Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species

The structure of FeO_x species supported on γ‐Al₂O₃ was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al₂O₃ and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe₂O₃ particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al₂O₃ surface.     

Ellipsometric study of anodic oxide films formed on niobium surfaces

Anodic oxide films formed potentiostatically on niobium surfaces, from open circuit potential (OCP) to 10 V, were studied by performing in situ and ex situ ellipsometric measurements. The kinetics of the film thickness growth in 1 M H₂SO₄ and complex indices of refraction of these films were determined. A strong influence of the surface preparation conditions on the complex refractive indices of the metal substrate and anodic oxide films was shown. By steady-state measurements at OCP, a small thickening of the natural air-formed oxide film with chemical composition Nb₂O₅ in 1 M H₂SO₄ solution was detected. With cathodic pre-treatment, only partial reduction and small thinning of the natural air-formed oxide film was possible. The thicknesses of the natural air-formed oxide films on fine mechanically polished and electropolished Nb surfaces were determined. The build up of the natural air-formed oxide film, at ex situ conditions, on the already formed anodic oxide films was confirmed. It was shown that electropolishing gives more similar optical surface properties to the bare metal than the fine mechanical polishing. Electronic Publication     

Highly selective aerobic oxidation of alkylarenes catalyzed by cobalt‐based nanocatalyst in aqueous solution

The catalytic aerobic oxidation of alkylarenes catalyzed by cobalt supported on a highly crystalline γ‐Al₂O₃ support (Co/Al₂O₃ nanocatalyst) is reported. The catalyst was prepared by a co‐precipitation method and characterized using scanning and high‐resolution transmission electron microscopies, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and surface area measurements. A wide range of alkylarenes were converted to corresponding ketones. The catalyst can be recovered by simple filtration is recyclable for up to six consecutive runs.     

Oxidation behavior of NiAl alloy at low temperatures

Oxidation behavior of NiAl alloy at low temperatures was studied. A NiAl plate was oxidized by exposure to ambient atmosphere at room temperature, heated at 473 K in air, and heated at 773 K in air. The oxide formed on the NiAl surface was investigated by angle‐resolved X‐ray photoelectron spectroscopy (AR‐XPS). Chemical composition and atomic concentration in the oxide layer were analyzed with factor analysis of XPS spectra. Exposure of the NiAl plate to the ambient atmosphere resulted in the formation of an Al₂O₃ layer along with a small amount of NiO. Oxidation of the NiAl plate at 473 K in air formed a film of double‐layered oxide; the top layer consisted of NiAl₂O₄ and a small amount of NiO, and the second layer was Al₂O₃. Successive oxidation at 773 K only changed the oxide‐layer thickness without changing the structure. Formation of oxide observed in the present study corresponds to the thermodynamic prediction for the oxidation behavior of NiAl at 1373 K. Copyright © 2007 John Wiley & Sons, Ltd.     

A Simple Method to Tune Up Screen‐Printed Carbon Electrodes Applicable to the Design of Disposable Electrochemical Sensors

We report an easy method to tune up screen‐printed carbon electrodes (SPCEs) for application in fabricating disposable electrochemical sensors. Simply by ultrasonic polishing a bare SPCE in a γ‐Al₂O₃ slurry, the surface roughness was drastically smoothed coupled with a large increase in hydrophilicity. The as‐generated micromorphology on the surface of the SPCE was found to be ideal for the immobilization of catechol to minimize the overpotential in the sensitive detection of nicotinamide adenine dinucleotide (NADH) and hydrazine. Physical characterization by both XPS and AFM studies specify that the adsorption behavior is related to the carbon surface functionalities and the trapping of γ‐Al₂O₃ on the polished‐SPCE.     

High‐temperature oxidation behavior of Ni‐based superalloys with Nb and Y and the interface characteristics of oxidation scales

Ni‐based superalloys with niobium (Nb) or/and yttrium (Y) were prepared by vacuum melting. The oxidation kinetics of these alloys was studied by thermogravimetry at 800 °C for 100 h in static air. Morphology of oxides was studied using SEM, and the composition was analyzed by X‐ray diffraction. Energy‐dispersive X‐ray spectrometer was employed to examine the linear element distribution of the cross section of the oxidation films. Results showed that the oxidation kinetics all followed a parabolic law at different stages. The oxide films were mainly comprised of Cr₂O₃, NiCr₂O₄, Al₂O₃ and TiO₂. All the oxide films exhibited layered structure owing to different oxidation stages. With the addition of Nb or Y, the high‐temperature oxidation resistance of the superalloy was improved significantly and the surface morphology of the oxidation film was ameliorated. The comprehensive effect of Nb and Y was remarkable in improving the high‐temperature oxidation resistance of Ni‐based alloys. Copyright © 2014 John Wiley & Sons, Ltd.     

