Showing papers on "Oxide published in 2004"

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface

Abstract: Polarity discontinuities at the interfaces between different crystalline materials (heterointerfaces) can lead to nontrivial local atomic and electronic structure, owing to the presence of dangling bonds and incomplete atomic coordinations. These discontinuities often arise in naturally layered oxide structures, such as the superconducting copper oxides and ferroelectric titanates, as well as in artificial thin film oxide heterostructures such as manganite tunnel junctions. If polarity discontinuities can be atomically controlled, unusual charge states that are inaccessible in bulk materials could be realized. Here we have examined a model interface between two insulating perovskite oxides--LaAlO3 and SrTiO3--in which we control the termination layer at the interface on an atomic scale. In the simple ionic limit, this interface presents an extra half electron or hole per two-dimensional unit cell, depending on the structure of the interface. The hole-doped interface is found to be insulating, whereas the electron-doped interface is conducting, with extremely high carrier mobility exceeding 10,000 cm2 V(-1) s(-1). At low temperature, dramatic magnetoresistance oscillations periodic with the inverse magnetic field are observed, indicating quantum transport. These results present a broad opportunity to tailor low-dimensional charge states by atomically engineered oxide heteroepitaxy.

Formation of hollow nanocrystals through the nanoscale Kirkendall effect

Abstract: Hollow nanocrystals can be synthesized through a mechanism analogous to the Kirkendall Effect, in which pores form because of the difference in diffusion rates between two components in a diffusion couple. Starting with cobalt nanocrystals, we show that their reaction in solution with oxygen and either sulfur or selenium leads to the formation of hollow nanocrystals of the resulting oxide and chalcogenides. This process provides a general route to the synthesis of hollow nanostructures of a large number of compounds. A simple extension of the process yielded platinum-cobalt oxide yolk-shell nanostructures, which may serve as nanoscale reactors in catalytic applications.

The Structure of Catalytically Active Gold on Titania

Abstract: The high catalytic activity of gold clusters on oxides has been attributed to structural effects (including particle thickness and shape and metal oxidation state), as well as to support effects. We have created well-ordered gold mono-layers and bilayers that completely wet (cover) the oxide support, thus eliminating particle shape and direct support effects. High-resolution electron energy loss spectroscopy and carbon monoxide adsorption confirm that the gold atoms are bonded to titanium atoms. Kinetic measurements for the catalytic oxidation of carbon monoxide show that the gold bilayer structure is significantly more active (by more than an order of magnitude) than the monolayer.

Thin films: unexpected magnetism in a dielectric oxide.

Abstract: It is generally accepted that magnetic order in an insulator requires the cation to have partially filled shells of d or f electrons. Here we show that thin films of hafnium dioxide (HfO2), an insulating oxide better known as a dielectric layer for nanoscale electronic devices, can be ferromagnetic even without doping. This discovery challenges our understanding of magnetism in insulators, because neither Hf4+ nor O2- are magnetic ions and the d and f shells of the Hf4+ ion are either empty or full.

Combined binary oxide semiconductor device

Abstract: A semiconductor device can include a channel including a first binary oxide and a second binary oxide.

Oxide Materials for Development of Integrated Gas Sensors—A Comprehensive Review

Abstract: In the recent past a great deal of research efforts were directed toward the development of miniaturized gas-sensing devices, particularly for toxic gas detection and for pollution monitoring. Though various techniques are available for gas detection, solid state metal oxides offer a wide spectrum of materials and their sensitivities for different gaseous species, making it a better choice over other options. In this article a critical parameter analysis of different metal oxides that are known to be sensitive to various gaseous species are thoroughly examined. This includes phase of the oxide, sensing gaseous species, operating temperature range, and physical form of the material for the development of integrated gas sensors. The oxides that are covered in this study include oxides of aluminum, bismuth, cadmium, cerium, chromium, cobalt, copper, gallium, indium, iron, manganese, molybdenum, nickel, niobium, ruthenium, tantalum, tin, titanium, tungsten, vanadium, zinc, zirconium, and the mixed or...

