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.     

Electrochemical properties of α-Fe2O3 /MWCNTs as anode materials for lithium-ion batteries

α-Fe₂O₃/MWCNTs composites were prepared by a simple hydrothermal process. The crystalline structure and the electrochemical performance of the as-synthesized samples were investigated. Results show that as anode materials for lithium-ion batteries, the α-Fe₂O₃/MWCNTs exhibit an initial discharge capacity of 1256 ± 5 mAh g⁻¹ and a stable specific discharge capacity of 430 ± 5 mAh g⁻¹ at ambient temperature, for up to 100 cycles with no noticeable capacity fading, while the initial discharge capacity of the bare Fe₂O₃ is 992.3 mAh g⁻¹, and the discharge capacity is 146.6 mAh g⁻¹ after 100 cycles. Moreover, the α-Fe₂O₃/MWCNTs composites also exhibit excellent rate performance.     

Hydrothermal synthesis and structural characterization of (1−x)α-Fe2O3-xSnO2 nanoparticles

Structural and morphological characteristics of (1−x)α-Fe₂O₃-xSnO₂ (x=0.0-1.0) nanoparticles obtained under hydrothermal conditions have been investigated by X-ray diffraction (XRD), transmission Mössbauer spectroscopy, scanning and transmission electron microscopy as well as energy dispersive X-ray analysis. On the basis of the Rietveld structure refinements of the XRD spectra at low tin concentrations, it was found that Sn⁴⁺ ions partially substitute for Fe³⁺ at the octahedral sites and also occupy the interstitial octahedral sites which are vacant in α-Fe₂O₃ corundum structure. A phase separation of α-Fe₂O₃ and SnO₂ was observed for x≥0.4: the α-Fe₂O₃ structure containing tin decreases simultaneously with the increase of the SnO₂ phase containing substitutional iron ions. The mean particle dimension decreases from 70 to 6 nm, as the molar fraction x increases up to x=1.0. The estimated solubility limits in the nanoparticle system (1−x)α-Fe₂O₃-xSnO₂ synthesized under hydrothermal conditions are: x≤0.2 for Sn⁴⁺ in α-Fe₂O₃ and x≥0.7 for Fe³⁺ in SnO₂.     

Pillaring and photocatalytic properties of mesoporous α-Fe2O3/titanate nanocomposites via an exfoliation and restacking route

Mesoporous α-Fe₂O₃-pillared titanate nanocomposites have been successfully synthesized through an exfoliation−restacking route. Powder X-ray diffraction and N₂ adsorption-desorption isotherms revealed that the α-Fe₂O₃ pillared titanate has an interlayer distance of 3.27 nm, a specific surface area of 66 m²/g and an average pore size of 7.6 nm, suggesting the formation of a mesoporous pillared structure. UV-vis diffuse reflectance spectra show a red shift, indicative of a narrow band gap energy of ∼2.1 eV compared to the host layered titanate, which is essential in creating a visible light photocatalytic activity. The results of degradation of rhodamine B reveal that the present pillared mesoporous composites exhibit better photocatalytic activities than those of the pristine materials under visible irradiation, based on the band gap excitement and the dye-sensitized path, originated from their high surface area, mesoporosity and the electronic coupling between the host and the guest components.     

Solvothermal synthesis and characterization of α-Fe2O3 nanodiscs and Mn3O4 nanoparticles with 1,10-phenanthroline

α-Fe₂O₃ nanodiscs and Mn₃O₄ nanoparticles have been prepared by the 1,10-phenanthroline as complexing agent in the presence of sodium hydroxide under hydrothermal conditions. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) spectra. The average diameter of α-Fe₂O₃ nanodiscs is of 2 μm. In the case of Mn₃O₄ sample, the Mn₃O₄ crystallites are nanoparticles with an average size of 34 nm. A formation mechanism for the α-Fe₂O₃ and Mn₃O₄ nanomaterials was proposed.     

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.     

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).     

Thickness dependent activity of nanostructured TiO2/α-Fe2O3 photocatalyst thin films

