H<Subscript>3</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript> immobilized chitosan/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> as a novel efficient,green and recyclable nanocatalyst in the synthesis of pyrano-pyrazole derivatives

A novel nanomagnetic composite heteropolyacid immobilized chitosan/Fe₃O₄ was prepared via a facile one-pot synthetic approach. This magnetically recoverable nanocatalyst, H₃PMo₁₂O₄₀/chitosan/Fe₃O₄ (PMo/chit/Fe₃O₄), was fully characterized by XRD, FTIR, SEM and EDX analysis methods. A rapid, efficient and the chemoselective synthesis of different pyrano-pyrazole derivatives was achieved in excellent yields via a one-pot four-component reaction in the presence of catalytic amount of PMo/Chit/Fe₃O₄.     

Nonstoichiometric Zn Ferrite and ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Composite Spheres: Preparation,Magnetic Properties,and Chromium Removal

Monodisperse and porous nonstoichiometric Zn ferrite can be prepared by a solvothermal method. Such non-Zn ferrite was used to be the precursor for synthesis of ZnFe₂O₄/Fe₂O₃ composite via calcination at 600°C for 3 h in air. X-ray powder diffractometer (XRD) and Energy Dispersive Spectrometer (EDS) proved the nonstoichiometry of Zn ferrite synthesized by solvothermal method and the formation of ZnFe₂O₄/Fe₂O₃ composite via calcination. TEM image showed that non-Zn ferrite spheres with wormlike nanopore structure were made of primary nanocrystals. BET surface area of non-Zn ferrite was much higher than that of ZnFe₂O₄/Fe₂O₃ composite. Saturation magnetization of non-Zn ferrites was significantly higher than that of ZnFe₂O₄/Fe₂O₃ composites. Calcination of non-Zn ferrite resulted in the formation of large amount of non-magnetic Fe₂O₃,which caused a low magnetization of composite. Because of higher BET surface area and higher saturation magnetization, non-Zn ferrite presented better Cr⁶⁺ adsorption property than ZnFe₂O₄/Fe₂O₃ composites.     

Optical,magnetic and photocatalytic properties of magnetically separable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-doped ZnO and pristine ZnO nanospheres

This work focussed on the optical, magnetic and photocatalytic properties of sol–gel-synthesized Fe₃O₄-doped ZnO nanospheres and was compared with pristine ZnO nanospheres. The crystalline phase of Fe₃O₄-doped ZnO nanospheres was studied with X-ray diffraction analysis and was well matched with standard pattern. Surface morphology was studied with HR-SEM images and EDAX spectrum. Furthermore, elemental mapping analysis was carried out to confirm the presence of Fe₃O₄ phase in Fe₃O₄-doped ZnO nanospheres. FT-Raman spectral studies show that a strong intense peak at 670 cm^?1 indicates the presence of Fe₃O₄ in Fe₃O₄-doped ZnO nanospheres. The mean crystallite size of Fe₃O₄-doped ZnO nanospheres was 34 nm as calculated by Debye–Scherrer’s formula which confirmed with HR-TEM image. The SAED pattern shows the presence of (100), (101), (102) and (202) of ZnO phase and (400) of Fe₃O₄ phase, confirming the crystalline nature of Fe₃O₄-doped ZnO nanospheres. The vibrating sample magnetometer (VSM) result shows that Fe₃O₄-doped ZnO nanospheres possess superparamagnetic nature and the composite nanospheres are magnetically separable. The optical properties have been studied by diffuse reflectance spectroscopy and time-resolved photoluminescence spectra. Implantation of Fe₃O₄ in ZnO nanospheres modifies the UV absorption edge, and it displays near-band gap emission and deep-level emission. The photocatalytic activity of Fe₃O₄-doped ZnO nanospheres studied against rhodamine B dye is found higher than that of pristine ZnO nanospheres which shows that Fe₃O₄-doped ZnO nanospheres are a promising photocatalyst.     

