Microwave synthesis, characterization, and electrochemical properties of α-Fe2O3 nanoparticles

Ultrafine α-Fe₂O₃ nanoparticles with an extremely narrow distribution were synthesized by microwave heating. Transmission electron microscopy (TEM) images showed that most primary particles have ellipsoid shapes, and the average diameter of the primary particles was less than 10 nm. The electron diffraction pattern and fringes in some particles in TEM images showed that these nanoparticles were single crystals. The BET surface area of the freeze-dried product was 217 m²/g. The initial discharge capacity of the α-Fe₂O₃ nanoparticles exceeded 1007 mA/g (cut-off voltage: 0.5 V). This large capacity corresponds to that calculated by assuming the reduction of Fe³⁺ to Fe⁰. The α-Fe₂O₃ nanoparticles also work as a rechargeable electrode material. The charge-discharge test between 4 V and 1.5 V gave a good rechargeable capacity of about 150 mAh/g.     

Role of Cr ions on superexchange coupling in α-Fe2O3 nanoparticles

Synthesis of nanocomposites of iron oxide & chromium oxide (α-Fe₂O₃–Cr₂O₃) with different concentrations was carried out by a wet-chemical method and the structural, optical and hyperfine properties have been investigated. The prepared nanocomposites were characterized by powder X-ray diffractometry (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV–VIS spectroscopy, Fourier transformed infrared (FTIR) spectroscopy and Mössbauer spectroscopy. XRD measurements confirmed the formation of pure phase composites having particle sizes in nanometer regime. The same has been corroborated by TEM micrographs, which revealed that the formation of monodispersed nanocomposites have the average particle size 44 nm. Mössbauer study of the samples showed the transition of iron oxide from anti-ferromagnetic state to paramagnetic state having a typical relaxation in the spectrum with increasing concentration of Cr₂O₃.     

Fabrication, characterization, and measurement of viscosity of α-Fe2O3-glycerol nanofluids

Magnetic nanofluids, ferrofluids, are a special category of smart nanomaterials, consisting of stable dispersion of magnetic nanoparticles in different fluids. In this study, magnetic nanoparticles of hematite, α-Fe₂O₃, were prepared by solvothermal method using Fe(NO₃)₃ as a starting material. The nanoparticles were characterized by X-ray diffraction (XRD) and transmission electronic microscope (TEM).To the best of our knowledge, this is the first research on the rheological properties of nanofluids of α-Fe₂O₃ nanoparticles and glycerol. The experimental results showed that the viscosity of α-Fe₂O₃-glycerol nanofluids increases with increasing the particle volume fraction and decreases with increasing temperature. Our results clearly showed that the α-Fe₂O₃-glycerol nanofluids are non-Newtonian shear-thinning and their shear viscosity depends strongly on temperature. The experimental data were compared with some theoretical models. The measured values of the effective viscosity of nanofluids are underestimated by the theoretical models.     

Exchange bias behavior of monodisperse Fe3O4/γ-Fe2O3 core/shell nanoparticles

We have carried out systematic studies on well-characterized monodisperse Fe₃O₄/γ-Fe₂O₃ core/shell nanoparticles of 2-30 nm having a very narrow size distribution and possessing a uniquely mono-layer of surface γ-Fe₂O₃. This unique core-shell structure, probably having a disordered magnetic surface state, leads us to three key observations of unusual magnetic properties: i) a very large magnetic exchange anisotropy reaching over 7 × 10⁶ erg/cm³ for the smaller particles, ii) exchange bias behavior in the magnetization data of the core/shell Fe₃O₄/γ-Fe₂O₃ nanoparticles, and iii) the temperature dependence of the coercive field following an unusual exponential behavior.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.     

Shape- and field-dependent Morin transitions in structured α-Fe2O3

We report shape- and field-dependent magnetic properties of ellipsoid-, spindle-, flattened- and rhombohedra-shaped α-Fe₂O₃ samples prepared by solvothermal technique. We observed that a magnetic spin-flip mechanism, mostly known as Morin transition (T_M), depends on the shape of α-Fe₂O₃ as well as on the applied magnetic field. In each of these structures the obtained value of T_M was less than its bulk value of 263 K. We observed that T_M shifted from highest 251.4 K for ellipsoid to lowest 220.8 K for rhombohedra structure, with intermediate values of T_M for the other two structures. However, for rhombohedra structure T_M shifted from 220.8 to 177.5 K under the external magnetic field of 100 Oe-30 kOe, respectively. The observed lowering of T_M in the structured sample was analyzed in terms of elementary size, shape of the nanocrystallites, lattice parameters and occupancy of Fe⁺³ ions as well. These parameters were determined from the Rietveld refinement process using MAUD software.     