Size- and Shape-Controlled Magnetic (Cr, Mn, Fe, Co, Ni) Oxide Nanocrystals via a Simple and General Approach

Abstract: A general, reproducible, and simple strategy using generic chemicals is introduced for controlling the size, shape, and size distribution of oxide nanocrystals. The reaction system was generally composed of the metal fatty acid salts, the corresponding fatty acids, and a hydrocarbon solvent. The method is based on the pyrolysis of metal fatty acid salts, the most common metal compounds compatible with nonaqueous solutions. Synthesis of nearly monodisperse Fe3O4 nanocrystals in a large size range (3−50 nm) was developed as the model system. The method was further applied for the growth of oxide nanocrystals of the other magnetic metals in the fourth rowCr2O3, MnO, Co3O4, and NiO nanocrystals. The size and shape control of the nanocrystals were achieved by varying the reactivity and concentration of the precursors. The reactivity was tuned by changing the chain length and concentration of the ligands, the fatty acids. Alcohols or primary amines could be used as the activation reagents when a given metal fat...

Selection of Oxygen Carriers for Chemical-Looping Combustion

Abstract: Chemical-looping combustion (CLC) has been suggested as an energetically efficient method for capture of carbon dioxide from the combustion of fuel gas. This technique involves the use of an oxygen carrier that transfers oxygen from the air to the fuel, preventing direct contact between them. The oxygen carrier is composed of a metal oxide as an oxygen source, and an inert as a binder for increasing the mechanical strength of the carrier. In this work, 240 samples composed of 40−80% of Cu, Fe, Mn, or Ni oxides on Al2O3, sepiolite, SiO2, TiO2, or ZrO2 were prepared by mechanical mixing as cylindrical extrudates. The samples were sintered at four temperatures between 950 and 1300 °C. The effects of the chemical nature and composition of the carrier and the sintering temperature were investigated by reactivity tests in a thermogravimetric analyzer using CH4 as fuel, and the mechanical strength of the solids. On the basis of these properties, the most promising carriers to be used in a CLC system were selecte...

Synthesis of Fe Oxide Core/Au Shell Nanoparticles by Iterative Hydroxylamine Seeding

Abstract: Water-soluble, Au-coated magnetic Fe oxide nanoparticles with diameters ∼60 nm were synthesized by the reduction of Au3+ onto the surfaces of ∼9 nm diameter particles consisting of either γ-Fe2O3 or partially oxidized Fe3O4 via iterative hydroxylamine seeding. The morphology and optical properties of the core/shell particles are dependent on the quantity of deposited Au, while the magnetic properties remain largely independent of Au addition. The Au-coated particles exhibit a surface plasmon resonance peak that blue-shifts from 570 to 525 nm with increasing Au deposition. SQUID magnetometry reveals that particle magnetic properties are not affected by the overlayer of a moderately thick Au shell.

Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3

Abstract: At the heart of modern oxide chemistry lies the recognition that beneficial (as well as deleterious) materials properties can be obtained by deliberate deviations of oxygen atom occupancy from the ideal stoichiometry. Conversely, the capability to control and confine oxygen vacancies will be important to realize the full potential of perovskite ferroelectric materials, varistors and field-effect devices. In transition metal oxides, oxygen vacancies are generally electron donors, and in strontium titanate (SrTiO3) thin films, oxygen vacancies (unlike impurity dopants) are particularly important because they tend to retain high carrier mobilities, even at high carrier densities. Here we report the successful fabrication, using a pulsed laser deposition technique, of SrTiO3 superlattice films with oxygen doping profiles that exhibit subnanometre abruptness. We profile the vacancy concentrations on an atomic scale using annular-dark-field electron microscopy and core-level spectroscopy, and demonstrate absolute detection sensitivities of one to four oxygen vacancies. Our findings open a pathway to the microscopic study of individual vacancies and their clustering, not only in oxides, but in crystalline materials more generally.