Comparison of the Solubility of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> in High Temperature Water

As the solubility is a direct measure of stability, this study compares the solubilities of ZnFe₂O₄, Fe₃O₄ and Fe₂O₃ in high temperature water. Through literature analysis and formula derivation, it is shown that it is reasonable to assume ZnFe₂O₄ and Fe(OH)₃ coexist when ZnFe₂O₄ is dissolved in water. Results indicated that the solubility of ZnFe₂O₄ is much lower than that of Fe₂O₃ or Fe₃O₄. The low solubility of ZnFe₂O₄ indicates that it is more protectively stable as an anticorrosion phase. Moreover, the gap between the solubility of ZnFe₂O₄ and that of Fe₃O₄ or Fe₂O₃ was enlarged with an increase of temperature. This means that ZnFe₂O₄ is more protective at higher temperatures. Further analysis indicated that with the increase of temperature, the solubility of ZnFe₂O₄ changed little while those of Fe₂O₃ or Fe₃O₄ changed a lot. Little change of the solubility of ZnFe₂O₄ with increase of temperature showed that ZnFe₂O₄ is stable. The very low and constant solubility of ZnFe₂O₄ suggests that it is more protective than Fe₂O₃ and Fe₃O₄, especially in water at higher temperature.     

Effect of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on structure and magnetic properties of Ni<Subscript>0.5</Subscript>Zn<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanofibers

Ni_0.5Zn_0.5Fe₂O₄ nanofibers with addition of 0–5 wt% Bi₂O₃ were synthesized by calcination of the electrospun polyvinylpyrrolidone/inorganic composite nanofibers at the temperature below the melting point of Bi₂O₃. The effects of Bi₂O₃ addition on the phase structure, morphology and magnetic properties of the nanofibers were investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, selected area electron diffraction and vibrating sample magnetometer. It is found that the nanofiber diameter, crystallite size and magnetic parameters can be effectively tuned by simply adjusting the amount of Bi₂O₃ addition. The average diameter of Ni_0.5Zn_0.5Fe₂O₄ nanofibers doped with different contents of Bi₂O₃ ranges from 40 to 63 nm and gradually decreases with increasing Bi₂O₃ content. The addition of Bi₂O₃ does not induce the phase change and all the samples are a single-phase spinel structure. The amorphous Bi₂O₃ tends to concentrate on the nanoparticle surface and/or grain boundary and can retard the particles motion as well as the grain growth, resulting in a considerable reduction in grain size compared to the pristine sample. The specific saturation magnetization and coercivity of the nanofibers gradually decrease with the increase of Bi₂O₃ amount. Such behaviors are explained on the basis of chemical composition, surface effect, domain structure and crystal anisotropy.     

Adsorption behavior of <Superscript>99</Superscript>Tc on Fe,Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>

Summary The adsorption of ⁹⁹Tc on the adsorbers Fe, Fe₂O₃ and Fe₃O₄ was studied by batch experiments under aerobic and anoxic conditions. The effects of pH and CO₃^2- concentration of the simulated ground water on the adsorption ratios were also investigated, and the valences of Tc in solution after the adsorption equilibrium were studied by solvent extraction. The adsorption isotherms of TcO₄- on the adsorbers Fe, Fe₂O₃ and Fe₃O₄ were determined. Experimental results have shown that the adsorption ratio of Tc on Fe decreases with the increase of pH in the range of 5-12 and increases with the decrease of the CO₃^2- concentration in the range of 10^-8M-10^-2M. Under aerobic conditions, the adsorption ratios of ⁹⁹Tc on Fe₂O₃ and Fe₃O₄ were not influenced by pH and CO₃^2-concentration. When Fe was used as adsorbent, Tc existed mainly in the form of Tc(IV) after equilibrium and in the form of Tc(VII) when the adsorbent was Fe₂O₃ or Fe₃O₄ under aerobic conditions. The adsorption ratios of Tc on Fe, Fe₂O₃ and Fe₃O₄ decreased with the increase of pH in the range of 5-12 and increased with the decrease of the CO₃^2- concentration in the range of 10^-8M-10^-2M under anoxic conditions. Tc existed mainly in the form of Tc(IV) after equilibrium when Fe, Fe₂O₃ and Fe₃O₄ was the adsorbent under anoxic conditions. The adsorption isotherms of TcO_4- on the adsorbers Fe, Fe₂O₃ and Fe₃O₄ are fairly in agreement with the Freundlich’s equation under both aerobic and anoxic conditions.     

