A novel kojic acid amperometric sensor based on hollow CuO/Fe2O3 hybrid microspheres immobilized in chitosan matrix

Hollow CuO/Fe₂O₃ hybrid microspheres with small uniform holes were synthesized using a convenient hydrothermal method and were applied to fabricated an amperometric sensor for kojic acid. The resulting materials were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) and then were immobilized into the chitosan (Chi) matrix onto a glassy carbon electrode to obtain CuO/Fe₂O₃–Chi/GCE. The potential utility of the constructed electrodes were demonstrated by applying them to the analytical determination of kojic acid concentration. The electrochemical behavior of kojic acid on CuO/Fe₂O₃–Chi/GCE was explored. The modified electrode displayed excellent amperometric response for kojic acid with a linear range from 0.2 μM to 674 μM with a detection limit of 0.08 μM at a signal-to-noise ratio of 3. In order to validate feasibility, the CuO/Fe₂O₃–Chi/GCE has been used for quantitative detecting kojic acid in real samples.     

A novel platform of hemoglobin on core–shell structurally Fe3O4@Au nanoparticles and its direct electrochemistry

A novel platform, which hemoglobin (Hb) was immobilized on core–shell structurally Fe₃O₄/Au nanoparticles (simplified as Fe₃O₄@Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe₃O₄@Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope (SEM) and energy dispersive spectra (EDS), were coated onto GCE mediated by chitosan so as to provide larger surface area for anchoring Hb. The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe₃O₄@Au NPs were discussed by UV–visible spectrum (UV–vis), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance technique (EQCM) and cyclic voltammetry (CV). The electrochemical parameters of Hb on Fe₃O₄@Au NPs modified GCE were further carefully calculated with the results of the effective working area as 3.61 cm², the surface coverage concentration (Γ) as 1.07 × 10⁻¹² mol cm⁻², the electron-transfer rate constant (K_s) as 1.03 s⁻¹, the number of electron transferred (n) as 1.20 and the standard entropy of the immobilized Hb (ΔS⁰′) as calculated to be −104.1 J mol⁻¹ K⁻¹. The electrocatalytic behaviors of the immobilized Hb on Fe₃O₄@Au NPs were applied for the determination of hydrogen peroxide (H₂O₂), oxygen (O₂) and trichloroacetic acid (TCA). The possible functions of Fe₃O₄ core and Au shell as a novel platform for achieving Hb direct electrochemistry were discussed, respectively.     

Functionalized magnetic core-shell Fe3O4@SiO2 nanoparticles as selectivity-enhanced chemosensor for Hg(II)

A colorimetric and ‘‘turn-on” fluorescent chemosensor Rho-Fe₃O₄@SiO₂ for Hg²⁺ in which N-(rhodamine-6G)lactam-ethylenediamine (Rho-en) is conjugated with the magnetic core-shell Fe₃O₄@SiO₂ NPs has been strategically designed and synthesized. The final product was characterized by X-ray power diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR) and UV-visible absorption and fluorescence emission. Fluorescence and UV-visible spectra results showed that the resultant multifunctional nanoparticles Rho-Fe₃O₄@SiO₂ exhibited selective ‘turn-on’ type fluorescent enhancements and distinct color changes with Hg²⁺. The selectivity of the Rho-Fe₃O₄@SiO₂ for Hg(II) ion is better than that of the Rho-en in the same conditions. In addition, the presence of magnetic Fe₃O₄ nanoparticles in the sensor Rho-Fe₃O₄@SiO₂ NPs would also facilitate the magnetic separation of the Hg(II)-Rho-Fe₃O₄@SiO₂ from the solution.     

磁性Fe3O4纳米粒子用作靶向药物载体的制备及分析

Fe3O4 magnetic nanoparticles were prepared by the aqueous co-precipitation of FeCl3-6H2O and FeCl2-4H2O with addition of ammonium hydroxide. The conditions for the preparation of Fe3O4 magnetic nanoparticles were optimized, and Fe3O4 magnetic nanoparticles obtained were characterized systematically by means of transmission electron microscope （TEM）, dynamic laser scattering analyzer （DLS） and X-ray diffraction （XRD）. The results revealed that the magnetic nanoparticles were cubic shaped and dispersive, with narrow size distribution and average diameter of 11.4 nm. It was found that the homogeneous variation of pH value in the solution via the control on the dropping rate of aqueous ammonia played a critical role in size distribution. The magnetic response of the product in the magnetic field was also analyzed and evaluated carefully. A 32.6 mT magnetic field which is produced by four ferromagnets was found to be sufficient to excite the dipole moments of 0.05 g Fe3O4 powder 2 cm far away from the ferromagnets. In conclusion, the Fe3O4 magnetic nanoparticles with excellent properties were competent for the magnetic carders of targeted-drug in future application.     

