Magnetically Recoverable PEI/Titanate@Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Photocatalysts: Fabrication and Photocatalytic Properties

The magnetically separable ternary polyetherimide/titanate@Fe₃O₄ (PTF) photocatalysts of special heterostructure between magnetite (Fe₃O₄) microspheres and titanates nanosheets modified by polyetherimide (PEI) were successfully fabricated via a simple facile hydrothermal deposition method. The as-prepared photocatalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Transmission electron microscopy and UV-vis diffuse reflectance spectroscopy etc. The results showed that the as-fabricated material had a structure of Fe₃O₄ microspheres coated with titanates nanosheets modified by PEI. The special interfacial contact between 3D microsphere and 2D nanosheets in the nanoarchitectures was formed via electrostatic attraction. Furthermore, the resulted photocatalysts were tested by degradation reaction of methylene blue under visible light irradiation and demonstrated an enhanced performance than the pure Fe₃O₄ microspheres, and the photocatalytic activity enhanced with the molar ratio of Fe₃O₄ microspheres and modified titanate gradually, which was attributed to the expansion of the surface area and the different electrostatic contact between the Fe₃O₄ microspheres and titanate nanosheets. Moreover, the obtained results revealed the high yield magnetic separation and efficient reusability of PTF-5 (96.7%) over 3 times reuse.     

Adsorption of BSA on carbon-coated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> microspheres activated with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride

Carbon-coated Fe₃O₄ (Fe₃O₄/C) microspheres activated with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) were prepared, characterized and applied to adsorb bovine serum albumin (BSA). The prepared magnetic microspheres had spherical core-shell structure with a uniform and continuous carbon coating coupled with activation by EDC, and possessed superparamagnetic characteristics. The experimental results showed that the adsorption amount of BSA on the EDC-activated Fe₃O₄/C (Fe₃O₄/C-EDC) microspheres was higher than that on the Fe₃O₄/C microspheres. The maximum adsorption of BSA on Fe₃O₄/C-EDC microspheres occurred at pH 4.7, which was the isoelectric point of BSA. At low concentrations (below 1.0 M), salt had no noticeable effect on BSA adsorption. The BSA adsorption of Fe₃O₄/C-EDC microspheres had a better fit to the Langmuir model than the Freundlich isotherm and Temkin isotherm model, and the kinetic data were well described by the pseudo-second-order model. The adsorption equilibrium could be reached within 20 min. High desorption efficiency (97.6%) of BSA from Fe₃O₄/C-EDC microspheres was obtained with 0.5 M Na₂HPO₄ (pH 9.4) as the desorbent.     

Preparation and electrochemical performance of spherical Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for Li-ion batteries

Fe₃O₄ nano-powder was prepared by the hydrothermal method. The structure and morphology of the product were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The as-prepared powder has regularly spherical morphology, and the average size of product is about 25 nm. The possible application use of this material as the active mass of anode for rechargeable Li batteries was examined by cyclic voltammeter (CV), galvanostatic charge/discharge. The experimental results showed that this material exhibited large specific capacity at the first cycle, and the discharge and charge capacity retention of this electrode are 37.04% and 48.76%, respectively. Furthermore, the impedance change of Fe₃O₄ electrode under different cycle number and potential was examined.     

Gap-plasmon of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@Ag core-shell nanostructures for highly enhanced fluorescence detection of Rhodamine B

A novel gap-plasmon of Fe₃O₄@Ag core-shell nanoparticles for surface enhanced fluorescence detection of Rhodamine B (RB) was developed. Fe₃O₄@Ag core-shell nanostructures with Ag shell and Fe₃O₄ core were synthetized by self-assembled method with the assistance of 3-mercaptopropyl trimethoxy silane (MPTS). To study the RB fluorescence enhanced by gap-plasmon, the fluorescence properties of RB on the substrates with different nanogap densities were systematically investigated, and the results showed that the fluorescence intensity of RB on Fe₃O₄@Ag core-shell NPs substrate was much stronger than that on bare glass substrate, and the fluorescence intensity was further improved by using multilayer Fe₃O₄@Ag core-shell NPs substrate which had higher nanogap density. Different from the mechanism that is based on the maximum overlap of the surface plasmon resonance (SPR) band and emission band, the mechanism of the fluorescence enhancement in our work is based on the localized surface plasmon (LSP) and the gap plasmon near-field coupling with the Fe₃O₄@Ag core-shell NPs. Besides, the detection limit obtained was as low as 1×10^-7 mol/L, and the Fe₃O₄@Ag core-shell NPs substrate had high selectivity for RB fluorophores. It was demonstrated that the Fe₃O₄@Ag core-shell NPs substrate had activity, good stability, and selectivity for fluorescence detection of RB. And the detection of RB by the surface plasmon enhanced fluorescence was more convenient and rapid than the traditional detection methods in previous works.     

