Showing papers on "Iron oxide published in 2010"

Light-Induced Water Splitting with Hematite: Improved Nanostructure and Iridium Oxide Catalysis†

Abstract: Revved-up rust! Light-induced water splitting over iron oxide (hematite) has been achieved by using a particle-assisted deposition technique and IrO2-based surface catalysis. Photocurrents in excess of 3 mA cm-2 were obtained at +1.23 V versus the reversible hydrogen electrode under AM 1.5 G 100 mW cm-2 simulated sunlight. These photocurrents are unmatched by any other oxide-based photoanode. FTO=fluorine-doped tin oxide. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin Films Produced by Vapor Deposition

Abstract: Thin films of three iron oxide polymorphs, hematite, maghemite, and magnetite, were produced on KBr substrates using a conventional electron beam deposition technique coupled with thermal annealing. This method allowed for iron oxide thin films free from chemical precursor contaminants. The films were characterized using Fourier-transform infrared spectroscopy (FTIR), Raman microspectroscopy, and ellipsometry. These spectroscopic techniques allowed for a clear assignment of the phase of the iron oxide polymorph films produced along with an examination of the degree of crystallinity possessed by the films. The films produced were uniform in phase and exhibited decreasing crystallinity as the thickness increased from 40 to 250 nm.

Nanocrystal Growth on Graphene with Various Degrees of Oxidation

Abstract: We show a general two-step method to grow hydroxide and oxide nanocrystals of the iron family elements (Ni, Co, Fe) on graphene with two degrees of oxidation. Drastically different nanocrystal growth behaviors were observed on low-oxidation graphene sheets (GS) and highly oxidized graphite oxide (GO) in hydrothermal reactions. Small particles pre-coated on GS with few oxygen-containing surface groups diffused and recrystallized into single-crystalline nickel hydroxide Ni(OH)2 hexagonal nanoplates or iron oxide Fe2O3 nanorods with well defined morphologies. In contrast, particles pre-coated on GO were pinned by the high-concentration oxygen groups and defects on GO without recrystallization into well-defined shapes. Adjusting reaction temperature can be combined to further control materials grown on graphene. For materials with weak interactions with graphene, increasing the reaction temperature can lead to diffusion and recrystallization of surface species into larger crystals even on highly oxidized and defective GO. Our results suggest an interesting new approach to controlling the morphology of nanomaterials grown on graphene by tuning the surface chemistry of graphene as substrates for crystal nucleation and growth.

Iron Oxide-Based Nanotube Arrays Derived from Sacrificial Template-Accelerated Hydrolysis: Large-Area Design and Reversible Lithium Storage

Abstract: We report a novel “sacrificial template-accelerated hydrolysis” (STAH) approach to the synthesis of iron oxide-based nanotube arrays including hematite α-Fe2O3 and magnetite Fe3O4 on centimeter-scale conducting alloy substrates. ZnO nanowire arrays are chosen as the inexpensive and sacrificial templates that do not contribute to the component of final iron oxide nanotubes but can be in situ dissolved by the acid produced from the Fe3+ precursor hydrolysis. Interestingly, the ZnO template dissolution in turn accelerates the Fe3+ hydrolysis, which is essential to initiating the nanotube formation. Such a STAH approach provides a morphology-reservation transformation, when various shaped ZnO templates are adopted. Moreover, by introducing glucose into the precursor solution, we also successfully obtain carbon/hematite(C/α-Fe2O3) composite nanotube arrays on large-area flexible alloy substrate, with a large number of pores and uniform carbon distribution at a nanoscale in the nanotube walls. These arrays have...

Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria

Abstract: Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.

The determination of the activities of different iron species in Fe-ZSM-5 for SCR of NO by NH3

Abstract: The activities of different iron species in Fe-ZSM-5 for the selective catalytic reduction (SCR) of NO by NH3 were determined in terms of their turnover frequencies (TOF values). The relative concentrations of different species were correlated with their measured NOx reduction efficiencies and NH3 oxidation activities. Our results suggest that the SCR of NO by NH3 is catalyzed by different active sites with different activation energies. At temperatures below 300 °C, the SCR activity was observed to be primarily caused by monomeric iron sites; however, at T > 300 °C, T ≥ 400 °C and T ≥ 500 °C, the contribution of dimeric iron species, oligomeric species (e.g., trimeric and tetrameric iron species) and partially uncoordinated iron sites in the outmost layer of iron oxide particles, respectively, become important. The activation energies for monomeric and dimeric sites were evaluated to be about 36 kJ/mol and 77 kJ/mol, respectively. Due to their high activation energies, dimeric sites contributed more to the overall SCR activity at higher temperatures than did monomeric sites. The clustered sites not only contributed to the SCR activity but also caused nonselective oxidation of NH3 at T ≥ 350 °C, whereas the dimeric species governed the NH3 oxidation activity up to T = 500 °C. The TOF values for dimeric species were estimated to be 70 ± 13 s−1 at 500 °C. Monomeric sites were found to be completely inactive for NH3 oxidation up to 500 °C.

