Preparation and characterization of α-Fe2O3–CeO2 composite

In our previous study we attempted to see the effect of cerium doping (Ce/Fe ratio 0.015 to 0.074) on goethite matrix and conversion of doped goethite to hematite. In the present communication, nano-structured α-Fe₂O₃–CeO₂ composite with Fe/Ce weight ratio as 1.1 has been synthesized by calcination of goethite-cerium hydroxide precursor prepared by co-precipitation method. It was observed that co-precipitation of cerium along with iron in hydroxide medium resulted in hindering the formation of crystalline order as the precursor formed showed poorly crystallized goethite and almost no crystallinity in Ce(OH)₄. Calcination of the precursor at 400 °C showed the formation of hematite together with a broad peak corresponding to cerium oxide whereas at 800 °C, two distinct phases of α-Fe₂O₃ and CeO₂ were observed. The Mössbauer spectra showed the presence of a paramagnetic component both for the precursor as well as for the sample calcined at 400 °C but on raising the calcination temperature to 800 °C, the paramagnetic component disappeared and the spectrum corresponding to pure α-Fe₂O₃ phase was observed. The microstructure of the product obtained by calcining at 800 °C showed rod like structure (30 to 50 nm width and 300 to 500 nm length) of α-Fe₂O₃ having equi-dimensional CeO₂ particles on and around the surface. Besides the rods, equi-dimensional particles and agglomerates corresponding to CeO₂ were also observed. The results show that co-precipitation followed by calcinations gives nanorods hematite with CeO₂ particles bonded to its surface.     

A new combustion route to γ-Fe2O3 synthesis

A new combustion route for the synthesis of γ-Fe ₂ O ₃ is reported by employing purified a-Fe ₂ O ₃ as a precursor in the present investigation. This synthesis which is similar to a self propagation combustion reaction, involves fewer steps, a shorter overall processing time, is a low energy reaction without the need of any explosives, and also the reaction is completed in a single step yielding magnetic iron oxide i.e. γ-Fe ₂ O ₃ .The as synthesized γ-Fe ₂ O ₃ is characterized employing thermal, XRD, SEM, magnetic hysteresis, and density measurements. The effect of ball-milling on magnetic properties is also presented.     

Green synthesis of α-Fe2O3 nanoparticles for photocatalytic application

In this study, the preparation of α-Fe₂O₃ nanoparticles using curcuma and tea leaves extract are reported. The curcuma and tea leaves are acted as a reductant and stabilizer. The crystal structure and particle size of the as-synthesized materials were measured through X-ray diffraction. X-ray diffraction patterns revealed that the as-prepared samples were α-Fe₂O₃ nanoparticles with well-crystallized rhombohedral structure and the crystallite sizes of the α-Fe₂O₃ nanoparticles are 4 and 5 nm. Scanning electron microscopy images showed that the prepared samples have spherical shape. The purity and properties of the as-synthesized α-Fe₂O₃ nanoparticles were measured by Raman spectroscopy. The chemical compositions of the as-prepared α-Fe₂O₃ nanoparticles have been analyzed by Fourier transform infrared spectroscopy. The absorption edge of the α-Fe₂O₃ nanoparticles are 561 and 551 nm. The photocatalytic activity of the α-Fe₂O₃ nanoparticles was measured by degradation of methylene orange and the α-Fe₂O₃ nanoparticles showed the excellent photocatalytic performance.     

A novel method for synthesis of α-Si3N4 nanowires by sol–gel route

Abstract

Silicon nitride (Si₃ N₄) nanowires have been prepared by carbothermal reduction followed by the nitridation (CTRN) of silica gel containing ultrafine excess carbon obtained by the decomposition of dextrose over the temperature range of 1200–1350 °C. This innovative process involves repeated evacuation followed by purging of nitrogen gas so that the interconnected nanopores of the gel are filled with nitrogen gas prior to heat treatment. During heat treatment at higher temperatures, the presence of nitrogen gas in the nanopores of the gel starts the CTRN reaction simultaneously throughout the bulk of the gel, leading to the formation of Si₃ N₄ nanowires. The in situ generated ultrafine carbon obtained by the decomposition of dextrose decreases the partial pressure of oxygen in the system to stabilize the nanowires. The nanowires synthesized by this process are of ～500 nm diameter and ～0.2 mm length. The product was characterized by scanning electron microscope (SEM), energy dispersive x-ray analysis (EDX), x-ray diffraction (XRD) and infrared (IR) spectra.     

