X-ray photoelectron spectroscopy investigation of perovskites La1−x Sr x FeO3−y (0 ≤x < 1.0), prepared via a mechanochemical route

Perovskite-structure oxides La_1?x Sr _x FeO_3?y (x = 0, 0.2, 0.6, 1) were synthesized by the mechanochemical method. In order to refine the stoichiometric composition and the charge state of ions, these samples were studied by X-ray photoelectron spectroscopy (XPS). An investigation of perovskites with x = 0, 0.2, and 0.6 in air at room temperature showed that these samples do not contain oxygen vacancies (y = 0), i.e., they are fully oxidized. Hence, to produce electrical neutrality, these samples should contain iron(4+) cations in an amount proportional to the degree of substitution (x) of strontium(2+) for lanthanum(3+). However, no Fe⁴⁺ cations were found in the oxides. All perovskites contain only Fe³⁺ cations, oxygen ions O^2? along with oxygen ions with reduced electron density (O^?). These data provid evidence of the possible electron density redistribution from oxygen ions to iron cations. The fact that the oxides contain oxygen ions with reduced electron density suggests that weakly bound lattice oxygen in substituted perovskites is represented by O^? ions.     

Thermodynamic properties and cation distribution of the ZnFe2O4Fe3O4 spinel solid solutions at 900°C

The thermodynamic properties of the Fe₃O₄ZnFe₂O₄ spinel solid solution were determined at 900°C by the use of the solid electrolyte galvanic cell Fe₂O₃ + Fe₃O₄|O^2?|Fe₂O₃ + Zn_xFe_3?xO₄The activity values obtained exhibit slight negative deviation from the ideal solution model. An analysis of the free energy of mixing of the spinel solid solution provided information on the distribution of cations between the tetrahedral and octahedral sites of the spinel lattice. This is the basis for the estimation of the free energy of formation of pure zinc ferrite from oxides. ΔG⁰_ZnFe2O4 = ?2740 ? 1.6 T cal mole^?1     

Electrochemical properties and state of paramagnetic centers in copper-modified complex vanadium and titanium oxides

Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu _x V_2?y Ti _y O_5?δ·nH₂O (0<y<1.33) have a layered structure and oxides Cu _x Ti_1?y V _y O_5+δ·nH₂O (0<y<0.25), an anatase structure. The intercalation of cations Cu²⁺ into the hydrates leads to oxidation of V⁴⁺. According to ESR data, V⁴⁺ exists in the oxides in the form of VO²⁺ and an octahedral surround of oxygen (V⁴⁺?O₆), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu²⁺ alters the content of V⁴⁺ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed.     

Solubility product and related thermodynamic quantities of silver and barium chromates in formamide

The values of ΔG⁰, ΔH⁰, and ΔS⁰ for the dissolution process, M₂(CrO₄)_x + solvent — 2 M^x+ (solvated) + xCrO₄^2? (solvated), where M is Ag or Ba, and x is 1 or 2, have been determined in formamide from solubility studies. The negative value of ΔS⁰ indicates that there is more order in the dissolved state than in the undissolved state.     

Phase formation in the system Zn(VO<Subscript>3</Subscript>)<Subscript>2</Subscript>–HCl–VOCl<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The phase and chemical compositions of precipitates formed in the system Zn(VO₃)₂–HCl–VOCl₂–H₂O at pH 1?3, molar ratio V⁴⁺: V⁵⁺ = 0.1?9, and 80°C were studied. It was shown that, within the range 0.4 ≤ V⁴⁺: V⁵⁺ ≤ 9, zinc vanadate with vanadium in a mixed oxidation state forms with the general formula Zn_xV⁴⁺ _yV⁵⁺ _2-yO₅ ? nH₂O (0.005 ≤ x ≤ 0.1, 0.05 ≤ y ≤ 0.3, n = 0.5?1.2). Vanadate Zn_xV₂O₅ ? nH₂O with the maximum tetravalent vanadium content (y = 0.30) was produced within the ratio range V⁴⁺: V⁵⁺ = 1.5?9.0. Investigation of the kinetics of the formation of Zn_xV₂O₅ ? nH₂O at pH 3 determined that tetravalent vanadium ions VO2+ activate the formation of zinc vanadate, and its precipitation is described by a second-order reaction. It was demonstrated that, under hydrothermal conditions at pH 3 and 180°C, zinc decavanadate in the presence of VOCl₂ can be used as a precursor for producing V₃O₇ ? H₂O nanorods 50–100 nm in diameter.     

