Magnetic properties of the double perovskites LaPbMSbO6 (M = Mn, Co and Ni)

New double perovskites LaPbMSbO6, where M2+ = Mn2+, Co2+, and Ni2+, were synthesized as polycrystals by an aqueous synthetic route at temperatures below 1000 oC. All samples are monoclinic, space group P21/n, as obtained from Rietveld analysis of X-ray powder diffraction patterns. The distribution of M2+ and Sb5+ among the two octahedral sites have 3% of disorder for M2+ = Ni2+, whereas for M2+ = Mn2+ and Co2+ less disorder is found. The three samples have an antiferromagnetic transition, due to the antiferromagnetic coupling between M2+ through super-superexchange paths M2+ - O2- - Sb5+ - O2- - M2+. Transition temperatures are low: 8, 10 and 17 K for Mn2+, Co2+, and Ni2+ respectively, as a consequence of the relatively long distances between the magnetic ions M2+. Besides, for LaPbMnSbO6 a small transition at 45 K was found, with ferrimagnetic characteristics, possibly as a consequence of a small disorder between Mn2+ and Sb5+. This disorder would give additional and shorter interaction paths: superexchange Mn2+ - O2- - Mn2+.Comment: 4 pages, 4 figures included. Manuscript submitted to IEEE Transactions on Magnetics, proceedings of the LAW3M 2013 conferenc

Tailoring the ground state of the ferrimagnet La2Ni(Ni1/3Sb2/3)O6

We report on the magnetic and structural properties of La2Ni(Ni1/3Sb2/3)O6 in polycrystal, single crystal and thin film samples. We found that this material is a ferrimagnet (Tc ~ 100 K) which possesses a very distinctive and uncommon feature in its virgin curve of the hysteresis loops. We observe that bellow 20 K it lies outside the hysteresis cycle, and this feature was found to be an indication of a microscopically irreversible process possibly involving the interplay of competing antiferromagnetic interactions that hinder the initial movement of domain walls. This initial magnetic state is overcome by applying a temperature dependent characteristic field. Above this field, an isothermal magnetic demagnetization of the samples yield a ground state different from the initial thermally demagnetized one.Comment: 21 pages, 8 figures, submitted to JMM

Perovskite oxides: Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations

Reflectividad infrarroja de SrRuO₃

En este trabajo presentamos los espectros de reflectividad infrarroja a temperatura ambiente y a 80K piara la perovskita distorsionada SrRuO₃. Con las relaciones de Krammers-Kronig calculamos las funciones ópticas y reconstruimos el espectro de reflectividad con un modelo basado en la generalización de la relación de Lyddane- Sachs-Teller y el modelo de Drude. Con estos datos calculamos el número de portadores, la movilidad efectiva y la conductividad óptica, comparando nuestros resultados con los conocidos para diferentes compuestos.Centro de Química Inorgánic

Phase coexistence of multiple copper oxides on AgCu catalysts during ethylene epoxidation

Alloy catalysts under reaction conditions are complex entities. In oxidizing atmospheres, multiple phases can coexist on a catalyst s surface as a result of phase segregation and preferential oxidation. Such a scenario can result in unusual substoichiometric and metastable phases that could play important roles in catalytic processes. For instance, AgCu alloys known to exhibit enhanced epoxide selectivity in partial oxidation of ethylene form an oxide like surface structure under reaction conditions. Under these conditions, copper oxides are stable, while silver oxides are not. Consequently, copper segregates to the alloy s surface and forms an oxide overlayer. Little is known about the structure or function of such overlayers, and it is unknown whether they play an active role in the catalyst s enhanced selectivity. In order to develop a clearer picture of such catalysts, the current work utilizes several in situ spectroscopic and microscopic techniques to examine the copper oxide phases that form when AgCu is exposed to epoxidation conditions. It is found that several forms of oxidic Cu coexist simultaneously on the active catalyst s surface, namely, CuO, Cu2O, and some previously unreported form of oxidized Cu, referred to here as CuxOy. Online product analysis, performed during the in situ spectroscopic measurements, shows that increased epoxide selectivity is correlated with the presence of mixed copper oxidation states and the presence of the CuxOy species. These results support previous theoretical predictions that oxidic copper overlayers on silver play an active role in epoxidation. These results furthermore emphasize the need for in situ spectromicroscopic methods to understand the complexity of alloy catalyst

The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons

Redox-active copper catalysts with accurately prepared oxidation states (Cu0, Cu+ and Cu2+) and high selectivity to C2 hydrocarbon formation, from electrocatalytic cathodic reduction of CO2, were fabricated and characterized. The electrochemically prepared copper-redox electro-cathodes yield higher activity for the production of hydrocarbons at lower oxidation state. By combining advanced X-ray spectroscopy and in situ micro-reactors it was possible to unambiguously reveal the variation in the complex electronic structure that the catalysts undergo at different stages (i.e. during fabrication and electrocatalytic reactions). It was found that the surface, sub-surface and bulk properties of the electrochemically prepared catalysts are dominated by the formation of copper carbonates on the surface of cupric-like oxides, which prompts catalyst deactivation by restraining effective charge transport. Furthermore, the formation of reduced or partially-reduced copper catalysts yields the key dissociative proton-consuming reactive adsorption of CO2 to produce CO, allowing the subsequent hydrogenation into C2 and C1 products by dimerization and protonation. These results yield valuable information on the variations in the electronic structure that redox-active copper catalysts undergo in the course of the electrochemical reaction, which, under extreme conditions are mediated by thermodynamics but, critically, kinetics dominate near the oxide/metal phase transitions

Modos vibracionales y frecuencias de plasma en SrTi₁₋ₓRuₓO₃ (0,00 ≤ x ≤ l,00)

Los espectros de reflectividad en el ultrarrojo lejano de las soluciones sólidas de SrTi₁₋ₓRuₓO₃ (0,00≤x≤l,00), son interpretados con un modelo para la función dieléctrica basado en la generalización de las relaciones de Lyddane- Sachs-Teller y con una contribución de Drude para el plasma. Los valores de las frecuencias de los modos transversales y longitudinales ópticos fueron comparados con los deducidos de las relaciones de Rrammers -Kronig.Far infrared reflectivity spectra of solid solutions SrTi₁₋ₓRuₓO₃ (0,00≤x≤l,00) are fitted with a model l'or the dielectric function. II is based on a generalization of Lyddane-Sachs-Teller relationship to vvhich a Drude confribution was also added. The optical parameters are compared with those calculated by Krammers- Kronig relalions.Centro de Química Inorgánic