XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy

We present a novel method for preparing an ultra-uniform Raney-Ni catalyst, which includes melt-quenching, hydrogen treatment and leaching in an alkali solution. The resultant catalyst shows superior activity in the reaction of cyclohexanone hydrogenation. X-ray diffraction (XRD) and XPS have been employed to characterize the catalysts. As demonstrated, the pretreatment with hydrogen caused a distinct phase transfer of the Ni-Al alloys, forming more of the Ni2Al3 component. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen-pretreated alloy appeared to be leached more easily and thus the aluminium species remaining on the catalyst surface is aluminium oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. Copyright (C) 2001 John Wiley & Sons, Ltd.

In situ UV-vis and EXAFS studies of ZnO quantum-sized nanocrystals and Zn-HDS formations from sol-gel route

We have pointed Out that. zinc-based particles obtained from zinc acetate sol-gel route is a mixture of quantum-sized ZnO nanoparticles, zinc acetate, and zinc hydroxide double salt (Zn-HDS). Aiming the knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, the thermohydrolysis of ethanolic zinc acetate solutions induced by lithium hydroxide ([LiOH]/[Zn2+] = 0.1) or water ([H2O]/[Zn2+] = 0.05) addition was investigated at different isothermal temperatures (40, 50, 60 and 70 degrees C) by in situ measurements of turbidity, UV-vis absorption spectra and extended X-ray absorption fine structures (EXAFS). Only the growth of ZnO nanoparticles was observed in sol prepared with LiOH, while a two-step process was observed in that prepared with water addition, leading the fast growth of Zn-HDS and the formation of ZnO nanoparticles at advanced stage. A mechanism of dissolution/reprecipitation governed by the water/ethanol proportion is proposed to account for relative amount of ZnO. (c) 2007 Elsevier Ltd. All rights reserved.

Formation of Ce1-xPdxO2-delta solid solution in combustion-synthesized Pd/CeO2 catalyst: XRD, XPS, and EXAFS investigation

Pd/CeO2 (1 at. %) prepared by the solution-combustion method shows a higher catalytic activity for CO oxidation and NO reduction than Pd metal, PdO, and Pd dispersed over CeO2 by the conventional method. To understand the higher catalytic properties, the structure of 1 at. % Pd/CeO2 catalyst material has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. The diffraction lines corresponding to Pd or PdO are not observed in the high-resolution XRD pattern of 1 at. % Pd/CeO2. The structure of 1 at. % Pd/CeO2 could be refined for the composition of Ce0.99Pd0.01O1.90 in the fluorite structure with 5% oxide ion vacancy. Pd(3d) peaks in the XPS in I at. % Pd/CeO2 are shifted by 3 eV indicating that Pd is in a highly ionic +2 state. EXAFS studies show the average coordination number of 3 around Pd2+ ion in the first shell of 1 at. % Pd/CeO2 at a distance of 2.02 Angstrom, instead of 4 as in PdO. The second shell at 2.72 Angstrom is due to Pd-Pd correlation which is larger than 2.69 Angstrom in PdO. The third shell at 3.31 Angstrom having 7 coordination is absent either in Pd metal or PdO, which can be attributed to -Pd2+-Ce4+- correlation. Thus, 1 at. % Pd/CeO2 forms the Ce1-xPdxO2-delta type of solid solution having -Pd2+-O-2-Ce4+- kinds of linkages.

XANES and EXAFS of copper compounds: Studies of copper carboxylates with metal-metal bonds and of the complex formed byPseudomonas aeruginosa

X-ray absorpion near edge structure (xanes) of copper compounds with copper in 1+, 2+ and 3+ states has been studied. Extended x-ray absorption fine structure (exafs) has been employed to determine bond distances and coordination numbers in several model copper compounds. Employing bothxanes andexafs, the structure of the copper complex formed by the micro-organismPseudomonas aeruginosa has been shown to be square-planar with the Cu-O distance close to that in cupric glucuronates and cupric acetylacetonate.exafs has been shown to be useful for studying metal-metal bonds in copper carboxylates.

