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.     

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.     

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)].     

Mössbauer Spectroscopy Study of the Superparamagnetism of Ultrasmall ϵ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanoparticles

The superparamagnetism of an ensemble of ?-Fe₂O₃ nanoparticles with a mean size of 3.9 nm dispersed in a xerogel SiO₂ matrix is studied by the Mössbauer spectroscopy method. It is shown that most nanoparticles at room temperature are in the superparamagnetic (unblocked) state. As the temperature decreases, the progressive blocking of the magnetic moments of the particles occurs, which is manifested in the Mössbauer spectra as the transformation of the quadrupole doublet into a Zeeman sextet. The analysis of the relative intensity of the superparamagnetic (quadrupole doublet) and magnetically split (sextets) spectral components in the range of 4–300 K provides the particle size distribution, which is in agreement with the transmission electron microscopy data. The values of the effective magnetic anisotropy constants (K_eff) are determined, and the contribution of surface anisotropy (K_S) is estimated for particles of various sizes. It is shown that the quantity K_eff is inversely proportional to the particle size, which indicates the significant contribution of the surface to the magnetic state of the ?-Fe₂O₃ nanoparticles with the size of several nanometers.     

Template-free synthesis of hollow <Emphasis Type="Italic">α</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> microspheres

Nearly monodisperse hollow α-Fe₂O₃ microspheres composed of nanoparticles have been successfully synthesized through a facile template-free hydrothermal method. The products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. It is shown that the hollow α-Fe₂O₃ microspheres consist of well-aligned α-Fe₂O₃ nanoparticles with a mean diameter of about 15 nm. This facile reaction route presents an efficient method for mass production of monodisperse hollow magnetic nanomaterials. The final α-Fe₂O₃ microspheres exhibit special magnetic properties with a small remnant magnetization of 0.09 emu g⁻¹ and a high coercivity of 1121.67 Oe at room temperature.     

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.     

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)     

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.     

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.     

Influence of Matrix Nature on the Structural Characteristics of In<Subscript>2</Subscript>O<Subscript>3</Subscript>–CeO<Subscript>2</Subscript> and SnO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> Composites Fabricated by the Impregnation Method

The structural characteristics, valence states, and distribution of cerium ions between the components in In₂O₃–CeO₂ and SnO₂–CeO₂ nanocomposites fabricated using the impregnation method were studied. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) were used to show that, during impregnation, cerium ions are not included into In₂O₃ crystals and are disposed only on their surface in the form of nano-sized crystallites or amorphous clusters. On the other side, under the contact of CeO₂ clusters with a surface of SnO₂ matrix crystals, cerium ions penetrate into the surface layer of these crystals. In contrast to an In₂O₃–CeO₂ system, where the addition of CeO₂ does not affect the conduction activation energy, where cerium oxide is added to SnO₂, the observed increase in the resistance of a SnO₂–CeO₂ composite is accompanied by a sufficient increase in activation energy. These data and the XPS spectra confirm the modification of the surface layers of conductive SnO₂ crystals as, a result of the penetration of cerium ions into these layers.     

Sol–gel synthesis and characterization of Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite solid electrolytes

Composite solid electrolytes in the system (1???x)Li₂CO₃–xAl₂O₃, with x?=?0.0–0.5 (mole), were synthesized by a sol–gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy-dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed an amorphous feature of Li₂CO₃ and traces of α-LiAlO₂, γ-LiAlO₂ and LiAl₅O₈. The prepared composite samples possess high ionic conductivities at 130–180 °C on account of the presence of lithium aluminates as well as the formation of a high concentration of an amorphous phase of Li₂CO₃ via this sol–gel preparative technique.     

Deep metastable eutectic nanometer-scale particles in the MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

Laboratory vapor phase condensation experiments systematically yield amorphous, homogeneous, nanoparticles with unique deep metastable eutectic compositions. They formed during the nucleation stage in rapidly cooling vapor systems. These nanoparticles evidence the complexity of the nucleation stage. Similar complex behavior may occur during the nucleation stage in quenched-melt laboratory experiments. Because of the bulk size of the quenched system many of such deep metastable eutectic nanodomains will anneal and adjust to local equilibrium but some will persist metastably depending on the time–temperature regime and melt/glass transformation.     

Effect of grain boundary on resistive magnetodielectric property of polycrystalline <Emphasis Type="Italic">γ</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

We have investigated the role of the grain boundary on the resistive magnetodielectric property of polycrystalline γ-Fe₂O₃ through impedance spectroscopy measurements. Depending on the sample preparation temperature, the dielectric constant of γ-Fe₂O₃ is significantly different especially at low frequencies (<10⁴ Hz) and high temperatures (>200 K). The value of the magnetodielectric effect at a specific frequency and the resonance frequency for the maximized magnetodielectric effect are different, although polycrystalline γ-Fe₂O₃ samples show a quite similar magnetoresistance. Through the experimentally obtained resistance ratio between the grain and the grain boundary, we can reproduce the magnetodielectric curves based on the Maxwell–Wagner model and the measured magnetoresistance.     

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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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.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

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.     

Study of the KNO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system by differential scanning calorimetry

The structural and the thermodynamic properties of potassium nitrate KNO₃ and its composites with nanosized aluminum oxide Al₂O₃ have been studied by differential scanning calorimetry. It has been found that an amorphous phase forms in composites (1–x)KNO_3–xAl₂O₃. The thermal effect corresponding to this phase has been observed at 316°C. It has been found that the phase transition heats of potassium nitrate decreased as the aluminum oxide fraction increased.