Alumina-supported iron oxide nanoparticles as Fischer–Tropsch catalysts: Effect of particle size of iron oxide

Abstract: The Fischer–Tropsch synthesis of unpromoted and nano-sized iron oxide supported on δ-Al2O3 was investigated using a fixed-bed reactor. The catalysts prepared from pre-synthesized iron oxide with varying particle size (2–12 nm) showed much higher catalytic activities than the one prepared by using conventional impregnation method. The best results for CO conversion were obtained when the catalyst had Fe particle size of 6.1 nm. With an increase in particle size, the reduction degree and C5+ selectivity was increased, whereas CH4 selectivity and the uptake of adsorbed CO were decreased. Turnover frequency (TOF) at 300 °C was increased from 0.02 to 0.16 s−1 when d(Fe0) was increased from 2.4 to 6.2 nm, and then it remains almost constant up to a particle size of 11.5 nm. Particle sizes of prepared iron oxide were analyzed by XRD and TEM, and the reduction behaviors of Fe/Al2O3 catalysts were studied by H2-TPR. The effective iron size, metal dispersion and reduction degree of Fe/Al2O3 catalysts were measured by CO chemisorption and O2 titration.

Electroless Deposition of Conformal Nanoscale Iron Oxide on Carbon Nanoarchitectures for Electrochemical Charge Storage

Abstract: We describe a simple self-limiting electroless deposition process whereby conformal, nanoscale iron oxide (FeOx) coatings are generated at the interior and exterior surfaces of macroscopically thick (∼90 μm) carbon nanofoam paper substrates via redox reaction with aqueous K2FeO4. The resulting FeOx-carbon nanofoams are characterized as device-ready electrode structures for aqueous electrochemical capacitors and they demonstrate a 3-to-7 fold increase in charge-storage capacity relative to the native carbon nanofoam when cycled in a mild aqueous electrolyte (2.5 M Li2SO4), yielding mass-, volume-, and footprint-normalized capacitances of 84 F g−1, 121 F cm−3, and 0.85 F cm−2, respectively, even at modest FeOx loadings (27 wt %). The additional charge-storage capacity arises from faradaic pseudocapacitance of the FeOx coating, delivering specific capacitance >300 F g−1 normalized to the content of FeOx as FeOOH, as verified by electrochemical measurements and in situ X-ray absorption spectroscopy. The addit...

Controlled synthesis of iron oxide nanoparticles over a wide size range.

Abstract: We report on the effect of using decanoic acid as capping ligand on the synthesis of iron oxide nanoparticles by thermal decomposition of an organic iron precursor in organic medium. This procedure allowed us to control the particle size within 5 nm and about 30 nm by modifying the precursor-to-capping ligand ratio in a systematic fashion and to further expand the particle size range up to about 50 nm by adjusting the final synthesis temperature. The nanoparticles also showed high saturation magnetization of about 80−83 emu/g at low temperature, almost size-independent and close to the value for the bulk counterpart. Decanoic acid-coated nanoparticles were transferred to water by using tetramethylammonium hydroxide, which allowed further coating with silica in a tetraethyl orthosilicate solution. Consequently, these iron oxide nanoparticles are tunable in size and highly magnetic, and they could become suitable candidates for various biomedical applications such as contrast agents for magnetic resonance i...

Highly Active Iron Oxide Supported Gold Catalysts for CO Oxidation: How Small Must the Gold Nanoparticles Be?†

Abstract: Highly Active Iron Oxide Supported Gold Catalysts for CO Oxidation : How Small Must the Gold Nanoparticles Be?

