Effect of Silver Nanoparticles on the Sorption Characteristics of La1 − xAgxMnO3 ± y

The effect silver nanoparticles have on the sorption characteristics of perovskite lanthanum manganite relative to methanol, benzene, and hexane vapors is studied by means of gravimetric equilibrium interval sorption. The state of silver particles is investigated using spectroscopic tools. Sorption data are compared to the catalytic activity in deep oxidation reactions of organic compounds over lanthanum manganite-based catalysts.

     

A Novel Calorimetric Approach to the Redox Thermochemistry of Non-stoichiometric Oxides enthalpy of Oxidation of La1−yCayCrO3−δ

A novel calorimetric approach to the energetics of redox reactions in non-stoichiometric oxides is presented. The method utilizes a step-wise heated adiabatic calorimeter for determination of average enthalpies of oxidation. The measurement uncertainty is dominated by the uncertainty in the determination of the mass increment due to the oxidation. An experimental investigation of the re-oxidation energetics of reduced La_1–yCa_yCrO_3– is presented. The variation of the average formal oxidation state with temperature and oxygen fugacity is calculated from the experimentally determined enthalpy of oxidation and an estimated (lattice and configurational) entropy of oxidation. The calculated curves are in good agreement with experimental determinations reported in literature.This revised version was published online in November 2005 with corrections to the Cover Date.     

Spectroscopic properties and luminescence concentration quenching of the Pr3+ ion in La1−xPrxOCl

Luminescence spectra ofLa_1−xPr_xOCl(0.01 ≤ x ≤ 0.3) were recorded at liquid helium and room temperature. From these spectra, the energy level diagram of Pr³⁺ in LaOCl was deduced. The decay times of the Pr³⁺ emission in La_1−xPr_xOCl were measured using a high-resolution dye laser system. The linear concentration quenching and exponential decay times are explained assuming cross relaxation and energy transfer between the Pr³⁺ ions.     

Electrical and electro-chemical characterisation of La0.99Fe1−x Ni x O3−δ perovskites

(LFN, 0<x<0.6) perovskites were synthesised by a solid-state route and were characterised by powder XRD, dilatometry, four-point DC conductivity measurements and electro-chemical impedance spectroscopy (EIS) on cone-shaped electrodes using a Ce_1.9Gd_0.1O_1.95 (CGO10) electrolyte. All the compounds were of single phase, and they belong to either the cubic or the hexagonal crystal system. The thermal expansion coefficient (TEC) was in the range 10.7*10⁻⁶ K⁻¹ to 13.4*10⁻⁶ K⁻¹, which continued to increase with increasing nickel content. The highest electronic conductivity was measured for the composition giving a value of 670 S/cm at 380 °C. The highest electro-chemical performance was measured for the composition giving an area specific resistance as low as 5.5 Ωcm² at 600 °C based on EIS measurements on a cone-shaped electrode. Composite cathodes made from and CGO10 revealed a rather low performance due to an un-optimised micro-structure.

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The promotion effect of catalytic activity by Ru substitution at the B site of La1−x Sr x Cr1−y Ru y O3−z for propane steam reforming

A series of La_1?x Sr _x Cr_1?y Ru _y O_3?δ (0.1 ≤ x ≤ 0.5, 0.05 ≤ y ≤ 0.15) materials was prepared by the sol–gel method to develop alternative catalysts for propane steam reforming. Catalyst characteristics were evaluated using physicochemical methods including X-ray diffraction, Brunauer–Emmett–Teller methods, H₂ temperature-programmed reduction, and thermogravimetry analysis (TGA). Effects of the amount of ruthenium (Ru) and strontium and the steam-to-carbon ratio (S/C) were investigated. An increase in Ru content led to increased propane conversion and H₂ yield, especially below 700 °C. Dramatic enhancement of catalytic activity was observed with La_0.8Sr_0.2Cr_0.85Ru_0.15O₃ under 600 °C, achieving propane conversion over 79% between 600 and 800 °C with maximum propane conversion and H₂ yield of 98.3% and 63.3%, respectively. Also, good resistance to carbon formation for the La_0.8Sr_0.2Cr_0.85Ru_0.15O₃ catalyst was confirmed by long-term testing and TGA analysis.