Controllable preparation and superior rate performance of spinel LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> hollow microspheres as cathode material for lithium-ion batteries

Spinel LiMn₂O₄ microspheres and hollow microspheres with adjustable wall thickness have been prepared using controllable oxidation of MnCO₃ microspheres precursors and following solid reactions with lithium salts. Scanning electron microscopy (SEM) investigations demonstrate that the microsphere morphology and hollow structure of precursors are inherited. The effect of hollow structure properties of as-prepared LiMn₂O₄ on their performance as cathode materials for lithium-ion batteries has been studied. Electrochemical performance tests show that LiMn₂O₄ hollow microspheres with small wall thickness exhibit both superior rate capability and better cycle performance than LiMn₂O₄ solid microspheres and LiMn₂O₄ hollow microspheres with thick wall. The LiMn₂O₄ hollow microspheres with thin wall have discharge capacity of 132.7 mA·h·g^-1 at C/10 (14.8 mA·g^-1) in the first cycle, 94.1% capacity retention at C/10 after 40 cycles and discharge capacity of 116.5 mAh·g^-1 at a high rate of 5C. The apparent lithium-ion diffusion coefficient (D _app) of as-prepared LiMn₂O₄ determined by capacity intermittent titration technique (CITT) varies from 10^-11 to 10^-8.5 cm²·s^-1 showing a regular “W” shape curve plotted with test voltages. The Dapp of LiMn₂O₄ hollow microspheres with thin wall has the largest value among all the prepared samples. Both the superior rate capability and cycle stability of LiMn₂O₄ hollow microspheres with thin wall can be ascribed to the facile ion diffusion in the hollow structures and the robust of hollow structures during repeated cycling.     

Solvothermal synthesis and electrochemical properties of octahedral cobalt oxide decorated with Ag<Subscript>2</Subscript>O

Octahedral CoO with nanostructures decorated with Ag nanoparticles was prepared via a facile solvothermal approach. After being annealed at 500 °C for 1 h, an electrochemical capacitor material of Co₃O₄ decorated with Ag₂O was obtained. The cyclic voltammetry and galvanostatic charge-discharge were used to evaluate the electrochemical properties of the as-prepared products. The results indicated that the as-prepared samples exhibited fine pseudo-capacitive performance, and the surface modifications of Ag₂O can significantly increase the capacitance of the Co₃O₄ material. The specific capacitance of Ag₂O/Co₃O₄ composite electrode was up to 217.6 F·g^?1, which was 3.35 times as high as that of pure Co₃O₄. Moreover, Ag₂O/Co₃O₄ composite showed an excellent cycle performance, and 65.3% of specific capacitance was maintained after 200 cycles.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@PAM@NTA-Ni<Superscript>2+</Superscript> Magnetic Composite Nanoparticles for Highly Specific Separation of His-tagged Proteins

A facile approach has been developed to synthesize Fe₃O₄@PAM (polyacrylamide) nanoparticles (NPs) with carboxyl groups on the surfaces by copolymerization with acrylamide and acrylic acid in Fe₃O₄ NPs aqueous suspension. Nitrilotriacetic acid (NTA) was conjugated to the magnetic NPs via well-known carboniimide chemistry using EDC and NHS. The Ni²⁺ ions loaded on the surface of NPs provide abundant docking sites for immobilization of His-tagged green fluorescent proteins (His-tagged GFP). The high magnetic property of Fe₃O₄@PAM@NTA-Ni²⁺ allows an easy separation of the NPs from solution under an external magnetic field, with high His-tagged protein binding capacity (42 μg protein/mg of NPs). The NPs can be recycled for at least four times without significant loss of binding capacity to proteins. These materials show great potential to separate His-tagged protein with low-cost purification at industrial scale.     