Multifuctional Fe3O4@C/YVO4:Dy nanopowers: Preparation,luminescence and magnetic properties

As-synthesized Fe₃O₄ nanoparticles were encapsulated with carbon layers through a simple hydrothermal process. Fe₃O₄/C nanoparticles were coated with YVO₄:Dy³⁺ phosphors to form bifunctional Fe₃O₄@C@YVO₄:Dy³⁺ composites. Their structure, luminescence and magnetic properties were characterized by XRD, SEM, TEM, HRTEM, PL spectra and VSM. The experimental results indicated that the as-prepared bifunctional composites displayed well-defined core–shell structures. The ∼12 nm diameter YVO₄:Dy³⁺ shell exhibited tetragonal structure. Additionally, the composites exhibited a high saturation magnetization (13 emu/g) and excellent luminescence properties, indicating their promising potential as multifunctional biosensors for biomedical applications.     

A novel method for the synthesis of Fe3O4 nanoparticles/CdS nanowires heterostructure nanocomposite and uses in photodegradation of methylene blue

We report here a simple, efficient, practical, and novel method for the preparation of Fe₃O₄ nanoparticles (NPs)/CdS nanowires. The CdS nanowire/Fe₃O₄ NP reported here was characterized by transmission electron microscopy (TEM), X-ray Diffraction (XRD), vibrating sample magnetometer (VSM), and energy-dispersive X-ray. Cadmium diethyl dithiophosphate has been used as a 3 in 1 precursor (cadmium, sulfur, and ligand source) for the synthesis of high-quality one-dimensional Fe₃O₄ NPs/CdS nanowires using a simple hydrothermal method in the presence of Fe₃O₄ NPs in water. Photocatalytic activity studies show that the nanocomposite has good photocatalytic activity toward the photodegradation of methylene blue in an aqueous solution.     

Synthesis of magnetic Pb/Fe3O4/SiO2 and its catalytic activity for propylene carbonate synthesis via urea and 1,2-propylene glycol

To facilitate the recovery of Pb/SiO₂ catalyst, magnetic Pb/Fe₃O₄/SiO₂ samples were prepared separately by emulsification, sol-gel and incipient impregnation methods. The catalyst samples were characterized by means of X-ray diffraction and N₂ adsorption-desorption, and their catalytic activity was investigated in the reaction for synthesizing propylene carbonate from urea and 1,2-propylene glycol. When the gelatin was applied in the preparation of Fe₃O₄ at 60°C and the pH value was controlled at 4 in the preparation of Fe₃O₄/SiO₂, the Pb/Fe₃O₄/SiO₂ sample shows good catalytic activity and magnetism. Under the reaction conditions of a reaction temperature of 180°C, reaction time of 2 h, catalyst percentage of 1.7 wt-% and a molar ratio of urea to PG of 1:4, the yield of propylene carbonate attained was 87.7%.     

Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes

The impedance rise that results from the accelerated aging of high-power lithium-ion cells containing LiNi_0.8Co_0.15Al_0.05O₂-based positive and graphite-based negative electrodes is dominated by contributions from the positive electrode. Data from various diagnostic experiments have indicated that a general degradation of the ionic pathway, apparently caused by surface film formation on the oxide particles, produces the positive electrode interface rise. One mechanistic hypothesis postulates that these surface films are components of the negative electrode solid electrolyte interphase (SEI) layer that migrate through the electrolyte and separator and subsequently coat the positive electrode. This hypothesis is examined in this article by subjecting cells with LiNi_0.8Co_0.15Al_0.05O₂-based positive and Li_4/3Ti_5/3O₄-based negative electrodes to accelerated aging. The impedance rise in these cells was observed to be almost entirely from the positive electrode. Because reduction products are not expected on the 1.55 V Li_4/3Ti_5/3O₄ electrode, the positive electrode impedance cannot be attributed to the migration of SEI-type fragments from the negative electrode. It follows then that the impedance rise results from mechanisms that are “intrinsic” to the positive electrode.     