     

Longitudinal conductivity of thin films of La1 − x Sr x F3 − x solid solutions on glass ceramics

The longitudinal conductivity of La_{1 ? x} Sr _x F_{3 ? x} solid solution films (x = 0–0.24) with thicknesses of 40–260 nm grown on glass ceramics at temperatures from room temperature to 300°C and frequencies of 10^?1–10⁶ Hz was studied by impedance spectroscopy. The concentration dependence of film conductivity on the SrF₂ content had a maximum near x = 0.05. An equivalent circuit was constructed on the basis of the impedance plots to describe migration processes. The DC conductivity was evaluated for all samples under study. The activation energies were estimated from the temperature dependences of the DC conductivities of the films. The resulting dependences of electrophysical parameters were compared with those for bulk materials in terms of the relaxation conductivity model.     

Mixed valence states of Cr and Fe in La1−xSrxFe0.8Cr0.2O3−y

The La_1?xSr_xFe_0.8Cr_0.2O_3?y (x = 0.2, 0.4, 0.6 and 0.8) phases were studied by X-ray photoelectron spectroscopy at room temperature and ⁵⁷Fe Mössbauer spectroscopy at different temperatures. Mixed valence states were observed both for chromium and iron ions, justifying the complex magnetic behaviour exhibited by these compounds. The Mössbauer results indicate the simultaneous presence of Fe³⁺, Fe⁴⁺ and Fe⁵⁺ at 4.2 K and the co-existence of Fe³⁺ and Fe⁽³⁺ⁿ⁾⁺ at T = 293 K, with the latter fraction increasing with increasing strontium content. The presence of Cr^3+/4+ is interpreted as being mainly responsible for the incomplete charge disproportionation reaction of iron at low temperature, as deduced from the Mössbauer results.     

Ab initio cluster study of the bilayer manganite La2−2xSr1+2xMn2O7

We have performed complete active space self-consistent field (CASSCF) cluster calculations for (MnO₆)⁹⁻ and (MnO₆)⁸⁻ complexes in the background potential appropriate for the bilayer manganite La_2−2xSr_1+2xMn₂O₇ at x=0.40. While the ground state of the (MnO₆)⁹⁻ complex is well-described by a restricted Hartree–Fock wavefunction, contributions from configurations with holes in oxygen orbitals are significant in the (MnO₆)⁸⁻ ground state wavefunction. Surprisingly, the CASSCF calculations including sufficient oxygen orbitals in the active space yields a doubly degenerate E (of the C_4v point group) as the ground state.     

A study of the thermal analysis of the solid solution (AgxK1−xNO3

The effect of partial replacement of K⁺ by Ag⁺ in the mixed system of KNO₃ and AgNO₃ during a set of DSC heating cycles was studied by means of a modern computerized DSC system. Thermal analysis was performed in the vicinity of the phase transition II I for pure KNO₃. The results revealed a large change in enthalpy and the phase transition temperature close to the morphotropic boundary x=0.5–0.6. At this boundary, the transformation enthalpy reached the maximum value of 101 J g^–1. On the basis of the data obtained from this accurate thermal analysis work, a model is suggested for the energy barrier of rotation of the nitrate ion in the mixed nitrate system.     

Preparation and properties of the systems Co1−xRhxS2, Co1−xRuxS2, and Rh1−xRuxS2

Members of the systems Co_1−xRh_xS₂ (0 ≤ x ≤ 0.6) were prepared, and their crystallographic and magnetic properties studied. The observed ferromagnetic moments for compositions where x ≤ 0.2 indicate a ferromagnetic alignment between Co(3d⁷) and Rh(4d⁷) electrons. This is the first observation of localized behavior of 4d electrons in the pyrite structure. Members of the systems Co_1−xRu_xS₂ (0 ≤ x ≤ 1) and Rh_1−xRu_xS₂ (0.5 ≤ x ≤ 1) were also prepared and their crystallographic and magnetic properties studied. From comparison with the Co_1−xRh_xS₂ system, it appears that the 4d electrons of Rh(4d⁷) are localized in the presence of Co(3d⁷) but are delocalized in the presence of Ru(4d⁶). The magnetic susceptibility of the Co_1−xRu_xS₂ system is sensitive to the homogeneity of the products and indicates that Ru(4d⁶) behaves as a diamagnetic ion.     