Strong metal-support interaction in Ni/TiO2 catalysts: in situ EXAFS and related studies

In situ EXAFS and X-ray diffraction investigations of Ni/TiO2 catalysts show that NiTiO3 is formed as an intermediate during calcination of catalyst precursors prepared by the wet-impregnation method; the intermediate is not formed when ion-exchange method is used for the preparation. On hydrogen reduction, NiTiO3 gives rise to Ni particles dispersed in the TiO2(rutile) matrix. The occurrence of the anatase-rutile transformation of the TiO2 support, the formation and subsequent decomposition/reduction of NiTiO3 as well as the unique interface properties of the Ni particles are all factors of importance in giving rise to metal-support interaction. Active TiO2(anatase) prepared from gel route gives an additional species involving Ni3+.

Structural characterization of DC magnetron-sputtered TiO2 thin films using XRD and Raman scattering studies

Titanium dioxide films have been deposited using DC magnetron sputtering technique onto well-cleaned p-silicon substrates at an oxygen partial pressure of 7 x 10(-5) mbar and at a sputtering pressure (Ar + O-2) Of I X 10(-3) mbar. The deposited films were calcinated at 673 and 773 K. The composition of the films as analyzed using Auger electron spectroscopy reveals the stoichiometry with an 0 and Ti ratio 2.08. The influence of post-deposition annealing at 673 and 773 K on the structural properties of the titanium dioxide thin films have been studied using XRD and Raman scattering. The structure of the films deposited at the ambient was found to be amorphous and the films annealed at temperature 673 K and above were crystalline with anatase structure. The lattice constants, grain size, microstrain and the dislocation density of the film are calculated and correlated with annealing temperature. The Raman scattering study was performed on the as-deposited and annealed samples and the existence of Raman active modes A(1g), B-1g and E-g corresponding to the Raman shifts are studied and reported. The improvement of crystallinity of the TiO2 films was also studied using Raman scattering studies. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

EXAFS and XRD analyses of the structural evolutions involved during drying of SnO2 hydrogels

In order to determine structural changes during drying of inorganic gels, the local and long-range order structure of SnO2-x(OH)2x xerogels resulting from drying hydrogels with different concentrations of electrolyte (Cl- and NH+ 4) have been measured by extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD) and N2 adsorption techniques. EXAFS measurements performed at the Sn K edge on the hydrogels and xerogels show the existence of microcrystallites with the cassiterite structure. Two drying modes have been used: freeze drying and drying by evaporation at 45°C. It is shown that the microcrystallite size determined by XRD and EXAFS techniques on the drying mode and on the electrolyte concentrations. The microcrystallite size measured on the freeze dried xerogels is similar to that of their parent hydrogels, whatever the concentration of electrolyte; however, during drying by evaporation, a preferential growth of microcrystallites along the c-axis of the cassiterite structure is observed. The size of these crystallites is enhanced with a decrease of the electrolyte concentration. Specific surface areas calculated by the Brunauer-Emmett-Teller method indicate that this preferential growth is related to the improvement of the network connectivity. The comparison of both drying processes indicates that crystallization and polycondensation are independent phenomena. © 1995 Elsevier Science B.V. All rights reserved.

Kaolinite platelet orientation for XRD and AFM applications

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. The nature of such forces is important to understand in order to manipulate the aggregate structure for applications such as settling and dewatering. A parallel particle orientation is required when conducting force measurements acting between the basal planes of clay mineral platelets using atomic force microscopy (AFM). In order to prepare a film of clay particles with the optimal orientation for conducting AFM measurements, the influences of particle concentration in suspension, suspension pH and particle size on the clay platelet orientation were investigated using scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. From these investigations, we conclude that high clay (dry mass) concentrations and larger particle diameters (up to 5 µm) in suspension result in random orientation of platelets on the substrate. The best possible laminar orientation in the clay dried film as represented in the XRD by the 001/020 intensity ratio of more than 150 and by SE micrograph assessments, was obtained by drying thin layers from 0.2 wt% of -5 µm clay suspensions at pH 10.5. These dried films are stable and suitable for close-approach AFM studies in solution.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

EXAFS studies of arsenic chalcogenide glasses

An EXAFS study at the AsK edge of the ternary glasses As2(S, Se)3 and As2(Se, Te)3 and the binary As2S3, As2Se3 and As2Te3 glasses has been carried out. Radial structure functions show that the environment of As in glasses of intermediate compositions is quite different from that in the binary glasses. In the As2(S, Se)3 system, this might arise from chemical disorder in the network while in the As2(Se, Te)3 system increased ionicity could be the cause of this behaviour. Glasses where the constituent atoms are of similar size seem to exhibit fewer peaks in the radial structure function.