Mixed oxides Ca2Fe2O5 and Ca2Co2O5 as anode materials for Li-ion batteries

The electrochemical performance of mixed oxides, Ca₂Fe₂O₅ and Ca₂Co₂O₅ for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca₂Fe₂O₅ showed a reversible capacity of 226 mAh/g at the 14th cycle and retained 183 mAh/g at the end of 50 cycles at 60 mA/g in the voltage window 0.005-2.5 V. A reversible capacity in the range, 365-380 mAh/g, which is stable up to 50 charge-discharge cycles is exhibited by Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V and at 60 mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca₂Co₂O₅ on cycling to an upper cut-off voltage of 3.0 V as compared to 2.5 V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V. Cyclic voltammetry results compliment the galvanostatic cycling data.     

Structure and electrochemical performance of nanostructured Fe3O4/carbon nanotube composites as anodes for lithium ion batteries

Polyvinyl alcohol (PVA) was used as a hydrogen bond functionalizing agent to modify multi-walled carbon nanotubes (CNTs). Nanoparticles of Fe₃O₄ were then formed along the sidewalls of the as-modified CNTs by the chemical coprecipitation of Fe²⁺ and Fe³⁺ in the presence of CNTs in an alkaline solution. The structure and electrochemical performance of the Fe₃O₄/CNTs nanocomposite electrodes have been investigated in detail. Electrochemical tests indicated that at the 145th cycle, the CNTs-66.7 wt.%Fe₃O₄ nanocomposite electrode can deliver a high discharge capacity of 656 mAh g⁻¹ and stable cyclic retention. The improvement of reversible capacity and cyclic performance of the Fe₃O₄/CNTs nanocomposite could be attributed to the nanosized Fe₃O₄ particles and the network of CNTs.     

The Effect of Trehalose Coating for Magnetite Nanoparticles on Stability of Egg White Lysozyme

In this study, the protein stability of hen egg-white lysozymes (HEWL) by Fe₃O₄ and Fe₃O₄-coated trehalose (Fe₃O₄@Tre) magnetic nanoparticles (NPs) is investigated. For this purpose, the co-precipitation method was used to synthesize magnetic NPs. The synthesized NPs were characterized by XRD, FT-IR spectroscopy, FE-SEM, and VSM analysis. In addition, the stability of HEWLs exposed to different NP concentrations in the range of 0.001–0.1 mg mL⁻¹ was investigated by circular dichroism (CD) spectroscopy, fluorescence, and UV-Vis analysis. Based on the results, in the NP concentration range of 0.001–0.04 mg mL⁻¹ the protein structure is more stable, and this range was identified as the range of kosmotropic concentration. The helicity was measured at two concentration points of 0.02 and 0.1 mg mL⁻¹. According to the results, the α-helix at 0.02 mg mL⁻¹ of Fe₃O₄ and Fe₃O₄@Tre was increased from 35.5% for native protein to 37.7% and 38.7%, respectively. The helicity decreased to 36.1% and 37.4%, respectively, with increasing the concentration of Fe₃O₄ and Fe₃O₄@Tre to 0.1 mg mL⁻¹. The formation of hydrated water shells around protein molecules occurred by using Fe₃O₄@Tre NPs. Hence, it can be concluded that the trehalose as a functional group along with magnetic NPs can improve the stability of proteins in biological environments.     

Corrosion mechanisms of Al2O3/MgAl2O4 by V2O5, NiO, Fe2O3 and vanadium slag

The effects of V₂O₅, NiO, Fe₂O₃ and vanadium slag on the corrosion of Al₂O₃ and MgAl₂O₄ have been investigated. The specimens of Al₂O₃ and MgAl₂O₄ with the respective oxides above mentioned were heated at 10 °C/min from room temperature up to three different temperatures: 1400, 1450 and 1500 °C. The corrosion mechanisms of each system were followed by XRD and SEM analyses. The results obtained showed that Al₂O₃ was less affected by the studied oxides than MgAl₂O₄. Alumina was only attacked by NiO forming NiAl₂O₄ spinel, while the MgAl₂O₄ spinel was attacked by V₂O₅ forming MgV₂O₆. It was also observed that Fe₂O₃ and Mg, Ni, V and Fe present in the vanadium slag diffused into Al₂O₃. On the other hand, the Fe₂O₃ and Ca, S, Si, Na, Mg, V and Fe diffused into the MgAl₂O₄ structure. Finally, the results obtained were compared with those predicted by the FactSage software.     