Temperature-dependent linear or nonlinear gas sensing characteristics of In2O3 mixed α-Fe2O3 nanorods with high sensitivity

Highly sensitive gas sensors are realized from In₂O₃ mixed α-Fe₂O₃ nanorods. At 200 °C, the sensitivity of the sensors upon exposure to 200 ppm ethanol is 31.3, and the sensors exhibit linear dependence of the sensitivity on the ethanol concentration at 100 °C and 200 °C. In contrast, nonlinear gas sensing characteristics are observed at 300 °C and 400 °C. The relationship between sensitivity and ethanol concentration is discussed by using the conduction model, and the experimental data are in good agreement with the obtained equations. Our results imply that In₂O₃ mixed α-Fe₂O₃ nanorods are good candidates for nano-scale gas sensors and the relationship between sensitivity and ethanol concentration is significantly influenced by temperatures.     

Preparation, characterization and dye adsorption properties of γ-Fe2O3/SiO2/chitosan composite

A γ-Fe₂O₃/SiO₂/chitosan composite was prepared by water-in-oil emulsification, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). Effects of various factors, including adsorbent dosage, initial dye concentration, solution pH, and competing anions, on the adsorption of methyl orange from aqueous solutions by the resulting composite were studied by batch adsorption experiments. The adsorption kinetics was found to follow the pseudo-second-order kinetic model, and intraparticle diffusion was related to the adsorption, but not as a sole rate-controlling step. The equilibrium adsorption data were well described by the Freundlich isotherm model. Evaluation of the thermodynamic parameters ΔG°, ΔH°, and ΔS° revealed that the adsorption process was naturally feasible, spontaneous, and exothermic. The composite was proven to be efficient, suitable and promising for the removal of methyl orange from aqueous solutions since it has a relatively higher adsorption capacity than other low-cost adsorbents.     

Preparation and photocatalytic property of α-Fe2O3 hollow core/shell hierarchical nanostructures

We report the preparation of a novel kind of α-Fe₂O₃ hollow core/shell hierarchical nanostructures self-assembled by nanosheets. A green precursor powder is first prepared using nontoxic and inexpensive FeCl₃ and urea in ethylene glycol by a surfactant-free solvothermal method at 160 °C for 15 h. The α-Fe₂O₃ hollow core/shell hierarchical nanostructures are obtained by the thermal treatment of the green precursor powder. The as-prepared α-Fe₂O₃ hollow core/shell hierarchical nanostructures are porous, and exhibit a good photocatalytic activity for the degradation of phenol. The samples are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM).     

Synthesis and characterization of β-Ga2O3 nanorods

A novel method was applied to prepare β-Ga₂O₃ nanorods. In this method, β-Ga₂O₃ nanorods have been successfully synthesized on Si(1 1 1) substrates through annealing sputtered Ga₂O₃/Mo films under flowing ammonia at 950 °C in a quartz tube. The as-synthesized nanorods are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR). The results show that the nanorod is single-crystalline Ga₂O₃ with monoclinic structure. The β-Ga₂O₃ nanorods are straight and smooth with diameters in the range of 200-300 nm and lengths typically up to several micrometers. The growth process of the β-Ga₂O₃ nanorods is probably dominated by conventional vapor-solid (VS) mechanism.     

Biomolecule-assisted hydrothermal synthesis of Sb2S3 and Bi2S3 nanocrystals and their elevated-temperature oxidation behavior for conversion into α-Sb2O4 and Bi2O3

We have developed a novel biomolecule-assisted hydrothermal method to prepare Sb₂S₃ and Bi₂S₃ nanocrystals with various sizes and shapes, in which cysteine combined with other sulfur source can exert the synergistic effect on products. The samples were characterized XRPD, TEM, HRTEM, FESEM, and PL techniques. First, we prepared a series of Sb₂S₃ and Bi₂S₃ nanocrystals by simply adjusting the composition of sulfur sources under hydrothermal conditions. Then, we studied the elevated-temperature oxidation behavior of these sulfides in air, which can lead to the formation of α-Sb₂O₄ and Bi₂O₃ samples at 600 °C for 3 h. The optical properties of the α-Sb₂O₄ and Bi₂O₃ samples were also discussed.     

