Oxygen intercalation in Ruddlesden-Popper type Sr3LaFe3O10-δ

The oxygen nonstoichiometry of Ruddlesden-Popper type Sr3LaFe3O10-δ, a promising parent material for mixed-conducting electrodes and membranes, was studied in the oxygen partial pressure range from 10−24 to 0.5 atm at 973–1223 K by coulometric titration and thermogravimetry. The p(O2)-T-δ diagram can be described using a statistical thermodynamic model relating the non-ideal behavior in oxidizing and strongly reducing atmospheres to the coulombic interaction between oxygen vacancies and electronic charge carriers. The results confirm a strong energetic affinity of anion vacancies to the central perovskite-like layers of the Ruddlesden-Popper structure, whilst the difference between crystallographic iron sites has no significant effects on the oxygen intercalation thermodynamics at elevated temperatures. No indications of long-range ordering in the oxygen sublattice were observed.publishe

Perovskite-related oxide materials for oxygen-permeable electrochemical membrans

This brief review is focused on the studies of mixed ionic-electronic conductors on the basis of lanthanum gallate doped with transition metal cations in the В sublattice. The substitution of gallium with iron, cobalt or nickel results in greater electronic conductivity, simultaneously keeping high level of the oxy-gen ionic transport. In particular, La0 90Sr0 10Ga0 65Ni0 20Mg0 1503d perovskite exhib-its attractive oxygen permeability, which is quite similar to that of La2Ni04- and (La,Sr)Co03-based phases The combination of appropriate transport and thermomechanical properties with sufficiently high thermodynamic stability en-ables to use Ni- or Fe-substituted LaGa03-based mixed conductors for the mem-brane electrocatalytic reactors for partial oxidation of light hydrocarbons

Weak Ferromagnetism in LaCo1-xRhxO3: Anomalous Magnetism Emerging between Two Nonmagnetic End Phases

Magnetization has been measured for polycrystalline samples of LaCo1-xRhxO3 (0 {\leq} x {\leq} 0.9) in order to investigate magnetism induced in the solid solution of two nonmagnetic end phases of LaCoO3 and LaRhO3. It is found that a ferromagnetic transition is observed below 15 K in the range of x from 0.1 to 0.4. The effective Bohr magnetic moment evaluated from the temperature dependence of magnetic susceptibility at around room temperature is independent of x for 0 < x < 0.5 (approximately 3 {\mu}B per formula unit), and rapidly decreases above x = 0.5. On the basis of detailed magnetization measurements, the spin state and magnetic ordering of LaCo1-xRhxO3 are discussed.Comment: 16 pages, 6 figures, to be published in J. Phys. Soc. Jp

Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp507826jWe report a joint experimental and theoretical study of the structural and vibrational properties of synthetic sphaerobismoite (beta-Bi2O3) at high pressures in which room-temperature angle-dispersive X-ray diffraction (XRD) and Raman scattering measurements have been complemented with ab initio total energy and lattice dynamics calculations. Striking changes in Raman spectra were observed around 2 GPa, whereas X-ray diffraction measurements evidence no change in the tetragonal symmetry of the compound up to 20 GPa; however, a significant change exists in the compressibility when increasing pressure above 2 GPa. These features have been understood by means of theoretical calculations, which show that beta-Bi2O3 undergoes a pressure-induced isostructural phase transition near 2 GPa. In the new isostructural beta' phase, the Bi3+ and O2- environments become more regular than those in the original beta phase because of the strong decrease in the activity of the lone electron pair of Bi above 2 GPa. Raman measurements and theoretical calculations provide evidence of the second-order nature of the pressure-induced isostructural transition. Above 20 GPa, XRD measurements suggest a partial amorphization of the sample despite Raman measurements still show weak peaks, probably related to a new unknown phase which remains up to 27 GPa. On pressure release, XRD patterns and Raman spectra below 2 GPa correspond to elemental Bi-I, thus evidencing a pressure-induced decomposition of the sample during downstroke.Financial support from the Spanish Consolider Ingenio 2010 Program (MALTA Project CSD2007-00045) is acknowledged. This work was also supported by Brazilian Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) under Project 201050/2012-9, Spanish MICINN under Projects MAT2010-21270-004-01/03/04 and MAT2013-46649-C4-2/3/4-P, Spanish MINECO under Project CTQ2012-36253-C03-02, and from Vicerrectorado de Investigacion de la Universitat Politecnica de Valencia under Projects UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. JAS. acknowledges Juan de la Cierva fellowship program for financial support.Pereira, ALJ.; Sans Tresserras, JÁ.; Vilaplana Cerda, RI.; Gomis, O.; Manjón Herrera, FJ.; Rodriguez-Hernandez, P.; Muñoz, A.... (2014). Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study. Journal of Physical Chemistry C. 118(40):23189-23201. https://doi.org/10.1021/jp507826jS23189232011184