Ti-doped α-Fe2O3 by quantum-chemical modeling

Structure and electronic properties of Ti-doped hematite (α-Fe₂O₃) crystal have been studied using a quantum-chemical method based on the Hartree–Fock theory. A supercell model employing a system consisting of 120 atoms has been exploited throughout the investigation. The impurity presence produces defect-inward displacement for the majority of Fe atoms whereas the O atoms experience both defect-inward and defect-outward shifts depending on their original position in the crystal. A small reduction in the band-gap width due to the Ti incorporation is also observed which might lead to some increase in the electrical conductivity in concordance to the available experimental measurements. Two new phenomena are discovered according to results of our modeling, being those of electron density redistribution between different 3d Atomic Orbitals (AOs) within the same Fe atom and extra valence electron escape from the Ti-surrounding region towards far-situated Fe atoms. The latter presumably could explain some contradictory results on saturation magnetization in Ti-doped α-Fe₂O₃ compounds.     

Kinetics of oxygen evolution at α-Fe2O3 photoanodes: a study by photoelectrochemical impedance spectroscopy

Photoelectrochemical Impedance Spectroscopy (PEIS) has been used to characterize the kinetics of electron transfer and recombination taking place during oxygen evolution at illuminated polycrystalline α-Fe(2)O(3) electrodes prepared by aerosol-assisted chemical vapour deposition from a ferrocene precursor. The PEIS results were analysed using a phenomenological approach since the mechanism of the oxygen evolution reaction is not known a priori. The results indicate that the photocurrent onset potential is strongly affected by Fermi level pinning since the rate constant for surface recombination is almost constant in this potential region. The phenomenological rate constant for electron transfer was found to increase with potential, suggesting that the potential drop in the Helmholtz layer influences the activation energy for the oxygen evolution process. The PEIS analysis also shows that the limiting factor determining the performance of the α-Fe(2)O(3) photoanode is electron-hole recombination in the bulk of the oxide.     

Kinetic Analysis Crystallization of α-Al2O3 by Dynamic DTA Technique

The phase transformation of seeded (5 mass% Fe₂O₃ as a Fe(NO₃)₃ solution) boehmite derived alumina gel to α-Al₂O₃ was studied with DTA technique and compared with unseeded and α-Al₂O₃ seeded boehmite gels. Data for kinetic analysis of α-Al₂O₃ crystallization were obtained from quantitative DTA curves. The kinetic parameters were analysed by traditional Kissinger analysis and Friedman and Ozawa-Flynn-Wall methods using the Netzsch Thermokinetics program. Results of the comparison of values of activation energies for all three gels and methods are the process of α-Al₂O₃ transformation for originally γ-AlOOH/Fe(NO₃)₃ gels goes like that of unseeded boehmite gels,only under lower temperatures (lower about 200°C). This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics and mechanism of light-driven oxygen evolution at thin film α-Fe2O3 electrodes

Rate constants for recombination and hole transfer during oxygen evolution at illuminated α-Fe(2)O(3) electrodes were measured by intensity-modulated photocurrent spectroscopy and found to be remarkably low. Treatment of the electrode with a Co(II) solution suppressed surface recombination but did not catalyse hole transfer. Intermediates in the reaction were detected spectroscopically.     

Activation energies for the rate-limiting step in water photooxidation by nanostructured α-Fe2O3 and TiO2

Competition between charge recombination and the forward reactions required for water splitting limits the efficiency of metal-oxide photocatalysts. A key requirement for the photochemical oxidation of water on both nanostructured α-Fe(2)O(3) and TiO(2) is the generation of photoholes with lifetimes on the order of milliseconds to seconds. Here we use transient absorption spectroscopy to directly probe the long-lived holes on both nc-TiO(2) and α-Fe(2)O(3) in complete PEC cells, and we investigate the factors controlling this slow hole decay, which can be described as the rate-limiting step in water oxidation. In both cases this rate-limiting step is tentatively assigned to the hole transfer from the metal oxide to a surface-bound water species. We demonstrate that one reason for the slow hole transfer on α-Fe(2)O(3) is the presence of a significant thermal barrier, the magnitude of which is found to be independent of the applied bias at the potentials examined. This is in contrast to nanocrystalline nc-TiO(2), where no distinct thermal barrier to hole transfer is observed.     