Fabrication of carbon paste electrode containing [PFeW11O39] polyoxoanion supported on modified amorphous silica gel and its electrocatalytic activity for H2O2 reduction

[PFeW₁₁O₃₉]⁴⁻ (PFeW₁₁) supported on the surface of 3-aminopropyl(triethoxy)silane modified silica gel was synthesized and used as a bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The electrochemical behavior of the modified electrode was investigated. Cyclic voltammetry studies showed that the PFeW₁₁ on the electrode surface sustained the same electrochemical properties as that of the PFeW₁₁ in solution. The preparation of chemically modified electrode is simple and quiet reproducible using inexpensive material. The modified electrode had high electrocatalytic activity toward H₂O₂ reduction and it was successfully applied as an electrochemical detector to monitor H₂O₂ in flow injection analysis (FIA). The electrocatalytic peak current was found to be linear with the H₂O₂ concentration in the range 10-200 μmol L⁻¹ with a correlation coefficient of 0.998 and a detection limit (3σ) of 7.4 μmol L⁻¹ H₂O₂. The electrode has the remarkable advantage of surface renewal owing to bulk modification, as well as simple preparation, good mechanical and chemical stability and reproducibility.     

Reduction and oxidation properties of Fe2O3/ZrO2 oxygen carrier for hydrogen production

Fe₂O₃ is a promising oxygen carrier for hydrogen production in the chemical-looping process. A set of kinetic studies on reduction with CH₄, CO and H₂ respectively, oxidation with water and oxygen containing Ar for chemical-looping hydrogen production was conducted. Fe₂O₃ (20 wt.%)/ZrO₂ was prepared by a co-precipitation method. The main variables in the TGA (thermogravimetric analyzer) experiment were temperatures and gas concentrations. The reaction kinetics parameters were estimated based on the experimental data. In the reduction by CH₄, CO and H₂, the reaction rate changed near FeO. Changes in the reaction rate due to phase transformation were observed at low temperature and low gas concentration during the reduction by CH₄, but the phenomenon was not remarkable for the reduction by CO and H₂. The reduction rate achieved using CO and H₂ was relatively faster than achieved using CH₄. The Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions was applied. A phase boundary controlled model (contacting sphere) was applied to the reduction of Fe₂O₃ to FeO by CH₄, and a different phase boundary controlled model (contacting infinite slab) was fit well to the reduction of FeO to Fe by CH₄. The reduction of Fe₂O₃ to Fe by CO and H₂ can be described by the former phase boundary controlled model (contacting sphere). This phase boundary controlled model (contacting sphere) also fit well for the oxidation of Fe to Fe₃O₄ by water and FeO to Fe₂O₃ by oxygen containing Ar. These kinetics data could be used to design chemical-looping hydrogen production systems.     

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

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

Estimation of the effectiveness factor of an outer-sphere redox couple (Fe3+/Fe2+) using rotating disk Ti/IrO2 electrodes of different loading

The effectiveness factor; E _f , defined as the fraction of the surface that participates effectively in a given reaction, is an important parameter when operating three-dimensional (3D) electrodes. The rotating disk electrode (RDE) technique with the Fe³⁺/Fe²⁺ redox couple as a probe reaction has been used for the evaluation of the effectiveness factor of 3D Ti/IrO₂ electrodes with different IrO₂ loading. For this purpose, steady-state polarization measurements using Ti/IrO₂ rotating disk electrodes in 0.5 M Fe³⁺/Fe²⁺ in 1 M HCl were carried out under well-defined hydrodynamic conditions. The low-field approximation relation has been used for the estimation of the exchange current densities j ₀, of the Fe³⁺/Fe²⁺ redox couple. It was found for this redox couple that the effectiveness factor is very low (<2%) and essentially the 2D electrode surface area works effectively in the steady-state polarization measurements.     