Facile solution synthesis of α-FeF3·3H2O nanowires and their conversion to α-Fe2O3 nanowires for photoelectrochemical application

We report for the first time the facile solution growth of α-FeF(3)·3H(2)O nanowires (NWs) in large quantity at a low supersaturation level and their scalable conversion to porous semiconducting α-Fe(2)O(3) (hematite) NWs of high aspect ratio via a simple thermal treatment in air. The structural characterization by transmission electron microscopy shows that thin α-FeF(3)·3H(2)O NWs (typically <100 nm in diameter) are converted to single-crystal α-Fe(2)O(3) NWs with internal pores, while thick ones (typically >100 nm in diameter) become polycrystalline porous α-Fe(2)O(3) NWs. We further demonstrated the photoelectrochemical (PEC) application of the nanostructured photoelectrodes prepared from these converted hematite NWs. The optimized photoelectrode with a ~400 nm thick hematite NW film yielded a photocurrent density of 0.54 mA/cm(2) at 1.23 V vs reversible hydrogen electrode potential after modification with cobalt catalyst under standard conditions (AM 1.5 G, 100 mW/cm(2), pH = 13.6, 1 M NaOH). The low cost, large quantity, and high aspect ratio of the converted hematite NWs, together with the resulting simpler photoelectrode preparation, can be of great benefit for hematite-based PEC water splitting. Furthermore, the ease and scalability of the conversion from hydrated fluoride NWs to oxide NWs suggest a potentially versatile and low-cost strategy to make NWs of other useful iron-based compounds that may enable their large-scale renewable energy applications.     

Facile hydrothermal route to the controlled synthesis of α-Fe2O3 1-D nanostructures

Single-crystalline α-Fe₂O₃ 1-D nanostructures can be obtained via a facile one-step hydrothermal synthetic route. It was found that the introduction of SnCl₄ played a key role in determining the composition and morphology of α-Fe₂O₃. The addition of SnCl₄ favours the formation of Fe₂O₃ rather than FeOOH, and the morphology can be tuned from nanorod to double-shuttle as the increase of SnCl₄ concentration. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). This simple method does not need any seed, catalyst, or template, thus is promising for large-scale and low-cost production.     

Top-down synthesis of mesocrystalline α-Fe2O3 submillimeter-sized rhombohedrons

ABSTRACT

Here, we focus on the obtaining of mesocrystalline submillimeter-sized (150/50 µm) rhombohedral hematite (α-Fe₂O₃) by thermal treatment in air of single crystalline submillimeter-sized (150/50 µm) rhombohedrons of ferrous carbonate (FeCO₃). Mass spectrometer-coupled thermogravimetric analysis and TGA-MS revealed the chemical reactions occurring during the thermal treatment of ferrous carbonate sample. The X-ray Diffraction (XRD) data sustain that the final product is hematite. The XRD line-profile analysis indicates that the resulted hematite is built of individual ordered crystallites with 66 ± 5 nm average sizes, confirmed by scanning electron microscopy and transmission electron microscopy images. Small-angle x-ray scattering investigation of hematite sample was presented. The log-log plot of scattering intensity decay showed the same slope, α = ?3.76, corresponding to both high and low scattering vector regions; the fractal surface is D_s = 2.24. This fractality is extended over a range of sizes and can touch high molecular dimensionality. The internal morphology and the synthesis mechanism of the obtained hierarchical superstructure were described.     

Novel process for synthesis of α-Fe2O3: microstructural and optoelectronic investigations

Novel chemical synthesis method has been successfully employed for the preparation of n type α-Fe₂O₃ nanoparticles. Thin films of annealed Fe₂O₃ powders processed on glass substrates using spin coating technique. The effects of process temperature on the structural, morphological, electrical transport and optical properties were studied. X-ray diffraction study revealed formation of single phase nanocrystalline hexagonal α-Fe₂O₃. Microstructural analysis confirms nanostructured morphology. Dc electrical conductivity measurement reveled the semiconducting nature with room temperature electrical conductivity increased from 10^?4 to 10^?3 (Ω cm)^?1 as process temperature of Fe₂O₃ increased from 400 to 700 °C respectively. The n-type electrical conductivity is confirmed from thermo-emf measurement with no appreciable change in thermoelectric power after increasing processing temperature. The decrease in the band gap energy from 3.88 to 2.62 eV was observed after increasing process temperature.     