Fabrication of chloroform sensor based on hydrothermally prepared low-dimensional β-Fe2O3 nanoparticles

Hydrothermally prepared as-grown low-dimensional nano-particles (NPs) have been characterized using UV–vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and electron dispersion spectroscopy (EDS). The uniformity of the nano-material was executed by the scanning electron microscopy, where the single phase of the nano-crystalline β-Fe₂O₃ was characterized using XRD techniques. β-Fe₂O₃ nanoparticles fabricated glassy carbon electrode (GCE) have improved chloroform-sensing performances in terms of electrical response (I–V technique) for detecting analyte in liquid phase. The analytical performances were investigated, which showed that the better sensitivity, stability, and reproducibility of the sensor improved significantly by using Fe₂O₃ NPs thin-film on GCE. The calibration plot was linear (R = 0.9785) over the large range of 12.0 μM to 12.0 mM. The sensitivity was calculated as 2.1792 μA cm⁻² mM⁻¹ with a detection limit of 4.4 ± 0.10 μM in short response time (10.0 s).     

Sol–gel route of synthesis of nanoparticles of MgFe2O4 and XRD,FTIR and VSM study

Nanoparticles of MgFe₂O₄ are synthesized using sol–gel autocombustion method. Structural studies are carried out using X-ray diffraction (XRD). The XRD pattern of MgFe₂O₄ provides information about single-phase formation of spinel structure with cubic symmetry. The grain size and lattice constant are obtained using XRD data. The cation distribution is also proposed theoretically. The change in site preference of cations in nano-MgFe₂O₄ is compared with its bulk counterpart. The structural morphology of the nanoparticles is studied using Scanning Electron Microscopy (SEM). Formation of spinel structure is conformed using Fourier transform infrared spectroscopy (FTIR), which also lends support for the cation distribution proposed using XRD data. The effect of nanoregime on parameters such as bond length, vibration frequency and force constant are discussed with the help of FTIR data. The M–H loop of MgFe₂O₄ has been traced using the Vibrating Sample Magnetometer (VSM) and magnetic parameters such as saturation magnetization (M_S), coercivity (H_C) and retentivity (M_R) are obtained from VSM data.     

Synthesis, characterization, and growth mechanism of α-Cr2O3 monodispersed particles

Monodispersed spherical particles of chromium (III) oxide, α-Cr₂O₃, were successfully synthesized from a diluted solution of KCr(SO₄)₂·12H₂O using the Aqueous Chemical Growth (ACG) technique. The spherical α-Cr₂O₃ particles obtained were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Raman spectroscopy for structural, surface morphological, chemical, and physical properties, as a function of deposition time. The XRD and Raman spectroscopy showed that aging had no apparent effect on the structure of the obtained uniform fine (in the range of micron-nano-level)-spherical particles of α-Cr₂O₃. The use of SEM demonstrated that aging had a clear influence on the size and the particles size distribution. Accordingly, the time dependence of the average diameter of α-Cr₂O₃ spherical particles follows the d³ law as required for diffusion-limited Ostwald ripening.     

Assembly of γ-Fe2O3/polyaniline nanofilms with tuned dipolar interaction

The internal morphology and magnetic properties of layer-by-layer assembled nanofilms of polyaniline (PANI) and maghemite (γ-Fe₂O₃—7.5-nm diameter) were probed with cross-sectional transmission electron microscopy (TEM) and magnetization measurements (magnetic hysteresis loops, magnetization using zero-field cooled/field-cooled protocols, and ac magnetic susceptibility). Additionally, simulations of the as-produced samples were performed to assess both the nanofilm’s morphology and the corresponding magnetic signatures using the cell dynamic system (CDS) approach and Monte Carlo (MC) through the standard Metropolis algorithm, respectively. Fine control of the film thickness and average maghemite particle–particle within this magnetic structure was accomplished by varying the number of bilayers (PANI/γ-Fe₂O₃) deposited onto silicon substrates or through changing the concentration of the maghemite particles suspended within the colloidal dispersion sample used for film fabrication. PANI/γ-Fe₂O₃ nanofilms comprising 5, 10, 25 and 50 deposited bilayers displayed, respectively, blocking temperatures (T _B) of 30, 35, 39 and 40 K and effective energy barriers (ΔE/k _B) of 1.0 × 10³, 2.3 × 10³, 2.8 × 10³ and 2.9 × 10³ K. Simulation of magnetic nanofilms using the CDS model provided the internal morphology to carry on MC simulation of the magnetic properties of the system taking into account the particle–particle dipolar interaction. The simulated (using CDS) surface–surface particle distance of 0.5, 2.5 and 4.5 nm was obtained for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm, respectively. The simulated (using MC) T _B values were 33.0, 30.2 and 29.5 K for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm, respectively. We found the experimental (TEM and magnetic measurements) and the simulated data (CDS and MC) in very good agreement, falling within the same range and displaying the same systematic trend. Our findings open up new perspectives for fabrication of magnetic nanofilms with pre-established (simulated) morphology and magnetic properties.     