Studies on fabricating α-Fe2O3 ultrafine particles by LB film technology

The α-Fe₂O₃ ultrafine particles were dispersed in the solutions of stearic acid/n-hexane/chloroform by the ultrasonic method, and fabricated by the Langmuir–Blodgett film technology. α-Fe₂O₃ ultrafine particles/stearic acid composite LB films were characteried by π–A curve, UV-visible absorption spectrum, IR spectrum, small angle X-ray diffraction, TEM and electron diffraction. The results showed the following: the αFe₂O₃ ultrafine particles were uniformly dispersed in organic solvents; the film-forming characterization of the α-Fe₂O₃ ultrafine particles/stearic acid monolayer was fine, the α-Fe₂O₃ ultrafine particles in the composite film had a small orientation; the α-Fe₂O₃ ultrafine particles/stearic acid composite film had a lamellar structure.     

A 3D α-Fe2O3 nanoflake urchin-like structure for electromagnetic wave absorption

An α-Fe(2)O(3) nanoflake urchin-like structure is formed via the thermal oxidation of micrometre-sized iron spheres in air at temperatures of 300-400 °C. The material consists of α-Fe(2)O(3) nanoflakes grown perpendicularly to the sphere surface, a layer of a mixture of α-Fe(2)O(3) and Fe(3)O(4) as the oxidation shell, and an iron core. The ranges of the tip diameters of the nanoflakes are 20-30 nm (300 °C), 30-50 nm (350 °C), and 60-100 nm (400 °C). A composite consisting of the α-Fe(2)O(3) nanoflake urchin-like structure and an epoxy resin exhibits an excellent electromagnetic (EM) wave absorption ability. A small tip diameter (20-30 nm) and a high density (3 × 10(13) nanoflakes m(-2)) lead to a good network structure and good EM wave absorption. A minimum reflection loss (RL) of -33.8 dB (99.93% of EM wave absorption) at 7.8 GHz can be achieved using a 70 wt% urchin-like material as the filler in the resin matrix. In addition, a composite containing 60 wt% unchin-like material exhibits dual-frequency EM wave absorption. The peaks of the minimum RL values are located at 9.7 GHz (-26.2 dB) and 25.2 GHz (-21.0 dB). The unique morphology of the α-Fe(2)O(3) nanoflake urchin-like material is believed to be a key factor in the enhancement of the EM wave absorption.     

Micro/Nanoengineered α-Fe2O3 Nanoaggregate Conformably Enclosed by Ultrathin N-Doped Carbon Shell for Ultrastable Lithium Storage and Insight into Phase Evolution Mechanism

The Fe-based transition metal oxides are promising anode candidates for lithium storage considering their high specific capacity, low cost, and environmental compatibility. However, the poor electron/ion conductivity and significant volume stress limit their cycle and rate performances. Furthermore, the phenomena of capacity rise and sudden decay for α-Fe₂O₃ have appeared in most reports. Here, a uniform micro/nano α-Fe₂O₃ nanoaggregate conformably enclosed in an ultrathin N-doped carbon network (denoted as M/N-α-Fe₂O₃@NC) is designed. The M/N porous balls combine the merits of secondary nanoparticles to shorten the Li⁺ transportation pathways as well as alleviating volume expansion, and primary microballs to stabilize the electrode/electrolyte interface. Furthermore, the ultrathin carbon shell favors fast electron transfer and protects the electrode from electrolyte corrosion. Therefore, the M/N-α-Fe₂O₃@NC electrode delivers an excellent reversible capacity of 901 mA h g⁻¹ with capacity retention up to 94.0 % after 200 cycles at 0.2 A g⁻¹. Notably, the capacity rise does not happen during cycling. Moreover, the lithium storage mechanism is elucidated by ex situ XRD and HRTEM experiments. It is verified that the reversible phase transformation of α↔γ occurs during the first cycle, whereas only the α-Fe₂O₃ phase is reversibly transformed during subsequent cycles. This study offers a simple and scalable strategy for the practical application of high-performance Fe₂O₃ electrodes.     

