Structural characterization of alumina-supported nickel molybdena catalysts

The object of our studies was a NiMo/Al₂O₃ catalyst thermally activated in oxygen, hydrogen, and in a mixture of hydrogen and hydrogen sulfide. On the surface of the oxide form of the catalyst there are different species, among them dimeric and polymeric octahedrally coordinated Mo⁶⁺ ions containing oxygen bridges are found. The presence of structures resembling α- and β-NiMoO₄ and 6-heteropolymolybdenates was determined. Reduction with hydrogen leads to formation of two nuclear structures with single and double bridges of [Mo₂⁵⁺ O₃] and [Mo⁵⁺ O₄] type, respectively, and partially reduced 6-heteropolymolybdenates. On the other hand, when the reduction and sulfiding take place at the same time, then terminal oxide ions are partially replaced by sulfide ones. The presence of [MoO₂S₂]²⁻ species has been observed, however, there is no evidence of the exchange —OH groups for —SH ones and exchange of oxygen bridged ions for sulfur ions. It has been also noted that the subsurface structures remained intact after reduction and sulfiding.     

Spectroscopic and magnetic behavior of xNd2O3(1−x)(3Bi2O3 · PbO) glasses

Glasses of the xNd₂O₃(1−x)(3Bi₂O₃ · PbO) system with 0?x?0.30 were obtained and studied by IR spectroscopy, X-ray photoelectron spectroscopy (XPS), density and magnetic susceptibility measurements. IR and density measurements show that the addition of neodymium ions produces structural changes and the neodymium ions play a network modifier role in the host glass matrix. XPS investigation permitted following the evolution of the structural disorder, of the degree of polymerization of bismuthate chains and of the fraction of bridging oxygens with respect to the neodymium ion concentration of the studied glasses. Magnetic susceptibility data show that the Nd³⁺ ions are present as isolated species for x?0.05 and as both isolated and exchange coupled species for higher x values.     

The Effect of Fluoride Concentration and Catalyst Preparation Method on Structural and Thermal Properties of CoMo/Al2O3 Catalysts

The effect of the sequence of incorporation of F⁻ ions on the properties of fluorinated CoMo/Al₂O₃ catalysts was investigated by the methods of X-ray diffraction, infrared spectroscopy and thermal analysis. Three kinds of samples were prepared into which the F⁻ ions were introduced either simultaneously with Co and Mo (sample labelled as CoMoF), or prior to them (F/CoMo) or after them (CoMo/F). The samples contained fixed amounts of Mo (15 wt.% MqO₃) and Co (3 wt.% CoO). Formation of surface di- and polymolybdate species as well as Al–F was evidenced in all samples. The concentration of molybdenum containing species was the highest in CoMoF sample, while that of fluoride containing species was the highest in CoMo/F samples.     

Effect of ion beam irradiation on the corrosion behavior of the melt-spun ribbon Ti60Ni40

Potentiodynamic polarization studies were carried out on unirradiated and irradiated Ti₆₀Ni₄₀ specimens in 1 M HNO₃ aqueous medium at room temperature. The irradiation was carried out using N⁺ 150 keV ions at a fluence of 1 × 10¹⁶ ions/cm². Polarization results revealed that the irradiated specimen exhibits less corrosion current density as compared to the unirradiated Ti₆₀Ni₄₀ specimen. X-ray photoelectron spectroscopy (XPS) studies were also carried out on the irradiated and unirradiated specimens after corrosion test. It was observed that the absence of Ti³⁺ species in the oxide film of the irradiated specimen as compared to the unirradiated specimen results in the improvement of the corrosion resistance. Polarization results are also corroborated by weight loss data.     

