Coercivity of homogenized ensembles of anisotropic γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The influence of interaction between anisotropic γ-Fe₂O₃ nanoparticles on their coercive force H _c is studied. In samples where the degree of homogenization of anisotropic γ-Fe₂O₃ nanoparticles is high owing to mechanical, ultrasonic, and magnetic dispersion with subsequent filtering of resulting suspensions, H _c is almost independent of volume concentration η of the particles when η varies between 4 × 10⁻⁴ and 10⁻¹. In samples homogenized only mechanically, the H _c versus logη dependence is linear.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

Fabrication of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> bi-functional composites with hierarchical and hollow structures and their application in water treatment

The α-Fe₂O₃/TiO₂ bi-functional composites with hierarchical and hollow structures are fabricated through a hydrothermal route. The adsorption performance and photocatalytic activity of the composites towards Pb²⁺ are investigated in this work. Different adsorption kinetics models and equilibrium models are used to explore the adsorption behavior of hierarchical α-Fe₂O₃/TiO₂ hollow spheres. Experimental data show that adsorption kinetics of the hierarchical α-Fe₂O₃/TiO₂ hollow spheres can be fitted well by the pseudo-second-order model, while the isothermal data can be perfectly described by the Langmuir adsorption model. The maximum adsorption capacity of the hierarchical α-Fe₂O₃/TiO₂ hollow spheres is 32.36 mg g^?1. Moreover, the hierarchical α-Fe₂O₃/TiO₂ hollow spheres possess photocatalytic oxidation character under simulated solar light irradiation. The results demonstrate that the hierarchical α-Fe₂O₃/TiO₂ hollow spheres, as effective and cheap materials, can be applied to the removal of heavy metal ions from wastewater.     

Spin-reorientation phase transition on the surface and in the bulk of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> single crystals

Direct comparison of the properties of a thin surface layer and the bulk of macroscopic hematite (α-Fe₂O₃) crystals was used to study the magnetic structure of the surface layer and the bulk and the processes attendant on spin-reorientation phase transition (SRT). The investigation tool was simultaneous γ-ray, X-ray, and electronic Mössbauer spectroscopy, which enabled us to study the bulk and surface properties of macroscopic samples simultaneously and to compare them directly. Direct evidence of the existence of a surface “transition layer” on hematite crystals is obtained. The existence of this layer was suggested and described by Krinchik and Zubov [JETP 69, 707 (1975)]. The study in the SRT region showed that (1) the Morin SRT in the crystal bulk occurs in a jump (as a first-order phase transition), whereas in the surface layer of about 200 nm thick, some smoothness appears in the mechanism of magnetic-moment reorientation; (2) SRT in the surface layer, as in the bulk, involves an intermediate state in which low-and high-temperature phases coexist; and (3) SRT in the surface layer occurs at a temperature several degrees higher than in the bulk. Our experimental evidence on the SRT mechanism in the surface layer correlates with the inferences from phenomenological theory developed by Kaganov [JETP 79, 1544 (1980)].     

Theoretical investigations of 3d-metal adsorption on the α-AL<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

Theoretical investigations of adsorption of 3d-metals from Ti to Cu on the α-Al₂O₃ (0001) surface are presented. The influence of adsorbates on the atomic and electronic structure of the aluminum oxide surface is considered. Values of the adsorption energy are calculated, and the equilibrium adatom positions on the surface are determined. A comparative analysis of the properties and mechanisms of 3d-metal interaction with atoms of the substrate is performed.     

Luminescence centers in α-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

Luminescence photoexcitation spectra of α-Bi₂O₃ ceramics are investigated. Luminescence spectra were deconvoluted into fundamental components using the Alentsev-Fok method. It is established that the luminescence spectra of α-Bi₂O₃ ceramics consist of three fundamental bands with maxima at 2.75, 2.40, and 1.97 eV. A comparison of the results with those from an investigation of luminescence of various modifications of bismuth oxide and bismuth germanates suggests that luminescence of these compounds is caused by radiation processes that occur in structural complexes that contain the bismuth ion in a nearest oxygen environment. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 672–676, September–October, 2008.     

Single-crystalline α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanohexahedron as outstanding anode material for lithium-ion batteries

In this paper, single-crystalline hexahedron hematite is successfully obtained by a simple hydrothermal approach with assistance of PVP as surfactant. SEM and XRD results show that the as-obtained α-Fe₂O₃ has a nanohexahedron shape with high uniformity and high crystallinity. The effects of a few factors influencing the morphology of α-Fe₂O₃, such as PVP amount, reaction temperature, etc., are investigated carefully. More importantly, time-dependent experiments are carried out to have in-depth insight into the formation of the single-crystalline α-Fe₂O₃ nanohexahedron. Based on the full characterization of as-obtained α-Fe₂O₃, it is concluded that PVP as surfactant plays an important role in the formation of the hexahedron shape of α-Fe₂O₃. Besides, the proposed formation mechanism of α-Fe₂O₃ nanohexahedron is that the shape of α-Fe₂O₃ evolves from the nuclei, needle-like shapes, and urchin-like aggregates to the hexahedron shape, driven by minimization of surface energy and Ostwald ripening. When used as an anode material for lithium-ion batteries, nanohexahedron α-Fe₂O₃ shows a high rate capability. Moreover, after 150 cycles, the storage capacity of α-Fe₂O₃ is still up to 680 mAh g^?1 and almost remains unchanged, suggesting high cyclability.