Synthesis of garnet structured Li7+x La3Y x Zr2-x O12 (x = 0–0.4) by modified sol–gel method

Preparation of lithium garnet Li₇La₃Zr₂O₁₂ (LLZ) in cubic phase by solid state method requires high temperature sintering around 1,200 °C for 36 h in Al₂O₃ crucible with intermittent grinding. Synthesis of LLZ in cubic phase at lower temperatures by wet chemical methods was reported earlier, however that decompose at high temperature around 850 °C. In this work we report the systematic studies on synthesis of garnet structured electrolytes by modified sol–gel method by the simultaneous substitution of Li⁺ and Y³⁺ for Zr⁴⁺ according to the formulae Li_7+x La₃Y _x Zr_2-x O₁₂ (x = 0, 0.1, 0.2, 0.3 and 0.4). The present investigation revealed that the cubic garnet phase is obtained at much lower temperature for Li₇La₃Zr₂O₁₂ and the simultaneous increase of both Li⁺ and Y³⁺ in Li_7+x La₃Y _x Zr_2-x O₁₂ requires slightly higher sintering temperatures for the formation of cubic garnet phase. SEM micrographs of the Li_7+x La₃Y _x Zr_2-x O₁₂ (x = 0, 0.1, 0.2, 0.3 and 0.4) annealed at minimum sintering temperature required for the formation of cubic garnet phase revealed the increase in grain size and relatively dense structure with increase of x in Li_7+x La₃Y _x Zr_2-x O₁₂.     

Effect of chlorine on solid solution formation in ruthenium titanium dioxide coatings

Rutile-type dioxides of titanium and ruthenium form partial solid solutions at temperatures above 1000°C, whereas the miscibility is complete in the temperature range of 350–600°C, when the oxides are coated on titanium or alumina substrates. The present work tends to show that the Ru_xTi_t?xO₂ coatings are metastable solutions wherein the chloride ions are likely to replace the oxide ions on the sublattice O^2? sites. The increase of a and c parameters in the overall composition range are compatible with a Cl/Ru ratio of 2.5 at.% in the rutile lattice. This ratio does not depend upon the titanium content and therefore it is thought that the Cl^? ions are compensated by reduced Ru³⁺ (or Ti³⁺) species. The electrical conductivity retains its metal-like characteristics in the composition range of 30–100% RuO₂, this is accounted for by the existence of RuO π1 bands along (110) directions. The reduced ions in equilibrium with Cl^? would provide additional paths for electron transport along the c-axis, explaining the high values of conductivity in the concentration range of 30–50% RuO₂.     

Distorsion cristalline et distribution des cations dans les spinelles de la serie CoMnxFe2−xO4

By using neutron diffraction together with anomalous dispersion X-ray diffraction, it has been possible to ascertain the distribution of close atomic numbered cations in CoMn_xFe_2?xO₄ system spinels.At 950°C, these compounds have a cubic structure in the range 0 ? x ? 1.25 and exhibit a macroscopic tetragonal distortion as soon as 60% of the Mn³⁺ ions occupy octahedral sites.The great mobility of cobalt between both types of sites has been pointed out; it can be related to oxidation and reduction phenomena. In these compounds, Fe³⁺ iron remains neutral towards four or six coordinences.     