Surface organic modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

The surface organic modification of Fe3O4 nanoparticles with silane coupling reagent KH570 was studied. The modified and unmodified nanoparticles were characterized by FT-IR, XPS and TEM. The spectra of FT-IR and XPS revealed that KH570 was coated onto the surface of Fe3O4 nanoparticles to get Fe-O- Si bond and an organic coating layer also was formed. Fe3O4 nanoparticles were spheres partly with mean size of 18,8 nm studied by TEM, which was consistent with the result 17.9 nm calculated by Scherrer＇s equation. KH570 was adsorbed on surface and formed chemistry bond to be steric hindrance repulsion which prevented nanoparticles from reuniting. Then glycol-based Fe3O4 magnetic liquids dispersed stably was gained.     

Preparation and characterization of superparamagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/CNTs nanocomposites dual-drug carrier

Fe₃O₄/carbon nanotubes (Fe₃O₄/CNTs) nanocomposites were prepared by polylol high-temperature decomposition of the precursor ferric chloride and CNTs in liquid triethylene glycol. After surface modification with hexanediamine, folate was covalently linked to the amine group of magnetic Fe₃O₄/CNTs nanocomposites. The products were characterized by Fourier-transform infrared spectroscopy, transmission electron microscopy, and vibrating sample magnetometry. Then Fe₃O₄/CNTs were used as a dual-drug carrier to co-delivery of the hydrophilic drug epirubicin hydrochloride and hydrophobic drug paclitaxel. The results indicated that the Fe₃O₄/CNTs had a favorable release property for epirubicin and paclitaxel, and thus had potential application in tumor-targeted combination chemotherapy.     

Synthesis and characterization of biomimetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/coke magnetic nanoparticles composite material

A composite material (Fe₃O₄/Coke) using coke supported Fe₃O₄ magnetic nanoparticles was successfully prepared via an in-situ chemical oxidation precipitation method and characterized by SEM, XRD, Raman, and FTIR. The results showed that the Fe₃O₄ nanoparticles existed steadily on the surface of coke, with better dispersing and smaller particle size. The catalytic ability of Fe₃O₄/Coke were investigatied by degrading p-nitrophenol (P-NP). The results showed that the apparent rate constant for the P-NP at 1.0 g·L^?1 catalyst, 30 mmol·L^?1 H₂O₂, pH=3.0, 30 °C and the best ratio of Coke/Fe₃O₄ 0.6, was evaluated to be 0.027 min^–1, the removal rate of COD_Cr was 75.47%, and the dissolubility of Fe was 2.42 mg·L^–1. Compared with pure Fe₃O₄, the catalytic ability of Fe₃O₄/Coke in the presence of H₂O₂ was greatly enhanced. And Fe₃O₄/Coke was a green and environmental catalyst with high catalytic activity, showing a good chemical stability and reusability.     

Synthesis and characterization of a new Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> pillared triple-layered perovskite KSr<Subscript>2</Subscript>Nb<Subscript>3</Subscript>O<Subscript>10</Subscript>

A n-Hexyl NH₃Sr₂Nb₃O₁₀ is obtained by the stepwise ion-exchange reaction, then is dispersed in aqueous solution of trinuclear acetato-hydroxo iron (III) nitrate, [Fe₃(OCOCH₃)₇OH·2H₂O]NO₃, and the interlayer potassium cations of the perovskite niobate are exchanged with the partially hydrolyzed trinuclear acetato complex ions. On heating, the exchanged complex ions are converted into iron oxide pillars which keep the perovskite sheets apart. The product is characterized by XRD, SEM, EDAX and surface area measurement respectively. Zhang Hui: Born in 1970 Funded by the National Natural Science Foundation of China (No. 50002007), Major Program of Ministry of Education (No. 0201) and Open Foundation of State Key Lab of Advanced Tech. for Materials Synthesis and Processing.     