A New Iron‐Based Carbon Monoxide Oxidation Catalyst: Structure–Activity Correlation

A new iron‐based catalyst for carbon monoxide oxidation, as a potential substitute for precious‐metal systems, has been prepared by using a facile impregnation method with iron tris‐acetylacetonate as a precursor on γ‐Al₂O₃. Light‐off and full conversion temperatures as low as 235 and 278 °C can be reached. However, the catalytic activity strongly depends on the loading; lower loadings perform better than higher ones. The different activities can be explained by variations of the structures formed. The structures are thoroughly characterized by a multimethodic approach by using X‐ray diffraction, Brunauer–Emmett–Teller surface areas, and Mössbauer spectroscopy combined with diffuse reflectance UV/Vis and X‐ray absorption spectroscopy. Consequently, isolated tetrahedrally coordinated Fe³⁺ centers and phases of AlFeO₃ are identified as structural requirements for high activity in the oxidation of carbon monoxide.     

Chemical composition and structural changes of porous templates obtained by anodising aluminium in phosphoric acid electrolyte

Ordered anodic aluminium oxide (AAO) films were first prepared by anodising in a phosphoric acid electrolyte and then studied extensively and characterised by field emission gun‐scanning electron microscopy (FEG‐SEM), X‐ray diffraction, Raman and infrared spectroscopy at a macroscopic scale. These analyses showed that the as‐prepared AAO film is in fact amorphous, partially hydrated and that its initial global chemical composition can be described, in agreement with previous works, as: Al₂O₃, 0.186AlPO₄ · 0.005H₂O. Additional analyses (thermogravimetric analysis, differential thermal analysis and FEG‐SEM) showed geometrical changes of the film structure at different scales, explained by various steps of dehydration and allotropic transformations of the resulting crystallised alumina. However, because their structure remains unchanged up to 900 °C, the phosphoric templates appear to be particularly suitable for applications or processes at medium or high temperatures, such as the preparation of carbon nanotubes or oxide rods. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of thermal annealing on the microstructure,hardness and corrosion behavior of TiAlSiCuN nanocomposite films

Nanocomposite TiAlSiCuN films were deposited on high speed steels by filtered magnetic arc ion plating. Detailed properties of the films annealed at various temperatures are studied. After thermal annealing at different temperatures ranging from 400 to 800 °C, changes in the film micro‐structure, chemical and phase composition, surface morphology, hardness and polarization curve properties were systematically characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, nano‐indenter and electrochemical workstation, respectively. It was found that the TiAlSiCuN films could be fully oxidized at 800 °C, Al and Ti atoms all diffused outwards and formed dense protective Al₂O₃ and TiO₂ layer. Simultaneously, the TiAlN phase gradually disappeared. The films annealed at 400 °C obtained the highest hardness because of the certain grain growth and little generated oxides. Besides, the certain formation of dense protective Al₂O₃ layer made the TiAlSiCuN film annealed at 600 °C present the least corrosion current density and the corrosion voltage. Copyright © 2016 John Wiley & Sons, Ltd.     

Ultrasensitive NOX Detection in Simulated Exhaled Air: Enhanced Sensing via Alumina Modification of In‐Situ Grown WO3 Nanoblocks