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Graphical Abstract ?

     

Kinetics of γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticle evolution from an organic precursor

-Fe₂O₃ particles with an average size of 10 nm were prepared by heating the precipitates obtained from a homogeneous solution of stearic acid and hydrated iron (III) nitrate. The compositional and thermal characteristics of the precipitates were studied with the aid of Fourier transform infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC). Presence of -Fe₂O₃ nanoparticles in the heat treated product was established by X-ray diffraction (XRD) investigations. The average particle size was estimated from the XRD patterns by single line profile analysis and directly from transmission electron microscopic (TEM) images. Kinetic analysis of the calorimetric data revealed that nucleation and growth type kinetic law remain operative during the process and the activation energy of the process is 115 kJ/mol.     

Thermal- and photo-induced transformations of luminescence centers in αd-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> anion-defective crystals

The thermal- and photo-induced transformations of luminescence centers in anion-defective crystals of α-Al₂O₃ have been investigated. It has been found that the exposure of crystals to ultraviolet light at temperatures in the range 50–900°C leads to substantial changes in their thermoluminescence and radioluminescence spectra. According to the optical absorption and photoluminescence data, the detected F-type centers have been identified and the temperature ranges of the F → F ⁺ → F ₂ transformations and their possible mechanisms have been determined. The special attention has been drawn to the detailed similarity in the formation of complex F ₂-type centers in the initially perfect α-Al₂O₃ crystals irradiated with fast neutrons and in the studied anion-defective crystals.     

Ag nanowire-modified 1D α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanotube arrays for photocatalytic degradation of methylene blue

An in-situ photoreduction strategy is applied to coat Ag nanowires (NWs) directly onto the surface of one-dimensional (1D) α-Fe₂O₃ nanotube arrays (NTAs) fabricated by anodization treatment, and their chemical composition, morphologies, optical properties, and stability are systematically characterized. Structural characterization results manifest that Ag NWs are successfully anchored on α-Fe₂O₃ NTAs with the average nanotube diameter of 80 nm and confirm the formation of Ag/α-Fe₂O₃ NTA heterostructure. An apparent red shift in absorption edges of Ag/α-Fe₂O₃ NTAs is observed. Particularly, the 30-min Ag/α-Fe₂O₃ NTAs with Ag NW’s average length of 100 nm display the best photocatalytic ability for photocatalytic degradation of methylene blue (MB) dye under visible light illumination, owing to the synergistic effect of the localized surface plasmon resonance (LSPR) on Ag NWs as well as the synergistic effect on the electron delivery and effective separation of photogenerated carriers between Ag NWs and α-Fe₂O₃ NTAs. In addition, the photogenerated holes (h⁺) and superoxide radicals (O₂ ^·?) played crucial roles during the photocatalytic process.

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Graphical abstract Schematic illustration of the synergistic effect between Ag NWs and α-Fe₂O₃ NTA combined with conjectural photocatalytic degradation MB mechanism.

     

Controlled flame synthesis of αFe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: effect of flame configuration,flame temperature,and additive loading

Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe₂O₃ and magnetite Fe₃O₄. We found that the synthesized nanoparticles were smaller (6–12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50–60 nm) when CH₄, O₂, Ar, and N₂ gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH₄, O₂, Ar gas flow rates were kept constant, and N₂ gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N₂ cooling demonstrated that particles no larger than 50–60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the outer annulus along with the CH₄ in the inverse diffusion flame configuration. When particles were synthesized in the presence of the TTIP additive, larger monodispersed individual particles (50–90 nm) were synthesized as observed by TEM. In this article, we show that iron oxide nanoparticles of varied morphology, composition, and size can be synthesized and controlled by varying flame configuration, flame temperature, and additive loading.     

Facile synthesis of nanosized ε-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> particles on the silica support

An approach is suggested to synthesize the ε-Fe₂O₃ particles supported on silica with the mean size of few nanometers, narrow size distribution and no admixture of any other iron oxide polymorphs. The facile synthesis is based on the pore filling impregnation method by iron sulfate (II) water solution with the following annealing procedure at ~1173 K. It is shown that the ε-Fe₂O₃ nanoparticles obtained are stable up to ~1173 K and possess superparamagnetic behavior up to ~870 K.     