Synthesis of polyaniline-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocomposites and their conductivity and magnetic properties

By using inorganic Fe₃O₄ nanoparticles of different content as nucleation sites, PAn-Fe₃O₄ nanorods were successfully synthesized through a simple, conventional, and inexpensive one-step in-situ polymerization method. The TEM images revealed the size and morphology of the resultant nanocomposite. The EDS pattern confirmed the existence of Fe₃O₄ in the composite. The FT-IR spectral analysis confirmed the formation of PAn encapsulated Fe₃O₄ nanocomposite. With the content of Fe₃O₄ increasing, the conductivity of the nanocomposites gradually decreases, meanwhile, the saturation magnetization increases and reveals a super paramagnetic behavior. With controllable electrical, magnetic, and electromagnetic properties, the well-prepared nanocomposites may have the potential applications in chemical sensors, catalysis, microwave absorbing, and electro-magneto-rheological fluids, etc.     

Optical and magnetic properties of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> nano-composite films

Fe₂O₃/SiO₂ nano-composite films were prepared by sol-gel technique combining heat treatment in the range of 100–900 °C. The particle size was observed by FE-SEM. Optical properties of the films were investigated by UV-visible spectra. Structural and magnetic characteristics were investigated through FT-IR and VSM. The transparency of the Fe₂O₃/SiO₂ nano-composite films decreased with the content of the Fe₂O₃. Water and organic solvent in the films were evaporated with heat treatment, so the transparency of the films was enhanced under high temperature. It is also found that the saturation magnetization (M _s) of the films increases with the temperature. As the content of the Fe₂O₃ increases, when the content of the Fe₂O₃ is around 30wt%, the M _s of the films has a maximum value.     

Influences of dopants on microstructure and magnetic properties of (Mg<Subscript>0.476</Subscript>Mn<Subscript>0.448</Subscript>Zn<Subscript>0.007</Subscript>)(Fe<Subscript>1.997</Subscript>Ti<Subscript>0.002</Subscript>)O<Subscript>4</Subscript> ferrites

Influences of addition of CaO, CoO and V2O5 on the microstructure and magnetic properties of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites were investigated. The powders of (Mg0.476Mn0.448Zn0.007) (Fe1.997Ti0.002)O4 composition were prepared by using a conventional ceramic powder processing technique. The experimental results showed that the average grain size of the sintered ferrites codoped with 0.03wt% CaO, 0.04wt% CoO and 0.06wt% V2O5 was about 15 μm; the saturation magnetization of ferrites was 68.78 emu/g. The addition of V2O5 in the ferrites can not only increase value of the saturation magnetization, but also decrease the average grain size of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites. Simultaneous incorporation of CoO, CaO and V2O5 dopants into (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites can not only improve the saturation magnetization of the materials, but also inhibit abnormal grain growth.     

Controlled synthesis and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> walnut spherical particles and octahedral microcrystals

Magnetite Fe₃O₄ walnut spherical particles and octahedral microcrystals were successfully synthesized from K₄ [Fe (CN)₆], K₃ [Fe (CN)₆] and NaOH reagents via a simple hydrothermal process. And the uniform morphology of octahedral microcrystals was obtained in the presence of ethylene glycol. The morphology and structure of products were characterized by powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results showed that the Fe₃O₄ walnut spherical particles and octahedral microcrystals were single crystals with the face-center cubic structure and with size distributions from 2.2 to 8.6 μm and 1.6 to 12.5 μm, respectively. Their magnetic properties were detected by a vibrating sample magnetometer at room temperature. The walnut spherical particles exhibited a ferromagnetic behavior with the coercive force (Hc), saturation magnetization (Ms) and remanent magnetization (Mr) being 150.57 Oe, 97.634 and 12.05 emu/g, respectively. For the octahedral microcrystals they were 75.28 Oe, 101.90 and 6.69 emu/g, respectively. Different sizes of walnut spherical particles were controlled synthesized through adjusting the NaOH concentration. It was found that ethylene glycol molecules have a significant effect on the formation of Fe₃O₄ octahedra. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ products. Supported by Fund of weinan Teachers University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Facile synthesis of nanocrystalline Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> thin film