Thermal Character of Geopolymers Synthesized from Class F Fly Ash Containing High Concentrations of Iron and α-Quartz

Abstract: This article reports the thermal characteristics of geopolymers prepared with a class F fly ash containing 15 wt% iron oxide and 20 wt%α-quartz. The characterization techniques used included dilatometry, TGA, DTA, XRD, and SEM. Geopolymer specimens were prepared with nominal ratios of Si:Al=2.3 and Na:Al=0.85. Iron oxide in the fly ash precursor was found to play a critical role in the thermal expansion and morphology of geopolymers at temperatures >500°C. Volume changes of quartz on either side of the α–β phase transition cause only minor variations in thermal expansion.

Large-Scale and Controlled Synthesis of Iron Oxide Magnetic Short Nanotubes: Shape Evolution, Growth Mechanism, and Magnetic Properties

Abstract: We present a facile approach to the production of magnetic iron oxide short nanotubes (SNTs) employing an anion-assisted hydrothermal route by simultaneously using phosphate and sulfate ions. The size, morphology, shape, and surface architecture control of the iron oxide SNTs are achieved by simple adjustments of ferric ions concentration without any surfactant assistance. The result of a formation mechanism investigation reveals that the ferric ions concentrations, the amount of anion additive, and the reaction time make significant contributions to SNT growth. The shape of the SNTs is mainly regulated by the adsorption of phosphate ions on faces parallel to the long dimension of elongated α-Fe2O3 nanoparticles (c axis) during nanocrystal growth, and the hollow structure is given by the preferential dissolution along the c axis due to the strong coordination of the sulfate ions. Moreover, the as-synthesized hematite (α-Fe2O3) SNTs can be converted to magnetite (Fe3O4) and maghemite (γ-Fe2O3) ferromagneti...

Increased Cellular Uptake of Biocompatible Superparamagnetic Iron Oxide Nanoparticles into Malignant Cells by an External Magnetic Field

Abstract: Superparamagnetic iron oxide nanoparticles (SPIONs) are used as delivery systems for different therapeutics including nucleic acids for magnetofection-mediated gene therapy. The aim of our study was to evaluate physicochemical properties, biocompatibility, cellular uptake and trafficking pathways of the custom-synthesized SPIONs for their potential use in magnetofection. Custom-synthesized SPIONs were tested for size, shape, crystalline composition and magnetic behavior using a transmission electron microscope, X-ray diffractometer and magnetometer. SPIONs were dispersed in different aqueous media to obtain ferrofluids, which were tested for pH and stability using a pH meter and zetameter. Cytotoxicity was determined using the MTS and clonogenic assays. Cellular uptake and trafficking pathways were qualitatively evaluated by transmission electron microscopy and quantitatively by inductively coupled plasma atomic emission spectrometry. SPIONs were composed of an iron oxide core with a diameter of 8-9 nm, coated with a 2-nm-thick layer of silica. SPIONs, dispersed in 0.9% NaCl solution, resulted in a stable ferrofluid at physiological pH for several months. SPIONs were not cytotoxic in a broad range of concentrations and were readily internalized into different cells by endocytosis. Exposure to neodymium-iron-boron magnets significantly increased the cellular uptake of SPIONs, predominantly into malignant cells. The prepared SPIONs displayed adequate physicochemical and biomedical properties for potential use in magnetofection. Their cellular uptake was dependent on the cell type, and their accumulation within the cells was dependent on the duration of exposure to an external magnetic field.

High-performance, superparamagnetic, nanoparticle-based heavy metal sorbents for removal of contaminants from natural waters.

Abstract: We describe the synthesis and characterization of high-performance, superparamagnetic, iron oxide nanoparticle-based, heavy metal sorbents, which demonstrate excellent affinity for the separation of heavy metals in contaminated water systems (i.e., spiked Columbia River water). The magnetic nanoparticle sorbents were prepared from an easy-to-synthesize iron oxide precursor, followed by a simple, one-step ligand exchange reaction to introduce an affinity ligand to the nanoparticle surface that is specific to a heavy metal or class of heavy metal contaminants. The engineered magnetic nanoparticle sorbents have inherently high active surface areas, allowing for increased binding capacities. To demonstrate the performance of the nanoparticle sorbents, river water was spiked with specific metals and exposed to low concentrations of the functionalized nanoparticles. In almost all cases, the nanoparticles were found to be superior to commercially available sorbent materials as well as the unfunctionalized iron oxide nanoparticles.