Iron oxide dissolution and solubility in the presence of siderophores

Abstract: Iron is an essential trace nutrient for most known organisms. The iron availability is limited by the solubility and the slow dissolution kinetics of iron-bearing mineral phases, particularly in pH neutral or alkaline environments such as carbonatic soils and ocean water. Bacteria, fungi, and plants have evolved iron acquisition systems to increase the bioavailability of iron in such environments. A particularly efficient iron acquisition system involves the solubilization of iron by siderophores. Siderophores are biogenic chelators with high affinity and specificity for iron complexation. This review focuses on the geochemical aspects of biological iron acquisition. The significance of iron-bearing minerals as nutrient source for siderophore-promoted iron acquisition has been confirmed in microbial culture studies. Due to the extraordinary thermodynamic stability of soluble siderophore-iron complexes, siderophores have a pronounced effect on the solubility of iron oxides over a wide pH range. Very small concentrations of free siderophores in solution have a large effect on the solution saturation state of iron oxides. This siderophore induced disequilibrium can drive dissolution mechanisms such as proton-promoted or ligand-promoted iron oxide dissolution. The adsorption of siderophores to oxide surfaces also induces a direct siderophore-promoted surface-controlled dissolution mechanism. The efficiency of siderophores for increasing the solubility and dissolution kinetics of iron oxides are compared to other natural and anthropogenic ligands.

An undoped, single-phase oxide photocatalyst working under visible light.

Abstract: A novel photocatalyst, PbBi2Nb2O9 has been discovered that shows high activities for degradation of organic pollutants, generation of photocurrent, and water decomposition into O2 or H2, all under visible right irradiation (λ ≥ 420 nm). This is the first example of an undoped, single-phase oxide photocatalyst that shows such reactivity. Its quantum yields are much higher than those for most of the previously reported materials, especially in water decomposition to generate oxygen (29%). Since it is an oxide, there is much less concern for stability under light irradiation.

Ethylene glycol-mediated synthesis of metal oxide nanowires

Abstract: A simple and convenient method has been demonstrated for large-scale synthesis of metal oxide (including TiO2, SnO2, In2O3, and PbO) nanowires with diameters around 50 nm and lengths up to 30 µm. In a typical procedure, tetraalkoxyltitanium, Ti(OR)4 (with R = –C2H5, –iso-C3H7, or –n-C4H9), was added to ethylene glycol and heated to 170 °C for 2 h under vigorous stirring. The alkoxide was transformed into a chain-like, glycolate complex that subsequently crystallized into uniform nanowires. Similarly, nanowires made of tin glycolate were synthesized by refluxing SnC2O4·2H2O in ethylene glycol at 195 °C for 2 h, and nanowires consisting of indium and lead glycolates were prepared by adding In(OOCC7H15)(OiPr)2 and Pb(CH3COO)2 to ethylene glycol, followed by heating at 170 °C for 2 h. The nanowires could be readily collected as precipitates after the reaction solutions had been cooled down to room temperature. By calcining at elevated temperatures, each glycolate precursor could be transformed into the corresponding metal oxide without changing the wire-like morphology. Electron microscopic and XRD powder diffraction studies were used to characterize the morphology, crystallinity, and structure of these nanowires before and after calcination at various temperatures. A plausible mechanism was also proposed to account for the one-dimensional growth of such nanostructures in a highly isotropic medium. This mechanism was supported by XRD, FT-IR, solid state 13C-NMR, and TGA measurements. As a demonstration of potential applications, the polycrystalline nanowires made of SnO2 were used as functional components to fabricate sensors that could detect combustible gases (CO and H2) with greatly enhanced sensitivity under ambient conditions.