One-Pot Synthesis of Novel Amino-Functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Hybrid Microspheres for Cu(II) Removal from Aqueous Solutions

In this work, we report the development of novel amino-functionalized Fe₃O₄ hybrid microspheres adsorbent from a facial and one-step solvothermal route by using FeCl₃·6H₂O as a single iron source and 3-aminophenoxy-phthalonitrile as ource of amino groups. During solvothermal process, the nitrile groups of 3-aminophenoxy-phthalonitrile would bond with the Fe₃O₄ through the phthalocyanine cyclization reaction to form the amino-functionalized Fe₃O₄ magnetic nano-material, which was confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermo-gravimetric analyzer (TGA). From the scanning electron microscope (SEM) and transmission electron microscopy (TEM) observation, the resulting monodispersed amino-functionalized Fe₃O₄ hybrid microspheres with the diameters of 180–200 nm were synthesized via the self-assembly process. More importantly, as-prepared Fe₃O₄ nano-materials with abundant amino groups exhibited high separation efficiency when they were used to remove the Cu(II) from aqueous solutions. Furthermore, the adsorption isotherms of Fe₃O₄ nano-material for Cu(II) removal fitted the Langmuir isotherm model, in which the calculated maximum adsorption capacity could increase from 5.51 to 16.25 mg g^–1 at room temperature. This work demonstrated that the amino-functionalized Fe₃O₄ magnetic nano-materials were promising as efficient adsorbents for the removal of heavy metal ions from wastewater in low concentration.     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Thiol-functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> microspheres with superparamagnetism and their adsorption properties for Au(III) ion separation

Thiol-functionalized Fe₃O₄/SiO₂ microspheres (Fe₃O₄/SiO₂-SH) with high saturation magnetization (69.3 emu g^–1), superparamagnetism, and good dispersibility have been prepared by an ethylene glycol reduction method in combination with a modified Stöber method. The as-prepared composite magnetic spheres are characterized with fourier transform infrared spectroscopy (FT-IR), zeta potential, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and superconducting quantum interference magnetometer, and tested in separation of Au(III) ions from aqueous solutions. The data for Au(III) adsorption on Fe₃O₄/SiO₂-SH are analyzed with the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models, and the pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetics models. The adsorption behaviors of Au(III) on Fe₃O₄/SiO₂-SH follow the Langmuir isotherm model, and the adsorption process conforms to the pseudo-second-order kinetic model. The maximum adsorption capacity of Au(III) on Fe₃O₄/SiO₂-SH is 43.7 mg g^–1. Acetate anions play an important role yet Cu(II) ions have little interference in the adsorption of Au(III) on the adsorbent. A satisfactory recovery percentage of 89.5% is acquired by using an eluent with 1 M thiourea and 5% HCl, although thiols have a high affinity to Au(III) ions based on the hard-soft acid-base (HSAB) theory by Pearson.     

Synthesis and characterization of Ni<Subscript>0.6</Subscript>Zn<Subscript>0.4</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nano-particles obtained by auto catalytic thermal decomposition of carboxylato-hydrazinate complex

Ni_0.6Zn_0.4Fe₂O₄ nano-particles have been synthesized by self-propagating auto-combustion of nickel zinc ferrous fumarato-hydrazinate complex. The precursor complex has been characterized by chemical analysis, IR, AAS, thermal analysis and isothermal mass loss studies. The precursor on ignition undergoes self-propagating auto combustion to give Ni_0.6Zn_0.4Fe₂O₄. The X-ray diffraction studies confirmed the single phase formation of nano-size ‘as synthesized’ Ni_0.6Zn_0.4Fe₂O₄. TEM observation showed the average particle size to be 20 nm. Infrared and magnetization studies were also carried out on the ‘as synthesized’ Ni_0.6Zn_0.4Fe₂O₄. The lower value of saturation magnetization and higher Curie temperature of ‘as synthesized’ ferrite also hint at the nano size nature.     