A novel LiTi2(PO4)3/MnO2 hybrid supercapacitor in lithium sulfate aqueous electrolyte

In this work, carbon-coated lithium-ion intercalated compound LiTi₂(PO₄)₃ and MnO₂ have been synthesized and they deliver a capacity of 90 and 60 mAh/g in 1 M Li₂SO₄ neutral aqueous electrolyte within safe potentials without O₂ and H₂ evolution, respectively. The novel hybrid supercapacitor in which MnO₂ was used as a positive electrode and carbon-coated LiTi₂(PO₄)₃ as a negative electrode was assembled and the LiTi₂(PO₄)₃/MnO₂ hybrid supercapacitor showed a sloping voltage profile from 0.7 to 1.9 V, at an average voltage near 1.3 V, and delivers a capacity of 36 mAh/g and an energy density of 47 Wh/kg based on the total weight of the active electrode materials. It exhibits a desirable profile and maintains over 80% of its initial energy density after 1000 cycles. The hybrid supercapacitor also exhibit an excellent rate capability, even at a power density of 1000 W/kg, it has a specific energy 25 Wh/kg compared with 43 Wh/kg at the power density about 200 W/kg.     

Study of intrinsic sulfidation behavior of Fe2O3 for high temperature H2S removal

Iron-based sorbent was preferable for desulfurization from coal-derived gas due to economic consideration and favorable dynamic property. The intrinsic behavior of Fe-based sorbent should be primarily understood in the sulfidation process for improving its performance. A series of tests were carried out with Fe₂O₃, Fe and other compounds containing-Fe (FO) made from the same precursor FeC₂O₄·2H₂O in H₂S-N₂ mixture in this study. The formation of H₂ was observed with Fe and FO as sorbents. While SO₂ was detected with FO and Fe₂O₃ as sorbents, its concentration in outlet was gradually decreased. The crystal phase and surface chemical state of fresh and sulfided Fe₂O₃ with different reaction times were characterized by XRD and XPS measurements. The result suggested that the intrinsic H₂S removal by Fe₂O₃ would produce multi-phase of sulfides. The possible mechanism of sulfidation reaction was discussed.     

A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes–manganese complex modified glassy carbon electrode

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20–100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1–12). The surface coverages and heterogeneous electron transfer rate constants (k_s) of immobilized Mn-complex were approximately 1.58 × 10⁻¹⁰ mole cm⁻² and 48.84 s⁻¹. The modified electrode showed excellent electrocatalytic activity toward H₂O₂ reduction. Detection limit, sensitivity, linear concentration range and k_cat for H₂O₂ were, 0.2 μM and 692 nA μM⁻¹ cm⁻², 1 μM to 1.5 mM and 7.96(±0.2) × 10³ M⁻¹ s⁻¹, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.     

Amperometric tyrosinase biosensor based on Fe3O4 nanoparticles-coated carbon nanotubes nanocomposite for rapid detection of coliforms

A tyrosinase (Tyr) biosensor was developed based on Fe₃O₄ magnetic nanoparticles (MNPs)-coated carbon nanotubes (CNTs) nanocomposite and further applied to detect the concentration of coliforms with flow injection assay (FIA) system. Negatively charged MNPs were absorbed onto the surface of CNTs which were wrapped with cationic polyelectrolyte poly(dimethyldiallylammonium chloride) (PDDA). The Fe₃O₄ MNPs-coated CNTs nanocomposite was modified on the surface of the glassy carbon electrode (GCE), and Tyr was loaded on the modified electrode by glutaraldehyde. The immobilization matrix provided a good microenvironment for retaining the bioactivity of Tyr, and CNTs incorporated into the nanocomposite led to the improved electrochemical detection of phenol. The Tyr biosensor showed broad linear response of 1.0 × 10⁻⁸-3.9 × 10⁻⁵ M, low detection limit of 5.0 × 10⁻⁹ M and high sensitivity of 516 mA/M for the determination of phenol. Moreover, the biosensor integrated with a FIA system was used to monitor coliforms, represented by Escherichia coli (E. coli). The detection principle was based on determination of phenol which was produced by enzymatic reaction in the E. coli solution. Under the optimal conditions, the current responses obtained in the FIA system were proportional to the concentration of bacteria ranging from 20 to 1 × 10⁵ cfu/mL with detection limit of 10 cfu/mL and the overall assay time of about 4 h. The developed biosensor with the FIA system was well suited for quick and automatic clinical diagnostics and water quality analysis.