Ab initio simulation of the photoelectron spectra of HCO− and DCO−

Large scale, vibrational CI calculations using a global ab initio potential energy surface are used to calculate multidimensional Franck-Condon overlaps from the ground vibrational state of HCO⁻ and DCO⁻ to all final bound and several quasibound vibrational states of HCO and DCO. The resulting Franck-Condon spectra are compared with recent experimental photoelectron spectra of HCO⁻ and DCO⁻.     

Magnetotransport properties of Mo substituted La0.7Ca0.3Mn1−xMoxO3 perovskites

We studied the effects of Mo substitution on the structural, transport, and magnetic properties of the La_0.7Ca_0.3Mn_1−xMo_xO₃ (x ≤ 0.1) samples. Powder X-ray diffraction analysis reveals that the samples studied crystallize in the orthorhombic structure with space group Pbnm. Both particle size and morphology change significantly as the Mo content x varies. The metal-insulator transition temperature (T_MI) and Curie temperature (T_C) decrease monotonically as x increases. Magnetization data reveal that long-range FM ordering persists in all samples and the saturation moment decreases linearly as x increases. The smaller depression rate of dT_C/dx observed is mainly ascribed to the increased amount of Mn²⁺ ions with Mo doping, which opens the FM coupling between Mn²⁺–O–Mn³⁺ in the samples.     

Structure,nonstoichiometry and magnetic properties of the perovskites Sr1−xCaxMnO3−δ

The structural, thermal and magnetic properties of the perovskite-type alkaline-earth manganites of the series Sr_1−xCa_xMnO_3−δ (0⩽x⩽1) were investigated. SrMnO_3−δ forms a hexagonal perovskite lattice and shows a first-order transformation to a highly defective cubic high-temperature modification. By substituting Ca for Sr (x>0.25) the hexagonal perovskite is suppressed and a cubic (or orthorhombic) lattice becomes stabilized for all temperatures. For x=0.5 and 0.75 cubic perovskites with a large nonstoichiometry (e.g., δ=0.25 for x=0.5) are obtained at 1400 °C. The defective perovskites are prepared by either quenching from high temperature or by cooling in an inert atmosphere. The oxygen vacancies are easily filled by subsequent reoxidation at low temperature (400–600 °C) and stoichiometric samples are obtained. Orthorhombic perovskites are formed at T⩽1200 °C with the nonstoichiometry δ increasing with increasing temperature (e.g., δ=0.06 at 1000 °C and δ=0.14 at 1200 °C for x=0.5). Slow cooling in air results in almost complete reoxidation (δ=0). CaMnO_3−δ is an orthorhombic perovskite with a large range of nonstoichiometry (0⩽δ⩽0.30). The cubic to hexagonal phase transformation of the Sr-rich samples is accompanied by a large expansion of the lattice that is reduced by Ca substitution. The Ca/Sr-manganites are antiferromagnets with T_N of 170 K for x=0.5 and δ=0.02 and 120 K for x=1 and δ=0.05.     

Atoms state and interatomic interactions in perovskite-like oxides: XXXII. Formation of paramagnetic clusters in the La1−0.33x Ca0.33x Fe x Al1−x O3 and La1−0.33x Sr0.33x Fe x Al1−x O3 solid solutions

Calcium- and strontium-containing lanthanum orthoferrites have been studied using magnetic dilution method. It has been shown that the iron-atom clusters with competing ferro- and antiferromagnetic exchange interactions can exist. By using Mossbauer spectroscopy, Fe(IV) atoms have been found in the La_1?0.33x Ca_0.33x Fe_xAl_1?x O₃ solid solutions and Fe(III) atoms in two different surroundings have been found in the La_1?0.33x Sr_0.33x Fe _x Al_1?x O₃ solid solutions. The compositions of paramagnetic clusters stable at the infinite dilution have been proposed basing of the magnetic susceptibility and Mossbauer spectroscopy data.     