Design of multifunctionalized γ-Fe2O3@SiO2 core–shell nanoparticles for enzymes immobilization

This article deals with the first covalent grafting of an enzyme on twice functionalized γ-Fe₂O₃@SiO₂ core–shell magnetic nanoparticles. First, amino-PEG functionalized nanoparticles were synthesized in order to comply with non-toxic platforms that would be stable in high concentration and would exhibit chemical groups to allow further coupling with biomolecules. This approach produces a colloidal suspension of covalently grafted enzymes that remains stable for months and mimics the enzyme–substrate interactions in solution. Secondly, nanoparticles synthesis and enzyme coupling process were reported and the catalytic properties of bound enzymes were measured and compared with that of the free one. These new materials appear to be useful tools for enzymatic catalysis research and may be extended to other biomolecules. Furthermore, magnetic properties of these materials open the way to separation, purification, and transport under magnetic field.     

The study of novel Fe3O4@γ-Fe2O3 core/shell nanomaterials with improved properties

The surface structure of the iron oxide nanoparticles obtained by the co-precipitation method has been investigated, and a thin layer of α-FeOOH absorbed on surface of the nanoparticle is confirmed by analyses of Fourier transform infrared (FTIR), X-ray photoelectron spectra (XPS) and surface photovoltage spectroscopy (SPS). After annealed at 400 °C, the α-FeOOH can be converted to γ-Fe₂O₃. The simple-annealed procedure resulted in the formation of Fe₃O₄@γ-Fe₂O₃ core/shell structure with improved stability and a higher magnetic saturation value, and also the simple method can be used to obtain core/shell structure in other similar system.     

Pressure induced phase transition of nanocrystalline and bulk maghemite (γ-Fe2O3) to hematite (α-Fe2O3)

Phase transition and bulk moduli of bulk and nanocrystalline γ-Fe₂O₃ were studied using synchrotron X-ray diffraction under high pressure. Contrary to most other nanomaterials, nanocrystalline γ-Fe₂O₃ begins to transform into α-Fe₂O₃ at the same pressure as bulk γ-Fe₂O₃, which is caused by a special structure of γ-Fe₂O₃, in which there exist vacancies of crystal. It is believed that phase transition starts from a certain site of vacancy because of the stress concentration at vacancy sites. Compared to bulk material, nanocrystalline γ-Fe₂O₃ has a larger bulk modulus, which is ascribed to the large ratio of surface to volume.     

Synthesis of α-Fe2O3 nanobelts and nanoflakes by thermal oxidation and study to their magnetic properties

α-Fe₂O₃ nanobelts and nanoflakes have been successfully synthesized by oxidation of iron-coated ITO glass in air. The X-ray diffraction, Raman spectrum and scanning electron microscopy are carried out to characterize the nanobelts and nanoflakes. The formation mechanism has been presented. Significantly, the magnetic investigations show that the magnetic properties are strongly shape-dependent. The magnetization measurements of belt-like and flake-like α-Fe₂O₃ in perpendicular exhibit ferromagnetic feature with the coercivity (H_c) and saturation magnetization (M_s) of 334.5 Oe and 1.35 emu/g, 239.5 Oe and 0.12 emu/g, respectively. For the parallel, belt-like and flake-like α-Fe₂O₃ also exhibit ferromagnetic feature with the H_c and M_s of 205.5 Oe and 1.44 emu/g, 159.6 Oe and 0.15 emu/g, respectively.     

Interparticle interaction effects on magnetic behaviors of hematite (α-Fe2O3) nanoparticles

The interparticle magnetic interactions of hematite (α-Fe₂O₃) nanoparticles were investigated by temperature and magnetic field dependent magnetization curves. The synthesis were done in two steps; milling metallic iron (Fe) powders in pure water (H₂O), known as mechanical milling technique, and annealing at 600 °C. The crystal and molecular structure of prepared samples were determined by X-ray powder diffraction (XRD) spectra and Fourier transform infrared (FTIR) spectra results. The average particle sizes and the size distributions were figured out using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The magnetic behaviors of α-Fe₂O₃ nanoparticles were analyzed with a vibrating sample magnetometer (VSM). As a result of the analysis, it was observed that the prepared α-Fe₂O₃ nanoparticles did not perform a sharp Morin transition (the characteristic transition of α-Fe₂O₃) due to lack of unique particle size distribution. However, the transition can be observed in the wide temperature range as “a continuously transition”. Additionally, the effect of interparticle interaction on magnetic behavior was determined from the magnetization versus applied field (σ(M)) curves for 26±2 nm particles, dispersed in sodium oxalate matrix under ratios of 200:1, 300:1, 500:1 and 1000:1. The interparticle interaction fields, recorded at 5 K to avoid the thermal interactions, were found as ∼1082 Oe for 26±2 nm particles.