Synthesis of Highly Magnetic Iron Carbide Nanoparticles via a Biopolymer Route

Abstract: In this article, we report a facile, one-pot route to phase-pure Fe3C nanoparticles (mean diameter = 20 nm) that show a remarkably high saturation magnetization (∼130 emu/g), higher than iron oxide (Fe3O4) and comparable to that of bulk Fe3C (∼140 emu/g). A readily available biopolymer (gelatin) is used as a matrix to disperse an aqueous iron acetate precursor. On heating, the biopolymer induces nucleation of magnetite (Fe3O4) nanoparticles before decomposing to form a carbon-rich matrix. This then acts as a reactive template for carbothermal reduction of the magnetite nanoparticles to Fe3C at a moderate temperature of 650 °C. This method represents a considerable advance over previous reports that often use high-energy procedures or costly and hazardous precursors. These homogeneous, highly magnetic nanoparticles have many potential applications in biomedicine and catalysis.

Iron oxide amended BioSand filters for virus removal

Abstract: Laboratory studies were performed to determine if the addition of iron oxides throughout biosand filter (BSF) media would increase virus removal due to adsorption. The proposed mechanism is electrostatic adsorption of negatively charged virion particles to positively charged iron oxides formed during the corrosion of zerovalent iron. Initial tests conducted using continuous flow, small-scale glass columns showed high MS2 bacteriophage removal in an iron-amended sand column (5log10) compared to a sand-only column (0.5log10) over 20 pore volumes. Additionally, two experiments with a column containing iron particles revealed 4log10 and 5log10 removal of rotavirus in the presence of 20 mg/L total organic carbon. Full-scale BSFs with iron particles removed>4log10 MS2 for the duration of the experiment (287 days), while BSF with steel wool removed>4log10 MS2 for the first 160 days. Plug flow for the BSF was shown to depend on uniformity between the iron oxide material and sand media grains. The results suggest that the duration of effective virus removal by iron-amended biosand filtration depends on source water conditions and the quantity and composition of iron material added. Overall, this study provides evidence that iron-amended BSFs may advance the field of point-of-use technologies and bring relief to millions of people suffering from waterborne diseases.

Effects of nanotubes pore size on the catalytic performances of iron catalysts supported on carbon nanotubes for Fischer–Tropsch synthesis

Abstract: In this report, the effects of pore diameter and structure of iron catalysts supported on carbon nanotubes (CNTs) on the reaction rates and product selectivities of Fischer–Tropsch (FT) reactions are presented. In order to study the effects of pore diameter, two types of CNTs with different average pore sizes (12 and 63 nm), however, with similar surface areas were prepared. The iron catalysts were prepared using incipient wetness impregnation method and characterized by ICP, BET, XRD, TPR, SEM and TEM analyses. According to the TEM images of iron catalysts supported on narrow pore CNTs (Fe/np-CNT) and wide pore CNTs (Fe/wp-CNT), a vast majority (∼80%) of the iron oxide particles were deposited inside the nanotubes’ pores. The TEM and XRD analysis showed that the iron oxide particles on the Fe/wp-CNT (17 nm) were larger than those on Fe/np-CNT sample (11 nm). Temperature programmed reduction analyses of the catalysts showed that the extent of reduction of the Fe/np-CNT catalyst was 17% higher compared to that of the Fe/wp-CNT catalyst. Finally, catalytic performances of both catalysts were evaluated in a fixed-bed reactor for FT reactions at 2 MPa and 275 °C. At these conditions, the activity of the np-CNT catalyst (%CO conversion of 30) was 2.5 times that of the wp-CNT catalyst (%CO conversion of 12). In addition, the Fe/wp-CNT was more selective toward lighter hydrocarbons with a methane selectivity of 41% compared to that of the np-CNT catalyst with methane selectivity of 14.5%. Deposition of metal particle on the CNT with narrow pore size resulted in more active and selective catalyst due to higher degree of reduction and higher metal dispersion.

Organic phase synthesis of monodisperse iron oxide nanocrystals using iron chloride as precursor

Abstract: Monodisperse iron oxide nanocrystals were synthesized by a simplified method using iron chloride as precursor. In the presence of Cl ions, the as-produced iron oxide nanocrystals preferred a cubic shape with {100} facets exposed. The function of halogens including Cl and Br ions on stabilizing {100} facets of spinel structured iron oxides, rather than the regulation of thermolysis kinetics and surfactants, was found influential on the shape control of nanocubes in this organic phase approach. The synthesis can be also extended for cobalt ferrite nanocubes and cobalt oxide polyhedrons.