Seedless growth of vertically aligned nanostructures, which can induce smoother transport and minimize Ohmic contact between substrate and semiconductor, can be fabricated by in situ growth utilizing modified hydrothermal methods. Such devices can be useful in designing non‐invasive ultrasensitive hand‐held sensors for diagnostic identification of volatile organic compounds (VOCs) in exhaled air, offering pain‐free and easier detection of long‐term diseases such as asthma. In the present work, WO₃ nanoblocks, with a high surface area and porosity, have been grown directly over transparent conducting oxide to minimize Ohmic resistance, facilitating smoother electron transfer and enhanced current response. Further modification with porous alumina (γ‐Al₂O₃), by electrodeposition, resulted in the selective and ultrasensitive detection of NO_X in simulated exhaled air. Crystal phase purity of as‐fabricated pristine as well modified samples is validated with X‐ray diffraction analysis. Morphological and microstructural analyses reveal the successful deposition of porous alumina over the surface of WO₃. Improved surface area and porosity is presented by porous alumina in the modified WO₃ device, suggesting more active sites for the gas molecules to get adsorbed and diffuse through the pores. Oxygen vacancies, which are detrimental in the transport phenomenon in the presented sensors, have been studied using X‐ray photoelectron spectroscopic (XPS) analysis. Gas sensing studies have been performed by fabricating chemiresistor devices based on bare WO₃ and Al₂O₃‐modified WO₃. The higher sensitivity for NO_X gas in case of γ‐Al₂O₃‐modified WO₃ based devices, as compared to bare WO₃‐based devices, is attributed to the better surface area and charge transport kinetics. The presented device strategy offers crucial understanding in the design and development of non‐invasive, hand‐held devices for NO gas present in the human breath, with potential application in medical diagnostics.     

Mesoporous Core–Shell Fenton Nanocatalyst: A Mild,Operationally Simple Approach to the Synthesis of Adipic Acid

Mesoporous nanoparticles composed of γ‐Al₂O₃ cores and α‐Fe₂O₃ shells were synthesized in aqueous medium. The surface charge of γ‐Al₂O₃ helps to form the core–shell nanocrystals. The core–shell structure and formation mechanism have been investigated by wide‐angle XRD, energy‐dispersive X‐ray spectroscopy, and elemental mapping by ultrahigh‐resolution (UHR) TEM and X‐ray photoelectron spectroscopy. The N₂ adsorption–desorption isotherm of this core–shell materials, which is of type IV, is characteristic of a mesoporous material having a BET surface area of 385 m² g^?1 and an average pore size of about 3.2 nm. The SEM images revealed that the mesoporosity in this core–shell material is due to self‐aggregation of tiny spherical nanocrystals with sizes of about 15–20 nm. Diffuse‐reflectance UV/Vis spectra, elemental mapping by UHRTEM, and wide‐angle XRD patterns indicate that the materials are composed of aluminum oxide cores and iron oxide shells. These Al₂O₃@Fe₂O₃ core–shell nanoparticles act as a heterogeneous Fenton nanocatalyst in the presence of hydrogen peroxide, and show high catalytic efficiency for the one‐pot conversion of cyclohexanone to adipic acid in water. The heterogeneous nature of the catalyst was confirmed by a hot filtration test and analysis of the reaction mixture by atomic absorption spectroscopy. The kinetics of the reaction was monitored by gas chromatography and ¹H NMR spectroscopy. The new core–shell catalyst remained in a separate solid phase, which could easily be removed from the reaction mixture by simple filtration and the catalyst reused efficiently.     

Thin films of vanadium oxide grown on vanadium metal: oxidation conditions to produce V2O5 films for Li‐intercalation applications and characterisation by XPS,AFM, RBS/NRA

Thin films of vanadium oxide were grown on vanadium metal surfaces (i) in air at ambient conditions, (ii) in 5 mM H₂SO₄ (aq), pH 3, (iii) by thermal oxidation at low oxygen pressure (10^?5 mbar) at temperatures between 350 and 550 °C and (iv) at near‐atmospheric oxygen pressure (750 mbar) at 500 °C. The oxide films were investigated by atomic force microscopy (AFM), X‐ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). The lithium intercalation properties were studied by cyclic voltammetry (CV). The results show that the oxide films formed in air at room temperature (RT), in acidic aqueous solution, and at low oxygen pressure at elevated temperatures are composed of V₂O₃. In air and in aqueous solution at RT, the oxide films are ultra‐thin and hydroxylated. At 500 °C, nearly atmospheric oxygen pressure is required to form crystalline V₂O₅ films. The oxide films grown at pO₂ = 750 mbar for 5 min are about 260‐nm thick, and consist of a 115‐nm outer layer of crystalline V₂O₅. The inner oxide is mainly composed of VO₂. For all high temperature oxidations, the oxygen diffusion from the oxide film into the metal matrix was considerable. The oxygen saturation of the metal at 450 °C was found, by XPS, to be 27 at.% at the oxide/metal interface. The well‐crystallized V₂O₅ film, formed by oxidation for 5 min at 500 °C and 750 mbar O₂, was shown to have good lithium intercalation properties and is a promising candidate as electrode material in lithium batteries. Copyright © 2005 John Wiley & Sons, Ltd.     