Synthesis,Characterization and Antimicrobial Properties of Superparamagnetic α-Fe2O3 Nanoparticles Stabilized by Biocompatible Starch

Journal of Cluster Science - In the present study we have synthesized α-Fe2O3 nanoparticles in a more conventionally established NaBH4 reduction, but using a bio-macromolecule, starch. The...     

Preparation of α-Fe2O3 Nanofiber via Electrospinning Process

A thin PVA/FeCl3 composite fiber was prepared by using sol-gel processing and electrospinning techniques. A nanofiber of α-Fe2O3 with the diameter of 50-150 nm was obtained via high temperature calcination of the PVA/FeCl3 composite fiber. The material was characterized by infra-red (IR) spectroscopy, X-ray diffraction(XRD), and scanning electron microscopy(SEM). The results show that the fiber after the calcination at 700℃ was a pure α-Fe2O3 nanofiber.     

Preparation of α-Fe2O3 Nanofiber via Electrospinning Process

A thin PVA/FeCl3 composite fiber was prepared by using sol-gel processing and electrospinning tech niques. A nanofiber of α-Fe2O3 with the diameter of 50-150 nm was obtained via high temperature calcina tion of the PVA/FeCl3 composite fiber. The material was characterized by infra-red(IR) spectroscopy, X-ray diffraction(XRD), and scanning electron microscopy(SEM). The results show that the fiber after the calci nation at 700 ℃ was a pure α-Fe2O3 nanofiber.     

Synthesis and photocatalytic properties of α-Fe2O3 nanoellipsoids

A simple and a novel chemical approach was used for the growth of α-Fe₂O₃ nanostructures. Field emission scanning electron microscopy analysis revealed the monodisperse nanoellipsoid morphology of α-Fe₂O₃ nanostructures. The sizes of the short axis and the long axis of these ellipsoids were in the ranges of 50–60 nm and 40–50 nm, respectively. XRD analysis revealed that the product exhibited α-Fe₂O₃ phase. Comprehensive TEM and HRTEM analysis revealed that α-Fe₂O₃ nanoellipsoids are single crystal in nature. The methylene blue decomposition kinetics was studied for different irradiation time. The methylene blue was totally decomposed by increasing the irradiation time up to 220 min.     

Preparation of Nanosized α-Fe2O3 Using Mechanical Activation

The processes occurring during the mechanical activation of a-Fe₂O₃ (hematite) in the presence of oleic acid in a centrifugal-planetary mill have been investigated. Mechanical activation for 10 h afforded hematite powder with particles size of 10–40 nm, as shown by means of X-ray diffraction analysis, FTIR spectroscopy, high-resolution transmission electron microscopy, and specific surface area measurements. Longer milling has led to mechanochemical transformation of hematite into Fe₃O₄ (magnetite).

     

Dynamics of photogenerated holes in nanocrystalline α-Fe2O3 electrodes for water oxidation probed by transient absorption spectroscopy

Transient absorption spectroscopy on the μs-s time scale is used to monitor the yield and decay dynamics of photogenerated holes in nanocrystalline hematite photoanodes. In the absence of a positive applied bias, these holes are observed to undergo rapid electron-hole recombination. The application of a positive bias results in the generation of long-lived (3 ± 1 s lifetime) photoholes.     

Synthesis and magnetic properties of hollow α-Fe2O3 nanospheres templated by carbon nanospheres

Hollow α-Fe₂O₃ nanospheres were synthesized by using novel carbon spheres as templates. By carefully controlling the fundamental experimental parameters, porous nanospheres with diameters of 60–80 nm and nanojujubes with diameters of 80–100 nm have been efficiently obtained, respectively. The growth mechanism and magnetic properties are also discussed in detail. The coercivity values of the hollow α-Fe₂O₃ nanospheres and nanojujubes are much higher than those of other α-Fe₂O₃ nanomaterials. Due to the unique morphology with cavum and porous wall, the ferromagnetic nanospheres could be promising candidates as a magnetic carrier for drug targeting.     