A novel and facile synthesis route for the manufacture of transparent and uniform self-assembled nanocrystalline Cr2O3 (nc-Cr2O3) thin films with different morphology was reported, utilizing chromium nitrate as the inorganic source and triblock copolymer F127 as the morphology-directing agent by the evaporation-induced assembly (EIA) method. X-ray powder diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC), N2-sorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the as-prepared nc-Cr2O3 thin films. The Cr2O3 thin film with different morphology was obtained by changing the relative humidity. The possible formation mechanism of the nc-Cr2O3 thin films with different morphologies was discussed.     

Thermal stability of LiFePO<Subscript>4</Subscript>/C-LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> blended cathode materials

Safety is important to lithium ion battery materials. The thermal stability of LiFePO₄/C-LiMn₂O₄ blended cathode materials is characterized by using TG, XRD, and SEM etc. The results show that LiFePO₄/C-LiMn₂O₄ possesses a worse thermal stability than pure spinel LiMn₂O₄ and pure olivine LiFePO₄/C. When LiFePO₄/C-LiMn₂O₄ blended cathode materials are sintered at 500°C under Ar atmosphere, the sintered cathode materials emit O₂, and appear impurity phases (Li₃PO₄, Fe₂O₃, Mn₃O₄). It is deduced that some chemical reactions take place between different materials, which leads to a worse discharge specific capacity. LiFePO₄/C-LiMn₂O₄ blended cathode materials, therefore, need to be managed and controlled strictly for the sake of thermal stability and safety.     

Modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles by L-dopa or dopamine as an enzyme support

Fe3O4 magnetic nanoparticles were prepared by co-precipitation of Fe^2＋ and Fe^3＋ in an ammonia solution, and its size was about 36 nm measured by an atomic force microscope. Fe3O4 magnetic nanoparticles were modified by L-dopa or dopamine using sonication method. The analysis of FTIR clearly indicated the formation of Fe-O-C bond. Direct immobilization of trypsin （EC： 3.4.21.4） on Fe3O4 magnetic nanoparticles with L-dopa and dopamine spacer was investigated using glutaraldehyde as a coupling agent. No significant changes in the size and magnetic property of the three kinds of magnetic nanoparticles linked with or without trypsin were observed. The existence of the spacer molecule on magnetic nanoparticles could greatly improve the activity and the storage stability of bound trypsin through increasing the flexibility of enzyme and changing the microenvironment on nanoparticles surface compared to the naked magnetic nanoparticles.     

Electrochemical behavior of magnolol on FeWO<Subscript>4</Subscript> nanoflower modified carbon paste electrode

In order to establish a simple, sensitive, and fast reliable detection method to determine the magnolol, FeWO₄ nanoflower was synthesised through a solvothermal technique and FeWO₄ nanoflower modified carbon paste electrode (CPE) was developed. The voltammetric behavior of magnolol on the modified electrodes was studied using cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV). The experimental results showed that the modified electrode remarkably enhanced the electrochemical response of the magnolol and exhibited a wide linear range for determination of the magnolol from 1.0×10^-7 to 1.0×10^-4 mol/L with a low detection limit of 5.0×10^-8 mol/L.     

Direct synthesis of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-modified Li(Ni<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>)O<Subscript>2</Subscript> cathode materials for lithium ion batteries

To improve the cyclic stability at high temperature and thermal stability, the spherical Al₂O₃-modified Li(Ni_0.5Co_0.2Mn_0.3)O₂ was synthesized by a modified co-precipitation method, and the physical and electrochemical properties were studied. The TEM images showed that Li(Ni_0.5Co_0.2Mn_0.3)O₂ was modified successfully with nano-Al₂O₃. The discharge capacity retention of Al₂O₃-modified Li(Ni_0.5Co_0.2Mn_0.3)O₂ maintained about 99% after 200 cycles at high temperature (55 °C), while that of the bare one was only 86%. Also, unlike bare Li(Ni_0.5Co_0.2Mn_0.3)O₂, the Al₂O₃-modified material cathode exhibited good thermal stability.