Solvent‐free synthesis of propargylamines catalyzed by an efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst

An efficient nanocatalyst of ZnO‐supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co‐precipitation method and characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/ZnO/Al₂O₃ nanocatalyst proved to be a very efficient catalyst on the synthesis of propargylamines under solvent‐free conditions in high yields. Moreover, the catalyst can be recyclable without reducing catalytic activity up to five times.     

The effect of iron phosphate,alumina and silica coatings on the morphology of carbonyl iron particles

Carbonyl iron powders were coated with iron phosphate using phosphating method and boehmite (γ‐AlOOH) or silicon hydroxide (Si(OH)₄) nanoparticles derived from the hydrolysis of tri‐sec‐butoxide (Al(OC₄H₉)₃) or tetramethylsilane (Si(OCH₃)₄) using sol–gel method. The coated powders were dried and calcined at 400 °C for 3 h in air. Cross‐section morphology of coated carbonyl iron powders were investigated by scanning electron microscopy energy dispersive X‐ray analysis. Coated Fe micro‐particles were spherical in shape with ‘shell/core’ structures. The shells consisted of an amorphous layer with varying thickness (100–800 nm) and the core represented a carbonyl iron. Gelatinous morphology of dried FePO₄ coating composed from nanoparticles of iron oxyhydroxides and hydrated iron phosphate with a shell thickness of ～100 nm around iron particles was observed. In coatings based on alumina or silica xerogels with a thickness of ～100–150 nm or ～200–500 nm, the coatings were composed of iron oxyhydroxides and γ‐AlOOH or Si(OH)₄. The resulting XRD diffractograms revealed the hematite (α‐Fe₂O₃) and magnetite (Fe₃O₄) that were formed in phosphated and sol–gel coated iron powders. The X‐ray diffraction patterns did not verify the presence of phosphates, alumina or silica and indicate the amorphous or nanocrystalline structure of FePO₄, γ‐Al₂O₃ and SiO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemical Liquid Phase Deposition of Thin Aluminum Oxide Films

Introduction Inorganic oxide films have attracted a lot of interest in the last several decades. Among them, silicon dioxide films are widely used in modern microelectronics, optics and mechanics. This material has been grown by various methods including thermal oxidation, chemical vapor phase deposition, plasma-enhanced chemical vapor phase deposition, and so on.1,2 Recently, Nagayama et al.3 have reported that SiO2 thin films could be produced by a new chemical method of liquid phase depos…     

Structural Characterization of Alumina‐Supported Rh Catalysts: Effects of Ceriation and Zirconiation by using Metal–Organic Precursors

The effects of the addition of ceria and zirconia on the structural properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ‐Al₂O₃) are studied. Ceria and zirconia are deposited by using two preparation methods. Method I involves the deposition of ceria on γ‐Al₂O₃ from Ce(acac)₃, and the rhodium metal is subsequently added, whereas method II is based on a controlled surface reaction technique, that is, the decomposition of metal–organic M(acac)_x (in which M=Ce, x=3 and M=Zr, x=4) on Rh/γ‐Al₂O₃. The structures of the prepared catalyst materials are characterized ex situ by using N₂ physisorption, transmission electron microscopy, high‐angle annular dark‐field scanning transmission election microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy (XPS), and X‐ray absorption fine structure spectroscopy (XAFS). All supported rhodium systems readily oxidize in air at room temperature. By using ceriated and zirconiated precursors, a larger rhodium‐based metallic core fraction is obtained in comparison to the undoped rhodium catalysts, suggesting that ceria and zirconia protect the rhodium particles against extensive oxidation. XPS results indicate that after the calcination and reduction treatments, a small amount of chlorine is retained on the support of all rhodium catalysts. EXAFS analysis shows significant Rh? Cl interactions for Rh/Al₂O₃ and Rh/CeO_x/Al₂O₃ (method I) catalysts. After reaction with H₂/He in situ, for series of samples with 1.6 wt % Rh, the EXAFS first shell analysis affords a mean size of approximately 30 atoms. A broader spread is evident with a 4 wt % rhodium loading (ca. 30–110 atoms), with the incorporation of zirconium providing the largest particle sizes.     