Spectroscopic Evidence for Fe(II)−Fe(III) Electron Transfer at the Iron Oxide−Water Interface

Abstract: Using the isotope specificity of 57Fe Mossbauer spectroscopy, we report spectroscopic observations of Fe(II) reacted with oxide surfaces under conditions typical of natural environments (i.e., wet, anoxic, circumneutral pH, and about 1% Fe(II)). Mossbauer spectra of Fe(II) adsorbed to rutile (TiO2) and aluminum oxide (Al2O3) show only Fe(II) species, whereas spectra of Fe(II) reacted with goethite (α-FeOOH), hematite (α-Fe2O3), and ferrihydrite (Fe5HO8) demonstrate electron transfer between the adsorbed Fe(II) and the underlying iron(III) oxide. Electron-transfer induces growth of an Fe(III) layer on the oxide surface that is similar to the bulk oxide. The resulting oxide is capable of reducing nitrobenzene (as expected based on previous studies), but interestingly, the oxide is only reactive when aqueous Fe(II) is present. This finding suggests a novel pathway for the biogeochemical cycling of Fe and also raises important questions regarding the mechanism of contaminant reduction by Fe(II) in the presenc...

Characterization and FTIR Studies of MnOx−CeO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NO with NH3

Abstract: A series of high-activity manganese−cerium oxide catalysts for the low-temperature (373−453 K) selective catalytic reduction (SCR) of NOx with ammonia were prepared. They were prepared by using the...

Electrochemical Characterization of La0.6Sr0.4Co0.2Fe0.8 O 3 Cathodes for Intermediate-Temperature SOFCs

Abstract: The electrochemical properties of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) have been assessed for its application as a cathode in intermediate-temperature solid oxide fuel cells. van der Pauw dc conductivity, two-electrode impedance, and three-electrode measurements were carried out to investigate the kinetics of the oxygen reduction reaction at various temperatures, oxygen partial pressures, and polarization values. A change in cathode behavior at temperatures around 600°C was observed. This is interpreted in terms of LSCF behaving as a mixed ionic electronic conductor at temperatures above around 600°C, oxygen reduction being stimulated by the formation of oxygen vacancies with increasing cathode overpotential. However, at temperatures below 600°C the contribution of mixed conductivity is low, and cathode behavior can then be interpreted in terms of the classical triple-phase-boundary model.

Alternating copolymerization of limonene oxide and carbon dioxide.

Abstract: The alternating copolymerization of (R)- or (S)-limonene oxide and CO2 using beta-diiminate zinc acetate catalysts is reported. At 100 psi CO2 and 25 degrees C, the catalyst exhibits a high selectivity for the trans isomer and produces regioregular polycarbonate. The copolymer contains >99% carbonate linkages, a narrow molecular weight distribution, and an Mn value consistent with the [epoxide]/[Zn] ratio.

Intelligent window coatings: Atmospheric pressure chemical vapor deposition of tungsten-doped vanadium dioxide

Abstract: Thin films of tungsten-doped vanadium(IV) oxide were prepared on glass substrates from the atmospheric pressure chemical vapor deposition of vanadium(IV) chloride, tungsten(VI) ethoxide, and water at 500−600 °C. The films were characterized by Raman microscopy, glancing angle X-ray diffraction (GAXRD), X-ray photoelectron spectroscopy (XPS), Rutherford backscattering (RBS), scanning electron microscopy (SEM), and vis/IR reflectance−transmittance. The films showed a reduction in thermochromic transition temperatures from 68 °C in VO2 to 42 °C in V0.99W0.01O2approaching that required for commercial use as an intelligent window coating.

Insight into Clustering in Poly(ethylene oxide) Solutions

Abstract: The clustering phenomenon has been observed in many macromolecular systems. Poly(ethylene oxide) solutions are characterized by a clustering effect that has been extensively discussed in the literature. Its origin has remained elusive. Using small-angle neutron scattering from PEO solutions in various deuterated solvents, the possible causes of clustering that have been given in the literature are analyzed here. These include impurities in water, possible PEO crystallization, a subtle phase transition whereby a concentrated phase coexists with free polymer coils, hydrogen-bond physical cross-linking, and finally chain ends effect. We have shown that under the experimental conditions considered here (4% PEO weight fraction) the mostly forgotten chain ends effect is at the origin of clustering in poly(ethylene oxide) solutions.