Fabrication and thermal evolution of nanoparticles in SiO2 by Zn ion implantation

SiO₂ samples were implanted with 45 keV Zn ions at doses ranging from 5×10¹⁵ to 1.0×10¹⁷ ions/cm², and were then subjected to furnace annealing at different temperatures. Several techniques, such as ultra-violet–visible spectroscopy (UV–vis), grazing incidence X-ray diffraction spectroscopy (GXRD) and atomic force microscopy (AFM), have been used to investigate formation of nanoparticles and their thermal evolution. Our results clearly show that Zn nanoparticles could be effectively formed in SiO₂ at doses higher than 5×10¹⁶ ions/cm². The subsequent thermal annealing at oxygen ambient could induce the growth of Zn nanoparticles at intermediate annealing temperature range. While at temperature above 600 °C, Zn nanoparticles could be transformed into ZnO, or even Zn₂SiO₄ nanoparticles. The results have been tentatively discussed in combination with Zn diffusion and migration obtained by Rutherford backscattering spectroscopy (RBS) measurements.     

Effect of Fluoride and Sodium Ions on Structural and Thermal Properties of γ-Al2O3

The structural properties of alumina as well as its fluoride and sodium modifications were characterized by X-ray diffraction, infrared spectroscopy and differential thermal analysis. We have shown, that fluoride ions interact with hydroxyls type Ia of γ-Al₂O₃ forming Al–F species, which then react at 400 °C forming β-Al₂O₃. Morever, F/Al₂O₃ sample heated up to 400 °C contain two acidic hydroxyls type IIa and III, which are also represented on a differential thermal curve as endoeffect with minima at 470 and 500 °C. For Na/Al₂O₃ sample the same types of hydroxyls interact with Na⁺ ions leading to substitution of their protons. After heating at 400 °C this sample contains also hydroxyls type IIa and III, which are represented by two endothermal effects with minima at 450 and 520 °C. Differential thermal analysis shown to be a powerful and simple technique to characterize surface hydroxyl types of Na and F samples supported on γ-alumina.     

Fabrication of ferric oxide/reduced graphene oxide/cadmium sulfide heterostructure photoelectrode for enhanced photoelectrochemical performance

A novel high‐efficiency photoelectrode (Fe₂O₃/reduced graphene oxide/CdS) built from heterostructure and conductive scaffold has been successfully designed and synthesized. Reduced graphene oxide works as a “bridge” which benefits for electron and hole transport. The obtained heterostructure photoelectrodes were systematically characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS). The photoconversion efficiency (η) and photocurrent densities vs. time (I‐t) curves responding to monochromatic lights have been further investigated in‐depth, which reveals that introduction of CdS and reduced graphene oxide played an important role in the enhancement of photoelectrochemical performance.     

Structural and magnetic behaviour of lead-bismuthate glasses containing rare earth ions

Lead-bismuthate glasses containing rare earth ions in the xR₂O₃(1 − x)[3Bi₂O₃⋅ PbO] (R = Nd, Eu, Er and Gd), xCeO₂(1 − x)[3Bi₂O₃⋅ PbO] and xTb₄O₇(1 − x)[3Bi₂O₃⋅ PbO] vitreous systems with x up to 0.25 were prepared and investigated by density, IR spectroscopy and magnetic susceptibility measurements. Density data show that the gradual addition of the rare earth ions leads not only to a simple incorporation of the rare earth ions in the host glass matrix but also generates structural changes of the vitreous matrix. FTIR data permitted to determine the Bi³⁺/Bi⁶⁺ ratio of the samples and to follow the compositional evolution of the structural changes for the studied systems. Magnetic susceptibility data show that the magnetic rare earth ions appear as isolated species for low rare earth oxide contents (x ≤ 0.03 ÷ 0.05) and as both isolated and magnetically coupled species for higher contents. All the magnetic rare earth ions present a very accentuated clustering tendency. Some of the studied rare earth ions appear in the host glass matrix in a single valence state (neodymium, gadolinium, and erbium), namely the 3+ one. Other rare earth ions appear in two valence states (i.e., cerium, europium and terbium), but the 3+ one is the most stable.     