The effect of thickness of TiO₂ coating on synergistic photocatalytic activity of TiO₂ (anatase)/α-Fe₂O₃/glass thin films as photocatalysts for degradation of Escherichia coli bacteria in a low-concentration H₂O₂ solution and under visible light irradiation was investigated. Nanograined α-Fe₂O₃ films with optical band-gap of 2.06 eV were fabricated by post-annealing of thermal evaporated iron oxide thin films at 400 °C in air. Increase in thickness of the Fe₂O₃ thin film (here, up to 200 nm) resulted in a slight reduction of the optical band-gap energy and an increase in the photoinactivation of the bacteria. Sol-gel TiO₂ coatings were deposited on the α-Fe₂O₃ (200 nm)/glass films, and then, they were annealed at 400 °C in air for crystallization of the TiO₂ and formation of TiO₂/Fe₂O₃ heterojunction. For the TiO₂ coatings with thicknesses ≤50 nm, the antibacterial activity of the TiO₂/α-Fe₂O₃ (200 nm) was found to be better than the activity of the bare α-Fe₂O₃ film. The optimum thickness of the TiO₂ coating was found to be 10 nm, resulting in about 70 and 250% improvement in visible light photo-induced antibacterial activity of the TiO₂/α-Fe₂O₃ thin film as compared to the corresponding activity of the bare α-Fe₂O₃ and TiO₂ thin films, respectively. The improvement in the photoinactivation of bacteria on surface of TiO₂/α-Fe₂O₃ was assigned to formation of Ti-O-Fe bond at the interface.     

Magnetic properties of nanosized γ-Fe2O3 and α-(Fe2/3Cr1/3)2O3, prepared by thermal decomposition of heterometallic single-molecular precursor

Thermal decomposition of the trinuclear complex [Fe₂CrO(CH₃COO)₆(H₂O)₃]NO₃ at 300, 400 and 500 °C gave γ-Fe₂O₃ nanoparticles along with amorphous chromium oxide, while decomposition of the same starting compound at 600 and 700 °C led to the formation of α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles. Size of γ-Fe₂O₃ nanoparticles, determined by X-ray diffraction, was in the range from 9 to 11 nm and increased with formation temperature growth. Average size of α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles was about 40 nm and almost did not depend on the temperature of its formation. γ-Fe₂O₃ nanoparticles possessed superparamagnetic behavior with blocking temperature 180-250 K, saturation magnetization 29-35 emu/g at 5 K, 44-49 emu/g at 300 K and coercivity 400-600 Oe at 5 K. α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles were characterized by low magnetization values (2.7 emu/g at 70 kOe). Such magnetic properties can be caused by non-compensated spins and defects present on the surface of these nanoparticles. The increase of α-(Fe_2/3Cr_1/3)₂O₃ formation temperature led to decrease of magnetization (being compared for the same fields), which may be caused by decrease of the quantity of defects or non-compensated spins (due to decrease of particles' surface).     

Preparation of pyrrole with iron oxide precipitated on the surface of graphite nanosheet

Fe₃O₄/NanoG was firstly prepared by precipitation reaction of iron oxide (Fe₃O₄) on the surface of graphite nanosheet (NanoG). Then composites PPy/NanoG, PPy/Fe₃O₄ and PPy/Fe₃O₄/NanoG were prepared by in-situ polymerization of the monomer pyrrole polymerized on the surface of NanoG, Fe₃O₄ and Fe₃O₄/NanoG. The structures of Fe₃O₄/NanoG, PPy, PPy/NanoG, PPy/Fe₃O₄ and PPy/Fe₃O₄/NanoG were characterized by scanning electron microscopy, energy dispersive spectroscopy, fourier transmission infrared spectroscopy and X-ray diffraction . Results show that NanoG and Fe₃O₄/NanoG are encapsulated by PPy for the layered structure and their high aspect ratio (300–500). From the thermogravimetric analysis it can be seen that the introductions of NanoG, Fe₃O₄ and Fe₃O₄/NanoG into PPy based composites lead them to exhibit better thermal stabilities than pure PPy. The measurements of electromagnetic parameters show that the reflection loss of PPy/Fe₃O₄/NanoG is below −15 dB at the X band (8.2–12.4 GHz) and the minimum loss value is −18.30 dB at 9.84 GHz, while the reflection loss of PPy/Fe₃O₄ is below −10 dB at 8.2–12.4 GHz and the minimum loss value is −14.02 dB at 10.26 GHz. The reflection loss of PPy/NanoG is below −10 dB at 8.2–12.4 GHz and the minimum loss value is −13.44 dB at 10.28 GHz. The microwave absorbing properties of PPy/Fe₃O₄/NanoG, PPy/Fe₃O₄ and PPy/NanoG are superior to that of PPy.     

