Lanthanum-based perovskites obtained in molten nitrates or nitrites

Lanthanum-based perovskites, LaMO₃ (where M = Mn, Fe, Co, Ni), have been synthesised from lanthanum precursors and corresponding 3d transition metal salts in molten alkali metal nitrates or nitrites. The reactivity of eight precursors in three molten salts of different basicity was analysed. Single phase orthorhombic LaMnO_3.11, and orthorhombic LaFeO₃ have been obtained in molten NaNO₂ at 723 K, for 2 h. LaCoO₃ is also formed in molten nitrite, but an increase of basicity, by adding Na₂O₂, was necessary to obtain LaNiO₃. The reaction systems were investigated by thermal analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and specific surface area measurements (BET method) were used to characterise the synthesised nanopowders.     

Reactions of Metal Salts and Alkali Metal Nitrates. Role of the Metal Precursors and Alkali Metal Ions in the Resulting Phase of Zirconia

Zirconia powders are prepared by reaction of a zirconium precursor with an alkali metal nitrate. The major part of the reactions takes place before the melting points and then the reactions go slowly to completion at 450°C in the molten salts. The roles of the precursor and the alkali metal ion are discussed considering the reaction between two precursors, octahydrated zirconium oxychloride and zirconium tetrachloride, and two nitrates, LiNO₃ and NaNO₃, and some resulting physico-chemical differences. The obtained zirconia powders contain very small amounts of alkali metal ions which act as stabilizing agent. Their effect on the balance tetragonal-monoclinic ZrO₂ depends upon the homogeneity of their distribution which is related to their ability to diffuse inside the bulk of particles and their polarizing power when located mainly on the surface.     

ESCA studies of some copper and silver selenides

Photoelectron and Auger spectra have been obtained for the copper and silver selenides CuSe, Cu ₂Se, Ag ₂Se, and AgCuSe as well as from CuS, Ag ₂O, Ag ₂S, Cu, and Ag. Binding-energy values, chemical shifts, and peak-shapes are reported for the Cu 3 d, Ag 4 d and Se 3 p electrons. Absence of multiplet splitting and shake-up structure is discussed in relation to the magnetic properties. It is shown that chemical shifts are much better revealed in the Auger spectra (Cu L₃M_4,5M_{4, 5} and Ag M₅N_{4, 5}N_{4, 5}) than in the direct photoelectron ones. In addition the use of the Auger parameter to characterize the series under study is emphasized. Finally the valence-band spectra have been examined and the electronic structures are interpreted.     

Synthesis,characterization, electrochemical behaviour and catalytic activity of manganese(II) complexes with linear and tripodal tetradentate ligands derived from Schiff bases

New manganese(II) complexes, [Mn(H₂L)(H₂O)₂]Cl₂· xH₂O, with linear and tripodal tetradentate ligands have been synthesized and characterized by elemental analysis, molar conductance, i.r. spectra, magnetic measurements and electronic and e.s.r. spectra. The data show that the ligands are neutral and coordinate to manganese in a tetradentate manner; the other axial sites are occupied by the water molecules. Magnetic and e.s.r. data show that manganese(II) adopts a high-spin configuration in the complexes. The electrochemical behaviour of the complexes, determined by cyclic voltammetry, shows that the chelate structure, ligand geometry and electron donating effect of the ligand substituents are among the factors influencing the redox potentials of the complexes. In addition, we note that linear ligands stabilize the manganese(III) state to a greater extent than tripodal ligands and their complexes vigorously catalyse the disproportionation of hydrogen peroxide in the presence of added imidazole.     

Structural study of bonding in halogeno ruthenium complexes: Application to ruthenium nitrosyls

The halogeno nitrosyl ruthenium complexes are studied using their structural characteristics as basis. The structures of K₂RuNOX ₅ (X=Cl, Br, I) have been determined or redetermined. The study of the bond lengths Ru-Cl is, in a first part, placed in the general frame of the chlorocomplexes of ruthenium having and+ type ligands. The comparison points to a lengthening of the Ru-Cl_axial bond in [RuNOCl₅]^2–, which is opposite to the trans shortening effect up to now considered. A second part deals with the deformation of the octahedral coordination of the ruthenium atom. In [RuNOX ₅]^2–, the distance from the ruthenium to the equatorial plane varies with the position ofX in the spectrochemical series. The role of thed _xy orbital in the geometry of these ions is discussed.     

Electrochemical promotion of propane deep oxidation on doped lanthanum manganites

Electrochemical catalysts based on LSM deposited on YSZ were used for propane deep oxidation. Electrochemical characterizations such as impedance spectroscopy and current–overpotential measurements were performed. Different thicknesses of LSM films were catalytically characterized and EPOC experiments were carried out on those electrochemical catalysts. It was found that the reaction rates can be in situ tuned by applying an anodic polarization but with weak promotional effects. The faradaic efficiency decreased as the applied potential, the temperature, and the thickness of the catalyst increased. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Study of the reaction of tungsten carbide in molten alkali metal nitrates. Syntheses of divalent (s and d blocks) metal tungstates

WC is tested as precursor to synthesize metal tungstates by reaction in molten alkali metal nitrates. This constitutes a complex redox system with two reducing agents, W and C, and an oxidizer having several oxidation states. The mass loss due to the evolution of gases reveals the reaction steps. The infrared analyses of the gas phase show what kind of reaction develops according to the temperature. WC produces a water-soluble alkali metal tungstate. The reaction of a mixture of WC and a divalent metal chloride (Mg, Ca, Ba, Ni, Cu, Zn) leads to water-insoluble metal tungstates. As the reactivity of the cations increases in the order Zn, Ni, Cu, the reaction of WC is modified by their presence. The physico-chemical characterizations of the products show that some of them are contaminated either by WC or by metal oxide. Some others are rather pure products. These differences, in relationship with the other analyses, allow to propose first reaction pathways of the tungsten carbide in molten salts.     

A new method for the preparation of Ru(IV) in non-complexing acid medium: Evidence for tetrameric Ru(IV)

A new method for the preparation of Ru(IV) in acid solutions is described. This method, avoiding the preparation of the highly reactive RuO₄, is based on the stoichiometric oxidation of Br^? ion of K₂RuBr₆ by BrO₃^? ion. Easy to control and reproducible the process leads to solutions of a well-known composition consisting of the tetrameric Ru(IV) ion.     

X-ray photoelectron emission studies of mixed selenides AgGaSe2 and Ag9GaSe6

Auger and direct electron specta from crystalline AgGaSe₂ and Ag₉GaSe₆ have been studied with X-ray photoelectron spectroscopy. It is shown that the AgM₅N_4,5N_4,5 and M₄N_4,5N_4,5 Auger spectra are more sensitive to the chemical environment than the Ag 3d direct photoelectron spectra. Furthermore the Auger parameter as defined by Wagner is used in order to characterize the chemical state of these compounds. Last, the XPS spectra of the valence-band region are investigated and chalcogen s and p and noble-metal d bands are clearly identified. The electronic structure of these two selenides does not seem to be determined predominantly by the crystal structure. As a whole, the spectral features are discussed in connection with the character of the chemical bonding and the physical properties of these compounds.