Nano-composite soda lime silicate glass prepared using silver ion exchange

Commercial soda lime silicate glasses have been subjected to ion exchange at different temperatures ranging from 320 to 500 °C in a molten mixture of AgNO₃ and NaNO₃ with molar ratio of 10:90, 02:98 and 50:50 for different time periods ranging from 40 to 180 min. Optical and structural properties of the ion exchanged glass are measured using UV–Vis–NIR absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence spectroscopy and transmission electron microscopy (TEM). Signature of silver nanoparticle formation is obtained from the UV–Vis–NIR spectra, which shows a peak at 425 nm due to surface plasmon resonance (SPR). Replacement of Na⁺ ions by Ag⁺ ions is inferred from FTIR spectra. Fluorescence spectra reveal the formation of Ag⁰ atoms from Ag⁺ ions at higher temperatures. TEM image shows the silver nanoparticles of average size 3.75 nm. At exchange temperature of 500 °C Ag nanoparticles are formed without post-exchange annealing treatment.     

Experimental observations of the thermal stability of high-k gate dielectric materials on silicon

High-k dielectric materials including zirconium oxide and hafnium oxide produced by atomic layer deposition have been evaluated for thermal stability. As-deposited samples have been compared with rapid thermal annealed samples over a range of source/drain dopant activation temperatures consistent with conventional complimentary metal oxide semiconductor polysilicon gate processes. Results of this initial investigation are presented utilizing analyses derived from X-ray diffraction (XRD), X-ray reflectometry (XRR), medium energy ion spectroscopy, high resolution transmission electron microscopy (HRTEM), tunneling atomic force microscopy, scanning electron microscopy, Auger electron spectroscopy and secondary ion mass spectroscopy. Changes in interface and surface roughness, percent crystallinity and phase identification for each material as a function of anneal temperature have been determined by XRD, XRR and HRTEM. Finally, high-k wet etch issues are presented relative to subsequent titanium silicide blanket film resistivity values.     

Preparation of hybrid CaCO3–pepsin hemisphere with ordered hierarchical structure and the application for removal of heavy metal ions

In this paper, a simple way for preparation of hybrid CaCO₃–pepsin material with ordered hierarchical structure was reported. It could be observed that the nanoparticles self-assembled into a lot of tetrahedral calcite crystals, which assembled into highly ordered surfaces of hemisphere-shaped CaCO₃ with hierarchical structures. These products were characterized by X-ray powder diffraction (XRD), Scanning electron microscope (SEM), High resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetry-differential thermal analyses (TG-DTA) and photoluminescence (PL). A rational mechanism was proposed for the formation of hybrid CaCO₃–pepsin material ordered hierarchical structure. Functional study using the hybrid CaCO₃–pepsin material as an adsorbent for removal of heavy metal ions demonstrates that its distinguishing features in water treatment involve not only high removal capacities, but also decontamination of trace ions. The acquired experimental data show that both the functional and hierarchical structural features of hybrid CaCO₃–pepsin material provide a promising adsorbent for removal of heavy metal ions.     

In situ synthesis of Ag–Cu bimetallic nanoparticles in silicate glass by a two-step ion-exchange route

Ag–Cu bimetallic nanoparticle/silicate glass composites were fabricated by means of a two-step ion-exchange and subsequently thermal treatment. Optical absorption spectroscopy and transmission electron microscopy (TEM) were used to study the influence of preparation conditions on the formation of Ag–Cu bimetallic nanoparticles in silicate glass. The results show that the volume fraction of copper nanoparticles increases with ion-exchange duration when keeping the same annealing temperature and duration in hydrogen atmosphere during the first stage of Cu doped glass. The Cu doped glass is beneficial to the formation of Ag nanoparticles during subsequent Ag⁺ for Na⁺ ion exchange. Extending Cu⁺ for Na⁺ ion exchange duration makes against the introduction of Ag ions into the Cu doped glass and the formation of Ag nanoparticles in the glass matrix. A few Cu₂O nanoparticles were found in the glass matrix due to the oxidization of small Cu nanoparticles.     