Effect of MnO2 and α-Fe2O3 on organic binders degradation investigated by Raman spectroscopy

Vibrational spectroscopy and GC–MS were used to investigate the effect of MnO₂ and α-Fe₂O₃ on the degradation of methyl linoleate and vegetal and animal fatty. The metal oxides are among the most employed pigments in rock art paintings, whereas the organic compounds were used to mimic organic binders potentially used in such paintings.Both oxides were very effective in the catalytic oxidation of the organic substrates and light had no significant effect, qualitatively or quantitatively, on the final products. In the case of methyl linoleate without metal oxide, the effect of light (visible) was investigated and it was demonstrated that the samples kept in the dark produced relatively less oxidation products, although the main products were the same (hexanal, methyl 9-oxononanoate and methyl octanoate). In the presence of MnO₂ and α-Fe₂O₃ methyl 9-oxononanoate was the main product, followed by hexanal. The spectral patterns of the oxidation products were different for manganese and iron oxide and GC–MS demonstrated that more compounds are formed in the former than with α-Fe₂O₃. Vegetal and animal fatty presented the same behavior that methyl linoleate did.The results here reported indicated that the two pigments considered actively contribute to fat degradation and the presence of inorganic pigments is the main factor to take into account when organic binders degradation in rock art paintings are investigated.     

Binary α-Fe2O3–Co3O4 nanostructures for advanced oxidation process: Role of synergy for enhanced catalysis

Iron and its binary oxides are meticulously exploited for environmental remediations. However, only limited studies have been carried out on the degradation of industrial organics by advanced oxidation process. In this study, iron oxide, cobalt oxide, and iron–cobalt binary oxides were synthesized by a modified hydrothermal method as heterogeneous Fenton-like catalysts for the removal of methylene blue (MB) from wastewaters. The oxide nanostructures were characterized by different analytical techniques. Studying the effects of various parameters such as catalyst dose, MB concentration, and H₂O₂ concentration, the reaction conditions were optimized to enhance the removal of MB dye. The results revealed that α-Fe₂O₃–Co₃O₄ shows much higher activity than both Co₃O₄ and α-Fe₂O₃ for the degradation of MB at room temperature and beyond. The binary α-Fe₂O₃–Co₃O₄ shows degradation efficiency of 96.4% at 65 °C within 60 min. Furthermore, the binary α-Fe₂O₃–Co₃O₄ catalyst retains its activity for up to four successive cycles. A probable mechanism is also proposed, involving the generation of ‧OH radical as well as Fe²⁺/Fe³⁺ or Co²⁺/Co³⁺ redox couple of the binary α-Fe₂O₃–Co₃O₄ catalyst.     

Synthesis of three-dimensional flower-like α-Fe2O3 microspheres for high efficient removal of radiocobalt

Journal of Radioanalytical and Nuclear Chemistry - In this study, three-dimensional flower-like α-Fe2O3 (F-Fe2O3) microspheres were synthesized by a facile chemical bath method and...     

Amorphous/Crystalline Hetero-Phase TiO2-Coated α-Fe2O3 Core–Shell Nanospindles: A High-Performance Artificial Nitrogen Fixation Electrocatalyst

Electrochemical nitrogen fixation techniques have emerged as a promisingly sustainable approach to face the challenge associated with nitrogen activation of ammonia synthesis by the Haber–Bosch process under ambient conditions. Herein, the performance of electrocatalytic nitrogen reduction for the production of α-Fe₂O₃ nanospindles coated with mesoporous TiO₂ with different crystallinity [denoted as α-Fe₂O₃@mTiO₂-X (X=300, 400, and 500 °C)] were investigated. The as-prepared α-Fe₂O₃@mTiO₂-400 composite exhibits a large NH₃ yield (27.2 μg h⁻¹ mg_cat.⁻¹) at −0. 5 V vs. the reversible hydrogen electrode and a high Faradaic efficiency (13.3 %) in 0.1 m Na₂SO₄, with excellent electrochemical durability. This work presents a novel avenue for the rational design of efficient unique hetero-phase nanocatalysts toward sustainable electrocatalytic N₂ fixation.