Thermal stability and features of the synthesis of mixed ceramic oxides La2−x Sr x CoO4

Thermal behavior of the mixed oxides La_2?x Sr _x CoO₄ (0.1 < x < 1.5) in the temperature range 1200–1700 K was studied. The use of the ceramic synthesis method makes it possible to obtain homogeneous samples at the calcination temperature of 1673 K. It was found by the high-temperature mass-spectrometry method that a charge can be depleted of cobalt oxide during the high-temperature synthesis.     

Weakly bound oxygen and its role in stability of solid solutions La1−x Sr x FeO3−δ

In the present study high-temperature X-ray diffraction, thermal analysis, and mass-spectrometry have been employed for investigation of samples in the La_1?x Sr _x FeO_3?δ family (0 ≤ x ≤ 1), the materials being solid solutions having perovskite structure. It has been shown that the loss of oxygen by the samples on heating to 1200°C in air (0 ≤ x ≤ 1) or in vacuum (x < 0.75) does not result in structural rearrangement of the solid solutions, but causes an increase in the lattice parameters. Heating of the compositions with x ≥ 0.75 in vacuum affords phases with ordered vacancies. The observed structural evolutions (growth of the unit cell parameter and vacancy ordering) are reversible, and on re-oxidation (on cooling in air or additional heating of the “vacuum” samples in air atmosphere) the original parameters of the oxides are recovered. The amount of oxygen evolved on heating increases in vacuum or in helium atmosphere, as compared to air, and also grows with rising strontium content, but under experimental conditions does not reach the maximum possible value (δ = x/2).     

Effect of the composition on the thermal behaviour of the SrSn1−xTixO3 precursor prepared by the polymeric precursor method

Strontium stannate titanate Sr(Sn, Ti)O₃ is a solid solution between strontium stannate (SrSnO₃) and strontium titanate (SrTiO₃). In the present study, it was synthesized at low temperature by the polymeric precursor method, derived from the Pechini process. The powders were calcined in oxygen atmosphere in order to eliminate organic matter and to decrease the amount of SrCO₃ formed during the synthesis. The powders were annealed at different temperatures to crystallize the samples into perovskites-type structures. All the compositions were studied by thermogravimetry (TG) and differential thermal analysis (DTA), infrared spectroscopy (IR) and X-ray diffraction (XRD). The lattice former, Ti⁴⁺ and Sn⁴⁺, had a meaningful influence in the mass loss, without changing the profile of the TG curves. On the other hand, DTA curves were strongly modified with the Ti⁴⁺:Sn⁴⁺ proportion in the system indicating that intermediate compounds may be formed during the synthesis being eliminated at different temperature ranges, while SrCO₃ elimination occurs at higher temperature as shown by XRD and IR spectra.     

Nonempirical calculations of the potential-energy fields of the nucleophilic addition of H− and F− to acetylene and methylacetylene molecules

By using the basis 3–21 + G, the minimum-energy routes for the nucleophilic addition to the F^– ion to methylacetylene have been calculated within the framework of the Hartree-Fock-Roothaan method according to and against the Markovnikov rule with the formation of the 1-fluoropropenyl and 2-fluoropropenyl anions. The results have been compared with data from previous calculations of the nucleophilic addition of H^– and F^– to acetylene with the formation of vinyl and fluorovinyl anions, as well as of the nucleophilic addition of H^– to methylacetylene according to and against the Markovnikov rule with the formation of the 1-propenyl and 2-propenyl anions. It has been established that the reaction with H^– is exothermic, while the reaction with F^– is endothermic. The activation energies of the reactions with F^– are lower than the activation energies of the corresponding reactions with H^–. It is shown that the reactions with H^– have a relatively early transition state, while the reactions with F^– are characterized by a later transition state.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 28, No. 1, pp. 5–11, January–February, 1992.