Synthesis and magnetic properties of CdS/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> hierarchical nanostructures

CdS/α-Fe₂O₃ hierarchical nanostructures, where the CdS nanorods grow irregularly on the side surface of α-Fe₂O₃ nanorods, were synthesized via a three-step process. The diameters and lengths of CdS nanorods can be tuned by changing the ethylenediamine (EDA) and Cd ion concentrations. The magnetic investigations by superconducting quantum interference device indicate that the hierarchical nanostructures have an Morin transition at lower temperature (230 K) than that of the single bulk α-Fe₂O₃ materials (263 K). Importantly, the hierarchical nanostructures exhibit weakly ferromagnetic characteristics at 300 K. A sharp peak assigned to the surface trap induced emission are observed in room temperature PL spectra. Combining with the optoelectronic properties of CdS, the CdS/α-Fe₂O₃ hierarchical nanostructures may be used as multi-functional materials for optoelectronic and magnetic devices. Supported by the National Natural Science Foundation of China (Grant Nos. 50772025 and 50872159), the Ministry of Science and Technology of China (Grant No. 2008DFR20420), the China Postdoctoral Science Foundation (Grant Nos. 20060400042 and 200801044), the Natural Science Foundation of Heilongjiang Province, China (Grant No. F200828), the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20070217002), and the Innovation Foundation of Harbin City (Grant No. RC2006QN017016)     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Facile fabrication of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Ag<Subscript>2</Subscript>S heterojunction with enhanced photoelectrochemical water splitting property

The α-Fe₂O₃/Ag₂S p-n heterojunction has been prepared via a facile room temperature successive ionic layer adsorption and reaction (SILAR) method. The heterojunction exhibits higher photoelectrochemical property compared to bare α-Fe₂O₃. The amount of Ag₂S has a significant effect on the PEC performance, which could be controlled by varying the number of SILAR cycles. The α-Fe₂O₃/Ag₂S p-n heterojunction prepared via 6 cycles of SILAR processes displays the best photoelectrochemical performance, which exhibits 1.8 times enhancement of photocurrent density and 70 mV cathodic shift of onset potential compared to bare α-Fe₂O₃. The improved PEC performance could be attributed to the formation of p-n junction between Ag₂S and α-Fe₂O₃, which not only enhanced the optical absorption ability, but also facilitated the separation efficiency of photogenerated charge carriers and passivized the surface state.     

Dye-sensitized solar cells with 3D flower-like α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-decorated reduced graphenes oxide as photoanodes

For the first time, we report a one-step fabrication of an environment-friendly approach to synthesize flower-like α-Fe₂O₃ hierarchical nanoparticles (NPs)/reduced graphene oxide (RGO) hybrids by combining the graphene oxide (GO) with the growth of α-Fe₂O₃ NPs. The GO sheet which possesses the functional group, such as hydroxyl (–OH) and carbonyl groups (–OOH), can be easily incorporated with the petal of the flower-like α-Fe₂O₃ in ethanol and water solution through a solvothermal process, during which GO is reduced to RGO without the addition of any strong reducing agent or requiring any post-high-temperature annealing process. The as-prepared samples are loose and porous with flower-like structure, and the RGO hybrids were wrapped up uniformly on the sheet of α-Fe₂O₃ NPs. To demonstrate the potential applications, we have fabricated dye-sensitized solar cells (DSSCs) from the as-synthesized hierarchical flower-like α-Fe₂O₃/RGO and investigated it for the photoanode of DSSCs. Results show that the hierarchical α-Fe₂O₃/RGO solar cell exhibits improved performances in comparison with the free α-Fe₂O₃ NPs. The enhancement of photovoltaic properties is attributed to the unique porous nature and good conductivity which allow more efficient diffusion of I^? ions and facilitate the transfer of electron in the network.     

Luminescence properties of Nd<Superscript>3+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in organic media

Nd³⁺-doped yttrium oxide nanoparticles (Y₂O₃:Nd) with cubic phase were obtained successfully by a glycine-nitrate solution combustion method. The results of Fourier transform infrared spectra (FTIR) showed that the –OH groups residing on the nanoparticles surfaces were reduced effectively by modifying with capping agent. The modified Y₂O₃:Nd nanoparticles displayed good monodispersity and excellent luminescence in N,N-dimethylformamide (DMF) solvent. Some optical parameters were calculated by Judd–Ofelt analysis based on absorption and fluorescence spectra. A relative large stimulated emission cross section, 1.7×10⁻²⁰ cm², of the ⁴F_3/2→⁴I_11/2 transition was calculated. Theses results show that the modified Y₂O₃:Nd nanoparticles display good luminescence behavior in organic media.     

Specific features of the magneto-optical properties of α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the IR region

The spectra of reflection and magnetoreflection of light from the crystalline insulator α-Al₂O₃ in the IR spectral region (λ = 2.5–25 μm) are investigated. Some features in the magnetoreflection spectra in the wavelength range corresponding to the excitation of optical phonon modes in α-Al₂O₃ are found. A significant increase in magnetoreflection is observed near these wavelengths. The amplitude and shape of the magnetore-flection spectra for the p and s polarizations of probe light are determined. It is shown that the optical and magneto-optical properties of α-Al₂O₃ in the IR region can be described on the basis of the theory of polaron excitation. A satisfactory correlation between the theoretical and experimental spectra is obtained, which indicates that polarons play an important role in determining the optical characteristics of nonmagnetic insulators and make the dominant contribution to the magnetoreflection spectra.