Optical properties of fluorine-substituted zinc bismuth phosphate glasses

The effects of the substitution of fluoride ions for oxide ions on the thermal and optical properties of ternary ZnO-Bi₂O₃-P₂O₅ glass with low-P₂O₅ content (20-25 mol%) were investigated. Fluoride ions were introduced into the glass up to about 12 mol% as ZnF₂. Raman spectra indicated that fluoride ions were substituted for oxide ions connected with bismuth ions. Deformation and glass transition temperatures decreased monotonically with fluorine concentration. The absorption edge shifted toward higher energies with increasing fluorine concentration by about 0.3 eV for 12 mol% ZnF₂ substitution. The blue shift of the absorption edge is attributable to two effects. One was a blue shift of an absorption band which was observed as a peak at 4.7 eV in the reflection spectra and was attributed to the spin forbidden 6s-6p interband transition in Bi³⁺ ions. The blue shift originates from a change in electron-donating ability through anions as expected from electronegativity or optical basicity. Another is a disappearance of a shoulder at around 4.3 eV in the reflection spectra. The latter was the major reason for the large blue shift of the absorption edge energy, because the band relating to the 4.3 eV shoulder is close to the absorption edge.     

Growth of heavy ion-induced nanodots at the SiO2–Si interface: Correlation with ultrathin gate oxide reliability

Scaling-down the oxide thickness induces weakness influencing its intrinsic reliability. Even unbiased, swift heavy ions irradiated devices clearly show oxide alteration. Despite numerous studies on oxide reliability, some results are not yet well understood. In this paper, we focus on the structural degradation induced in thin silicon oxide films on silicon substrate after a 210 MeV low fluence gold ion irradiation and on its effect on the reliability of MOS devices in radiation-harsh environments. We describe such degradation as a local silicon growth in the SiO₂ layer, near the SiO₂–Si interface. Experimental results can bring some emergent elements to explain earlier works in the field of oxide reliability. Based on the specific behavior of heavy ion-irradiated oxides, this paper aims to link together thermal spike model, heavy ion-induced nanodots and reliability of ultrathin gate oxides. We propose to evaluate the possible sensitivity of some high-k materials in radiation-harsh environments with respect to their thermal conductivity property.     

XAFS investigations of nitrided NbN–SiO2 sol–gel derived films

This work presents the results of the structural analysis of xNbN–(100-x)SiO₂ (x = 100, 80, 60 mol%) thin films by X-ray absorption spectroscopy (XAS). To prepare the films, thermal nitridation of sol–gel derived coatings have been performed. The resulting films have a granular structure with NbN grains distributed in the SiO₂ matrix. The size of the grains depends on the NbN/SiO₂ molar ratio. A detailed X-ray absorption fine structure (XAFS) data analysis shows that in all the samples both nitrogen and oxygen atoms are present as nearest neighbours of Nb. The intra-granular phase is an ordered NbN phase, whereas the shells around the grains are formed mainly by an oxide phase and, possibly, by other niobium nitride phases (probably with low nitrogen content). Two possible origins of the inter-granular oxide phase were considered: incomplete nitridation of Nb₂O₅ and addition of SiO₂. Both of them are connected with the sample preparation method. The obtained XAS results allowed us to correlate the thickness and stoichiometry of the films under study with the electronic structure of the Nb ions and with the local geometric structure in their environment.     

Effect of sulphate ions on iron precipitation from aqueous solutions

In the present work, the effects of sulphate ions on the iron precipitation from aqueous solution were investigated. It was shown that sulphate ions delayed the iron precipitation when this ion was added in form of Na₂SO₄. This effect became less significant in presence of magnesium or calcium. The iron precipitates were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). In all experiments iron oxide hydroxide (FeOOH) precipitates were obtained. The sulphate ions were adsorbed on the surfaces of the iron precipitates. The effect of temperature on these precipitates was also studied. At 237 °C, the iron oxide hydroxide precipitates obtained from NaCl solution was transformed in crystallized hematite, Fe₂O₃. At 793 °C, the hematite was partially transformed into magnetite (Fe₃O₄). In presence of sulphate ions, this transformation was not detected. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Iron redox equilibrium, structure and properties of zinc iron phosphate glasses