Hydrolysis precipitation synthesis of monodisperse α-Fe2O3 nanorods/graphene oxide nanocomposites

A nanocomposite of graphene oxide supported by monodisperse rod-like α-Fe₂O₃ nanocrystals (GO/α-Fe₂O₃ nanocomposites) has been fabricated through a simple hydrolysis precipitation route in a water–ethanol system. The nanocomposites were characterized by X-ray diffraction, Raman spectra and transmission electron microscopy, respectively. The GO/α-Fe₂O₃ nanocomposites are GO nanosheets decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 20–30 nm, while only hollow α-Fe₂O₃ microspheres constructed by the radically oriented single-crystalline nanorods are observed in the absence of GO. Compared with pure α-Fe₂O₃ nanoparticles, α-Fe₂O₃/GO nanocomposites exhibited excellent photocatalytic activity as evident from the degradation of rhodamine B in water under UV irradiation. The superior photocatalytic activity performance of α-Fe₂O₃/GO nanocomposites could be attributed to the synergetic effect between the conducting GO nanosheets and monodisperse α-Fe₂O₃ nanorods.     

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.     

Magneto-optic Faraday effect in maghemite nanoparticles/silica matrix nanocomposites prepared by the Sol–Gel method

Bulk monolithic samples of γ-Fe₂O₃/SiO₂ composites with different iron oxide/silica ratios have been prepared by the sol–gel technique. Iron oxide nanoparticles are obtained in-situ during heat treatment of samples and silica matrix consolidation. Preparation method was previously optimized to minimize the percentage of antiferromagnetic α-Fe₂O₃ and parallelepipeds of roughly 2×5×12 mm³, with good mechanical stability, are obtained. RT magnetization curves show a non-hysteretic behavior. Thus, magnetization measurements have been well fitted to an expression that combines the Langevin equation with an additional linear term, indicating that some of the nanoparticles are still superparamagnetic as confirmed by X-ray diffraction and electron microscopy measurements. Zero field cooled /field cooled experiments show curves with slightly different shapes, depending on the size and shape distribution of nanoparticles for a given composition. Magneto-optical Faraday effect measurements show that the Faraday rotation is proportional to magnetization of the samples, as expected. As a demonstration of their sensing possibilities, the relative intensity of polarized light, measured at 5° from the extinction angle, was plotted versus applied magnetic field.     

Preparation and characterization of bifunctional, Fe3O4/ZnO nanocomposites and their use as photocatalysts

Bifunctional magnetic-optical Fe₃O₄/ZnO nanocomposites with different molar ratio were successfully synthesized by a facile two-step strategy. Compared with the other methods, it was found to be mild, inexpensive, green, convenient and efficient. Fe₃O₄ nanocrystal was used as seed for the deposit and growth of ZnO nanoparticle. A series of the characterizations manifested that the combination of Fe₃O₄ with ZnO nanoparticles was successful. Photocatalytic activity studies confirmed that as-prepared nanocomposites had excellent photodegradating behavior to Methyl Orange (MO) compared to the pure ZnO nanoparticles. The results showed that the degradation percentage of MO was about 93.6% for 1 h when the amount of catalyst was 0.51 g L⁻¹ and initial concentration of MO was 6 × 10⁻⁵ mol L⁻¹ in the pH 7 solution. Moreover, the kinetics of photocatalytic degradation reaction could be expressed by the first-order reaction kinetic model. Furthermore, the Fe₃O₄/ZnO nanocomposites could be also served as convenient recyclable photocatalysts because of their magnetic properties.     

Formation of γ-Fe2O3 hierarchical nanostructures at 500 °C in a high magnetic field

Three-dimensional (3-D) hierarchical nanostructures of γ-Fe₂O₃ are prepared by a solvothermal process combined with subsequent thermal treatment in air at 500 or 350 °C with the aid of a high magnetic field. The experimental results indicate that γ-Fe₂O₃ instead of α-Fe₂O₃ forms in air at 500 °C in a 12 T field. The products are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The magnetization curves measured at room temperature exhibit superparamagnetic characteristics.     

Structure, band offsets and photochemistry at epitaxial α-Cr2O3/α-Fe2O3 heterojunctions

We test the hypothesis that electron-hole pair separation following light absorption enhances photochemistry at oxide/oxide heterojunctions which exhibit a type II or staggered band alignment. We have used hole-mediated photodecomposition of trimethyl acetic acid chemisorbed on surfaces of heterojunctions made from epitaxial α-Cr₂O₃ on α-Fe₂O₃(0001) to monitor the effect of UV light of wavelength 385 nm (3.2 eV) in promoting photodissociation. Absorption of photons of energies between the bandgaps of α-Cr₂O₃ (E_g = 4.8 eV) and α-Fe₂O₃ (E_g = 2.1 eV) is expected to be strong only in the α-Fe₂O₃ layer. The staggered band alignment should then promote the segregation of holes (electrons) to the α-Cr₂O₃ (α-Fe₂O₃) layer. Surprisingly, we find that the α-Cr₂O₃ surface alone promotes photodissociation of the molecule at hν = 3.2 eV, and that any effect of the staggered band alignment, if present, is masked. We propose that the inherent photoactivity of the α-Cr₂O₃(0001) surface results from the creation of bound excitons in the surface which destabilize the chemisorption bond in the molecule, resulting in photodecomposition.     