Thermal decomposition synthesis of 3D urchin-like α-Fe2O3 superstructures

Urchin-like α-Fe₂O₃ superstructures have been deposited on Si substrate using thermal decomposition FeCl₃ solution at 200–600 °C in the oven. The morphologies and structures of the synthesized urchin-like superstructures have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The results show that urchin-like α-Fe₂O₃ superstructures were a polycrystal with the rhombohedral structure and typical diameters of 16–20 nm and lengths up to 1.0 μm. The as-prepared α-Fe₂O₃ superstructures have a high Brunauer–Emmett–Teller (BET) surface area of about 60.24 m²/g. The photoluminescence spectrum of the urchin-like α-Fe₂O₃ superstructures consists of one weak emission peak at 548 nm (2.26 eV). A possible new mechanism for the formation of the urchin-like superstructures was also preliminarily discussed.     

Solvothermal synthesis and characterization of acicular α-Fe2O3 nanoparticles

Nanometer-sized α-Fe₂O₃ particles have been prepared by a simple solvothermal method using ferric acetylacetonate as a precursor. The products were characterized by X-ray diffraction (XRD), energy dispersive X-ray microanalysis (EDAX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transition electron microscopy (TEM), infrared spectroscopy (IR) and thermal analysis (TG-DTA). XRD indicates that the product is single-phase α-Fe₂O₃ with rhombohedral structure. Bundles of acicular shaped nanoparticles are seen in TEM images with an aspect ratio ～ 12; typically 8–12 nm wide and over 150 nm long. The α-Fe₂O₃ nanoparticles posses a high thermal stability, as observed on thermal analysis traces.     

Prospects for the incorporation of cobalt into α-Fe2O3 nanorods during hydrothermal synthesis

A feasibility study on the incorporation of cobalt into α-Fe₂O₃ nanorods (NRs) during hydrothermal synthesis (HS) is presented as a function of FeCl₃ and CoCl₂ concentration, phosphate surfactant concentration and pH value, with samples assessed using X-ray diffractometry, transmission electron microscopy, selected area electron diffraction and energy dispersive X-ray analysis. No evidence was found for the incorporation of cobalt into α-Fe₂O₃ NRs at low pH, whilst synthesis at intermediate and high pH values favoured the formation of CoFe₂O₄ NPs. The critical role of pH value over the precipitation, size and phase purity of the nanostructured reaction products is emphasised. At pH ~2, large, well crystalline α-Fe₂O₃ nanoparticles (NPs) and NRs were grown from FeCl₃ solution in the absence and presence of phosphate, respectively, whilst no evidence was found for Co precipitation or incorporation in α-Fe₂O₃ following HS in the presence of CoCl₂. At pH ~8, smaller α-Fe₂O₃ NPs, as well as Co₃O₄ and CoFe₂O₄ NPs were synthesised from FeCl₃, CoCl₂, or a mixture thereof. HS at pH ~12 produced a mixture of larger CoFe₂O₄ NPs and α-Fe₂O₃ NPs depending on the Fe:Co molar ratio. The formation of intermediate metastable (oxy)hydroxide phases is considered pH dependent, providing for a variety of different reaction pathways. Further, inclusion of preformed Co₃O₄ and CoFe₂O₄ NPs to the FeCl₃ solution at pH ~2 in the presence of phosphate surfactant resulted in the synthesis of α-Fe₂O₃ NRs with residual Co₃O₄ and CoFe₂O₄ NPs attached to their surfaces. The CoFe₂O₄ NPs encouraged local dissolution leading to the formation of α-Fe₂O₃ NR surface corrugations.     

Effect of mechanical activation on the synthesis of α-Fe2O3-Cr2O3 solid solutions

Continuous -Fe₂O₃-Cr₂O₃ solid solution series have been synthesized by two methods: (i) direct heating of coprecipitated hydroxides, and (ii) mechanical pre-treatment followed by heating. It is shown that mechanical treatment leads to a decrease in the preparation temperature of the solid solutions to 623 K. The formation of a continuous solid solution series by direct heating begins only at 773 K. The formation of the solid solutions was established by X-ray diffraction analysis, infrared and Mössbauer spectroscopy. The decrease in synthesis temperature of the -Fe₂O₃-Cr₂O₃ solid solutions is attributed to activation of the samples during their mechanical treatment. The samples obtained have large specific surface areas (up to 130 m² g^–1).     