Iron redox equilibrium, structure and properties were investigated for the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glasses melted at different temperatures. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, Raman spectroscopy and differential thermal analysis. Mössbauer spectroscopy indicated that the concentration of Fe²⁺ ions increased in the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glass with increasing melting temperature. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio increased from 0.18 to 0.38 as the melting temperature increased from 1100 to 1300 °C. The measured isomer shifts showed that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination. It was shown that the dc conductivity strongly depended on Fe²⁺/(Fe²⁺ + Fe³⁺) ratio in glasses. The dc conductivity increases with the increasing Fe²⁺ ion content in these glasses. The conductivity arises from the polaron hopping between Fe²⁺ and Fe³⁺ ions which suggests that the conduction is electronic in nature in zinc iron phosphate glasses.     

XPS characterization of corrosion films formed on the crystalline, amorphous and nanocrystalline states of the alloy Ti60Ni40

X-ray photoelectron spectroscopy investigations were carried out on the crystalline, amorphous and nanocrystalline states of the alloy Ti₆₀Ni₄₀ after corrosion test in 1 M HNO₃ aqueous medium using potentiodynamic polarization method. Polarization plots revealed that the nanocrystalline state is more corrosion resistant than the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀. The XPS characterization of the oxide film formed after corrosion tests revealed that a multiple phase oxide film is formed on the crystalline and amorphous specimens of the alloy Ti₆₀Ni₄₀ consisting of Ti²⁺, Ti³⁺ and Ti⁴⁺ species along with some unoxidized Ti in metallic form (Ti⁰) in the case of crystalline specimen whereas the oxide film formed on nanocrystalline specimen consists of only Ti²⁺ and Ti⁴⁺ species. The high corrosion resistance of nanocrystalline state is attributed to the presence of fewer oxide species in the oxide film than that of the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀.     

X-ray absorption spectroscopy and high-energy XRD study of the local environment of copper in antibacterial copper-releasing degradable phosphate glasses

Phosphate-based glasses of the general formula Na₂O–CaO–P₂O₅ are degradable in an aqueous environment, and therefore can act as antibacterial materials through the inclusion of ions such as copper. In this study, CuO and Cu₂O were added to Na₂O–CaO–P₂O₅ glasses (1–20 mol% Cu) and X-ray absorption spectroscopy (XAS) and high-energy X-ray diffraction (HEXRD) used to probe the local environment of the copper ions. Copper K-edge X-ray absorption near-edge structure (XANES) spectra confirm the oxidation state of copper to be predominantly 2+ in all samples regardless of which copper oxide was used in the preparation. The XANES results suggest the structural environment of copper to be octahedral with respect to oxygen in all samples. The HEXRD results yield a Cu–O nearest-neighbour distance of 1.98 Å and associated coordination number of approximately six, both consistent with octahedral coordination. Analysis of the extended X-ray absorption fine structure (EXAFS) data also yields structural parameters consistent with copper in an octahedral environment. The HEXRD and EXAFS results reveal a Cu–P distance of 3.13 Å, which confirms that the copper ions are coordinated within the phosphate glass network and not phase-separated in domains of copper oxide.     

Synthesis of Nb2O5·nH2O nanoparticles by water-in-oil microemulsion

Hydrous niobium oxide (Nb₂O₅·nH₂O) nanoparticles had been successfully prepared by water-in-oil microemulsion. They were characterized by X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), BET surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the nanoparticle was exactly Nb₂O₅·nH₂O with spherical shape. Their BET surface area was 60 m² g⁻¹. XRD results showed that Nb₂O₅·nH₂O nanoparticles with crystallite size in nanometer scale were formed. The crystallinity and crystallity size increased with increasing annealing temperature. TT-phase of Nb₂O₅ was obtained when the sample is annealed at 550 °C.