Preparation and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>composite particles

Using Fe₃O₄ nano-particles as seeds, a new type of Fe₃O₄/Au composite particles with core/shell structure and diameter of about 170 nm was prepared by reduction of Au³⁺ with hydroxylamine in an aqueous solution. Particle size analyzer and transmission electron microscope were used to analyze the size distribution and microstructure of the particles in different conditions. The result showed that the magnetically responsive property and suspension stability of Fe₃O₄ seeds as well as reduction conditions of Au³⁺to Au⁰are the main factors which are crucial for obtaining a colloid of the Fe₃O₄/Au composite particles with uniform particle dispersion, excellent stability, homogeneity in particle sizes, and effective response to an external magnet in aqueous suspension solutions. UV-Vis analysis revealed that there is a characteristic peak of Fe₃O₄/Au fluid. For particles with d(0.5)=168 nm, the λmax is 625 nm.     

Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.     

Catalytic Properties of TiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles in Plasma Chemical Treatment

We proposed here a new process coupling dielectric barrier discharge (DBD) plasma with magnetic photocatalytic material nanoparticles for improving yield in DBD degradation of methyl orange (MO). TiO₂ doped Fe₃O₄ (TiO₂/Fe₃O₄) was prepared by the sol-gel method and used as a new type of magnetic photocatalyst in DBD system. It was found that the introduction of TiO₂/Fe₃O₄ in DBD system could effectively make use of the energy generated in DBD process and improve hydroxyl radical contributed by the main surface Fenton reaction, photocatalytic reaction and catalytic decomposition of dissolved ozone. Most part of MO (88%) was degraded during 30 min at peak voltage of 13 kV and TiO₂/Fe₃O₄ load of 100 mg/L, with a rate constant of 0.0731 min^?1 and a degradation yield of 7.23 g/(kW h). The coupled system showed higher degradation efficiency for MO removal.     

Synthesis and Characterization of the Superparamagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Ag Nanocomposites

The study of superparamagnetic Fe₃O₄/Ag nanocomposites have received great research attention due to their wide range of potential applications in biomedicine. In this report, an easy microemulsion reaction was employed to synthesis Fe₃O₄/Ag nanocomposites with self-aggregated branch like nanostructures. The Fe₃O₄ nanoparticles were initially prepared and subsequently AgNO₃ was reduced as Ag by chemical reduction method. The results showed that the average size of the Fe₃O₄/Ag nanocomposites were in the range of 10 ± 2 nm. These nanoparticles were self-aggregated as a branch like nanostructure. The optical properties of Fe₃O₄ nanoparticles were modified with surface plasmon resonance of Ag nanoparticles. The observed saturation magnetization of superparamagnetic Fe₃O₄/Ag nanocomposites were 40 emu/g.     

The hemoglobin-modified electrode with chitosan/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocomposite for the detection of trichloroacetic acid

A hemoglobin (Hb)-modified electrode based on chitosan/Fe₃O₄ nanocomposite coated glassy carbon has been constructed for trichloroacetic acid (TCA) detection. The structure of chitosan/Fe₃O₄ nanocomposite was investigated using energy-dispersive X-ray analysis (EDS) and X-ray diffraction (XRD) patterns. The electron transfer rate constant (k _s) of Hb was estimated for as high as 3.12 s^?1. The immobilized Hb exhibited excellent electro-catalytic activity toward the reduction of TCA. The response current regressed to the concentration of TCA within the range of 5.70 μM to 205 μM with a detection limit of 1.9 μM (S/N = 3).     