Novel and simple route for the synthesis of core–shell chitosan–gold nanocomposites

This work presents a novel and simple route for the synthesis of water-soluble core–shell chitosan–gold nanocomposites. The experimental procedure can be summarized by the following steps: (i) chitosan deacetylation, (ii) chitosan depolymerization, (iii) chitosan nanoparticles’ formation and (iv) chitosan–gold nanocomposite formation. FT-IR spectroscopic results indicate that the formation of chitosan nanoparticles (ChtNPs) occurs via NH₃⁺ and PO⁻ groups electrostatic interactions, while UV–vis spectra points to a possible embedding of gold nanoparticles into the ChtNPs. This feature was confirmed by electronic transmission microscopy measurements. Chitosan and gold are biocompatible materials. Added to this, the obtained chitosan–gold nanocomposites presented thermal and absorbance properties which strongly point to their potential use in phototherapeutic processes.     

A novel wet chemistry/two-step calcining process for the synthesis of ultrafine α-Al2O3 particles

Ultrafine α-Al₂O₃ particles have been synthesized via a wet chemistry/two-step calcining process. X-ray diffraction (XRD) analysis shows that the as-synthesized particles are of single-phase α-Al₂O₃. The grain size of the particles is examined by TEM analysis and is found to be around 80–100 nm. The study demonstrates a novel process for the synthesis of ultrafine α-Al₂O₃ particles.     

Simple and rapid synthesis of α-Fe2O3 nanowires under ambient conditions

We propose a simple method for the efficient and rapid synthesis of one-dimensional hematite (α-Fe₂O₃) nanostructures based on electrical resistive heating of iron wire under ambient conditions. Typically, 1–5 μm long α-Fe₂O₃ nanowires were synthesized on a time scale of seconds at temperatures of around 700 ° ⊂. The morphology, structure, and mechanism of formation of the nanowires were studied by scanning and transmission electron microscopies, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman techniques. A nanowire growth mechanism based on diffusion of iron ions to the surface through grain boundaries and to the growing wire tip through stacking fault defects and due to surface diffusion is proposed. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

A simple complex-copolymer route to the fabrication of single crystalline α-Fe2O3 nanoplatelets in high yield

Uniform single crystalline α-Fe₂O₃ nanoplatelets with a diameter of about 100 nm and a thickness of about 20 nm were fabricated in high yield through a simple complex-copolymer hydrothermal method. Contrast experiments indicated that formation of the single crystalline α-Fe₂O₃ ellipsoids could be ascribed to the cooperative effect of PEO₂₀PPO₇₀PEO₂₀ (P123) triblock copolymer template and citrate complexation. Compared with the bulk counterpart, thus-prepared α-Fe₂O₃ nanoplatelets exhibited a wider band gap of 2.25 eV, which could be ascribed to the nanosize effect.     

Enhanced ethanol sensing properties based on α-Fe2O3/In2O3 hollow microspheres

α-Fe₂O₃ and In₂O₃ hollow microspheres were synthesized via a simple green hydrothermal route, and the α-Fe₂O₃/In₂O₃ composite sample was prepared by mixing two products above together in a molar ratio of 1:1. Traditional ceramic tube structure gas sensors were fabricated and their gas sensing characteristics were obtained. The results indicated that the α-Fe₂O₃/In₂O₃ sample showed an improved sensitivity and selectivity to ethanol, compared with either α-Fe₂O₃ or In₂O₃ sample. Moreover, the sensitivities of both In₂O₃ and α-Fe₂O₃/In₂O₃ sensors were good linear with gas concentrations (1–500?ppm) to ethanol, and the response was found to remain stable for 150?days. In addition, the gas sensing mechanism of ethanol detection has been discussed.     

Hydrothermal synthesis of monodisperse dodecahedron α-Fe2O3 nanocrystals with high photocatalytic activity

Novel α-Fe₂O₃ dodecahedron nanocrystals were prepared by a facile one-step hydrothermal method without using any templates. The samples were analyzed by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, respectively. The results revealed that the as-prepared nanocrystals with the average diameters of 200 nm are well-shaped symmetric hexagonal bipyramidal structure. The homogeneous dodecahedron nanoparticles were obtained by optimizing the experimental conditions including reaction temperatures and time. A possible formation mechanism was also proposed. To demonstrate potential applications, the photocatalytic activity of the as-prepared samples was evaluated by photo-degradation of rhodamine B from aqueous solution at room temperature. Results show that the α-Fe₂O₃ dodecahedron with exposed (012) plane exhibits significantly improved photocatalytic activities for degradation of rhodamine B in aqueous solution under visible light irradiation.