Effects of preheating on diaspore: Modifications in colour centres, structure and light emission

The thermal properties and thermal stability of diaspore-corundum (AlOOH-Al₂O₃), from Goian (Pontevedra, Spain) were studied by means of differential thermal analysis (DTA), thermogravimetry (TG), high temperature X-ray diffraction (HTXRD) and thermally stimulated luminescence (TL) techniques. The samples were annealed to link the combined effect of (i) dehydroxylation, (ii) oxidation-reduction of chromophores (Mn 0.5%, Fe₂O₃ 0.12%, TiO₂ 0.021% and Cr 80 ppm) determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and (iii) phase transitions whilst sample heating (i.e. α-AlOOH→α′-Al₂P₃→α-Al₂O₃). The blue colour of diaspore, attributed to the Ti⁴⁺-Fe²⁺ intervalence-charge-transfer mechanism, turns to white (circa 500 °C) in good agreement with the DTA endothermic peak (dehydroxylation). The coexistence of α-AlOOH and α′-Al₂P₃ phases has been detected by in situ HTXRD and could be correlated to the thermoluminescence tests performed on preheated aliquots (up to 500 °C).     

One-step solution synthesis of Fe2O3 nanoparticles at low temperature

A new synthesis method of α-Fe₂O₃ nanoparticles was developed, in which the ferrous and ferric salts as well as polyaniline acted as the precursor and dispersant, respectively. From the investigation of X-ray diffraction and FT-IR spectra, the α-Fe₂O₃ nanoparticles can be directly prepared by the co-precipitation method without high-temperature calcining. Transmission electron microscope (TEM) and scanning electron microscope (SEM) observation revealed that the α-Fe₂O₃ nanoparticles had average diameters ranging from 30.0 to 75.0 nm. Compared with previous methods, this present method shows an easy processing and can be applied on the large-scale produce of α-Fe₂O₃ nanoparticles in one step.     

Synthesis and magnetic properties of platelet γ-Fe2O3 particles for medical applications using hysteresis-loss heating

Platelet γ-Fe₂O₃ particles of particle size less than 100 nm were prepared for medical applications that use the hysteresis-loss heating of ferromagnetic particles. The γ-Fe₂O₃ particles were obtained through the dehydration, reduction, and oxidation of platelet α-FeOOH particles, which were synthesized by the precipitation of ferric ions in an alkaline solution containing ethanolamine, and the crystals grown using a hydrothermal treatment. The γ-Fe₂O₃ particles contained dimples formed by the dehydration of α-FeOOH particles. The coercive force and the saturation magnetization of the γ-Fe₂O₃ particles were in the ranges 11.9 to 12.7 kA/m (150 to 160 Oe), and 70 to 72 Am²/kg (70 to 72 emu/g), respectively. The specific loss power of the γ-Fe₂O₃ particles, estimated from their temperature-raising property measured under a peak magnetic field of 50.9 kA/m (640 Oe) and at a frequency of 117 kHz, was 590 W/g. This value is higher than that of spherical cobalt-containing iron oxide particles having equivalent coercive force and saturation magnetization, reflecting the larger area of the minor hysteresis loop measured under a peak magnetic field of 50.9 kA/m (640 Oe).     

Interaction of H2S with α-Fe2O3(0 0 0 1) surface

The atomic-scale structural changes in an α-Fe₂O₃ (hematite) (0 0 0 1) surface induced by sulfidation and subsequent oxidation processes were studied by X-ray photoemission spectroscopy, LEED, and X-ray standing wave (XSW) measurements. Annealing the α-Fe₂O₃(0 0 0 1) with a H₂S partial pressure of 1 × 10⁻⁷ Torr produced iron sulfides on the surface as the sulfur atoms reacted with the substrate Fe ions. The oxidation state of the substrate Fe changed from 3+ to 2+ as a result of the sulfidation. The XSW measured distance of the sulfur atomic-layer from the unrelaxed substrate oxygen layer was 3.16 Å. The sulfide phase consisted of three surface domains identified by LEED. Formation of the two-dimensional FeS₂ phase with structural parameters consistent with an outermost layer of (1 1 1) pyrite has been proposed. Atomic oxygen exposure oxidized the surface sulfide to a sulfate () and regenerated the α-Fe₂O₃(0 0 0 1) substrate, which was indicated by a (1 × 1) LEED pattern and the re-oxidization of Fe to 3+.