Formation and thermal properties of nanocrystalline Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>

Mechanism by which nanocrystalline Bi₄Ti₃O₁₂ is formed in thermal treatment of coprecipitated hydroxides was studied. It was shown that the onset of the active formation is correlated with the melting point of the surface phase based on bismuth oxide. The technological synthesis parameters of Bi₄Ti₃O₁₂, at which crystallite sizes in the range 35–60 nm are provided, were determined.     

Facile ultrasonic-assisted preparation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Ag<Subscript>3</Subscript>VO<Subscript>4</Subscript> nanocomposites as magnetically recoverable visible-light-driven photocatalysts with considerable activity

In this work, a facile ultrasonic-assisted method was applied for preparation of Fe₃O₄/Ag₃VO₄ nanocomposites with different compositions. The as-prepared products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive analysis of X-rays, UV–Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometery. Photocatalytic degradation of rhodamine B under visible-light irradiation was investigated, and it was found that weight ratio of Fe₃O₄–Ag₃VO₄ has significant influence on the photocatalytic activity and the nanocomposite with 1:4 weight ratio of Fe₃O₄–Ag₃VO₄ has superior activity. In addition, the nanocomposite showed great activities in degradations of methylene blue and fuchsine, which are comparable with activity of the pure Ag₃VO₄. More importantly, this nanocomposite displayed remarkable saturation magnetization, leading to easily and quickly separation of its suspension from treated system by applying a magnetic field.     

Stabilization of Oil-in-Water Emulsions with SiO<Subscript>2</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles

Stabilization of oil-in-water Pickering emulsions with SiO₂ and Fe₃O₄ nanoparticles has been studied. Emulsions containing three-dimensional gel networks formed by aggregated nanoparticles in the dispersion media have been shown to be stable with respect to flocculation, coalescence, and creaming. Concentration ranges in which emulsions are kinetically stable have been determined. Stabilization with mixed Ludox HS-30 and Ludox CL SiO₂ nanoparticles leads to the formation of stable emulsions at a weight ratio between the nanoparticles equal to 2 and pH 6.7. In the case of stabilization with Ludox CL and Fe₃O₄ nanoparticles, systems resistant to aggregation and sedimentation are obtained at pH 8. The use of mixed Ludox HS-30 and Fe₃O₄ nanoparticles has not resulted in the formation of emulsions stable with respect to creaming, with such emulsions appearing to be resistant only to coalescence at pH 2–6.     

Preparation and adsorption of magnetic Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>-chitosan nanoparticles

In this paper, magnetic chitosan microspheres were prepared by the emulsification cross-linking technique, with glutaraldehyde as the cross-linking agent, liquid paraffin as the dispersant, and the Span-80 as emulsifier. The time of cross-linking and the ratio of Co_0.5Ni_0.5Fe₂O₄/chitosan were investigated. The morphology was studied by different instruments. The adsorption performance was investigated and the effects of initial concentration of methyl orange, the time of cross-linking, and the amount of adsorbent were discussed. It is found that the product has uniform morphology when the ratio of magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan is 1 : 2 and the time of cross-linking is 5 h; At room temperature, magnetic Co_0.5Ni_0.5Fe₂O₄–chitosan has a good adsorption toward methyl orange when the magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan dosage is 20 mg.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Au composite nano-particles and their optical properties

Fe₃O₄/Au composite particles with core/shell structure were prepared by reduction of Au³⁺ with hydroxylamine in the presence of an excess of Fe₃ O₄ as seeds. The resultant colloids, with an average diameter of less than 100 nm, were obtained; the remaining non-reacted Fe₃O₄ seeds can be removed by treatment with diluted HCl solution. The Fe₃O₄/Au colloids exhibit a characteristic peak of UV-visible spectra, which largely depend on the size of the particle and the suspension medium. The localized surface plasmon resonance peaks red shift and broaden with increased nanoparticle diameter or increased solvent ionic strength. The optical property is very important in the establishment of means for the detection of biomolecules.