A Novel Way to Prepare TiO2 and γ‐Al2O3 Supported Catalysts with Large Surface Areas

Several TiO₂ and γ‐Al₂O₃ supported catalyst systems were prepared by a novel way and characterized by X‐ray diffraction, Raman spectroscopy and BET surface area measurement. The results show: (1) all the samples, including MoO₃/TiO₂, WO₃/TiO₂, V₂O₅/TiO₂, FeSO₄/γ‐Al₂O₃, Al₂ (SO₄)₃/γ‐Al₂O₃, K₂CO₃/‐Al₂O₃ and so on, prepared by impregnating TiO₂·H₂O or pseudo‐boehmite AlO(OH) with the active components then calcining at a high temperature exhibit much larger surface areas than that of pure TiO₂ or γ‐Al₂O₃ calcined at the same temperature; (2) the surface area of the sample increases with the increase in the coverage of active component on the surface of the support; (3) when the content of active component reaches its utmost monolayer dispersion capacity, the surface area of the sample is the largest, and then decreases when the content of active component exceeds its dispersion threshold.     

Highly increased capacitance and thermal stability of anodic oxide films on oxygen-incorporated Zr-Ti alloy

Heat treatment of Zr-24 at% Ti alloy with barrier-type dielectric anodic oxide films was conducted at 473 K in air to examine the thermal stability of the dielectric oxide films for possible electrolytic capacitor application. The anodic oxide film was formed by anodizing of the alloy at 50 V for 30 min in 0.1 mol dm^?3 ammonium pentaborate electrolyte. The anodic oxide film of 125 nm thickness was crystalline, containing both monoclinic and tetragonal ZrO₂ phase. It was found that marked thickening of the oxide film with generation of cracks occurred during heat treatment at 473 K. Thus, the dielectric loss was largely increased along with the capacitance increase. In contrast, the anodic oxide film formed on the oxygen-incorporated alloy remained uniform, and no significant increase in dielectric loss was observed even after the heat treatment. The capacitance of the anodic film became as high as 4.8 mF m^?2, which was nearly twice that on Ta. The high capacitance was associated with the preferential formation of tetragonal ZrO₂ phase in the anodic oxide film on the oxygen-incorporated alloy. Findings indicated that the oxygen-incorporated Zr-Ti alloy is a promising novel material for capacitor application.     

Generation of Methyl Vinyl Ketone from Oxidation of Levulinic Acid Oxidized by Cupric Oxide Complex

Methyl vinyl ketone (MVK) is a kind of high‐value chemical which has been widely used in many fields. In this paper, it is formed from oxidation of levulinic acid–a hydrolysis product of biomass. Copper oxide supported on cerium dioxide (CuO/CeO₂) and alumina (CuO/Al₂O₃) were prepared and used for the oxidation of levulinic acid (LA). The oxidants were characterized by means of X‐ray diffraction (XRD), H₂‐temperature programmed reduction (H₂‐TPR) and atomic force microscope (AFM) techniques. CuO/CeO₂ and CuO/Al₂O₃ show a different behavior with respect to pure CuO. The experiments revealed that CuO/CeO₂ and CuO/Al₂O₃ can oxidize LA and get methyl vinyl ketone [yield of 15.5% detected by head space‐gas chromatograph‐mass spectrometer (HS‐GC‐MS)] under mild reactive conditions, while pure CuO oxidizes LA to produce butanone (MEK).     

Chemical‐Bath‐Deposited Indium Oxide Microcubes for Solar Water Splitting

We fabricated films of cubic indium oxide (In₂O₃) by chemical bath deposition (CBD) for solar water splitting. The fabricated films were characterized by X‐ray diffraction analysis, Raman scattering, X‐ray photoelectron spectroscopy, and scanning electron microscopy, and the three‐dimensional microstructure of the In₂O₃ cubes was elucidated. The CBD deposition time was varied, to study its effect on the growth of the In₂O₃ microcubes. The optimal deposition time was determined to be 24 h, and the corresponding film exhibited a photocurrent density of 0.55 mA cm^?2. Finally, the film stability was tested by illuminating the films with light from an AM 1.5 filter with an intensity of 100 mW cm^?2.