and morphology of hybrids are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron-microscopy (TEM). The effect of PEI on the distribution of Fe₃O₄ nanoparticles and the microwave absorbing properties of hybrid microwave absorber of Fe₃O₄/MWNTs were investigated. The TEM results show that Fe₃O₄ nanoparticles are attached homogeneously on MWNTs, which indicates that the adding of PEI is effective to control the distribution of Fe₃O₄ nanoparticles on the surface of MWNTs. The microwave absorbing properties results show that the maximum reflection loss (RL) of PEI modified Fe₃O₄/MWNTs hybrids is improved significantly, which is ?30.69 dB at 7.24 GHz and ?10 dB bandwidth is 1.84 GHz. However, the RL of the Fe₃O₄/MWNTs without PEI is ?21.96 dB at 7.02 GHz and ?10 dB bandwidth is 1.2 GHz.     

Encapsulation of magnetic nanoparticles with polystyrene via emulsifier-free miniemulsion polymerization

Magnetite nanoparticles (Fe₃O₄), with an average size of about 10 nm, were encapsulated with polystyrene using a new method based on emulsifier-free miniemulsion polymerization in the presence of 2, 2′ azobis (2-amidinopropane) dihydrochloride (V-50) as a cationic ionizable water-soluble initiator and hexadecane as a hydrophobe. Transmission electron microscopy (TEM) proved the presence of magnetite in polymer particles which appeared to be monodisperse in size, approximately 100-300 nm in diameter, through TEM and scanning electron microscopy (SEM). Thermogravimetric analysis (TGA) measurement was used to determine the percentage of magnetite in the products. The results of emulsifier-free miniemulsion polymerization were compared with those of conventional emulsifier-free emulsion polymerization using (V-50) as the initiator in both cases.