Sur de nouveaux ferrites oxyfluorés d'yttrium ou de gadolinium à structure grenat

The oxyfluoride garnets of formula Y₃Fe_5?xM_xO_12?xF_x and Gd₃Fe_5?xM_xO_12?xF_x (M = 3d transition element) result from partial substitution of O^2? by F^? in Y₃Fe₅O₁₂ and Gd₃Fe₅O₁₂ oxides. The cationic charge compensation is obtained by replacing the Fe³⁺ ions by divalent ions as Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ or Zn²⁺ ions. The site occupied by some of these ions (Mn²⁺, Ni²⁺, Zn²⁺) is determined by magnetic or Mössbauer measurements.     

Homogeneity range of neodymium manganite in air

The solubility boundaries for Nd₂O₃ and manganese oxides in NdMnO_{3 ± δ} have been determined by X-ray powder diffraction analysis of homogeneous phases and heterogeneous compositions of the general formula Nd_{2 ? x} Mn _x O_{3 ± δ} (0.90 ≤ x ≤ 1.20; Δx = 0.02) prepared by ceramic technology from constituent oxides in air in the temperature range 900–1400°C. The results are presented in the form of a fragment of the Nd-Mn-O phase diagram in air. It is suggested that the Nd₂O₃ solubility in NdMnO_{3 ± δ} is due to crystal defects and the solubility of manganese oxides is in addition due to the disproportionation reaction 2Mn³⁺ = Mn²⁺ + Mn⁴⁺ and the subsequent partial substitution of divalent for tervalent manganese ions in the cuboctahedral positions of the perovskite-like crystal lattice. To verify this suggestion, it is necessary to systematically study the oxygen nonstoichiometry δ in Nd_{2 ? x} Mn _x O_{3 ± δ} as a function of x and synthesis temperature and structurally study this oxide with these parameters being varied.     

Mössbauer spectroscopic study of γ-ray irradiated potassium borate glasses

Potassium borate glasses denoted by the formula xK₂O · (100 ? x)B₂O₃ · 7Fe₂O₃ were irradiated with ⁶⁰Co-γ-rays at room temperature. Mössbauer parameters for the irradiated glasses containing alkali equal to or higher than 20 mole% showed that the s-electron density at the iron nucleus increased without any change of the steric configuration of oxygen atoms around the iron nucleus. The increase of s-electron density was ascribed to electron transfer from the nonbridging oxygen to the iron nucleus. The presence of the nonbridging oxygen was also confirmed by the irradiation effect of the borate glass (x = 30) prepared using the enriched isotope of ⁵⁷Fe₂O₃. Mössbauer parameters for the irradiated glass suggest that the newly observed Fe²⁺ ions are in tetrahedral symmetry.     

Application of EPR spectroscopy for elucidation of vanadium speciation in VO x /ZrO2 catalysts subject to redox treatment

Application of EPR spectroscopy corroborated by spectra simulation in speciation studies of the tetravalent vanadium in supported VO _x /ZrO₂ catalyst has been discussed. Implementation of genetic algorithms into automated analysis of the EPR spectra has greatly improved the simulation efficiency. The performance of the new procedure has been benchmarked against common simplex method using the multi-component model and real EPR spectra of tetravalent vanadium in VO _x /ZrO₂ catalysts. The analysis has revealed speciation of vanadium into surface isolated and clustered vanadyl entities and isolated bulk V _Zr ^x ions due to formation of Zr_1?x V _x O₂ solid solution in the near to surface region. The structural heterogeneity of vanadium can be controlled by the calcination temperature and the redox treatment.     

Magnetic properties in the system BaCo1−xMnxO3 and SrCo1−xMnxO3 (0 ≦ x ≦ 1)

The compounds in the systems of BaCo_1?xMn_xO₃ (0 ≦ x ≦ 1) and SrCo_1?xMn_xO₃ (0 ≦ x ≦ 1) were prepared at an oxygen pressure of 1400 bars. The former had a two-layer hexagonal structure and that of the latter was cubic perovskite type. From the variation of the unit-cell parameters and of the magnetic properties, it is found that the Co⁴⁺ ions change from the low-spin to the high-spin state. In the system of SrCo_1?xMn_xO₃, the change of magnetic property from ferromagnet to antiferromagnet is related to the spin state of Co⁴⁺ ions located at the octahedral sites.     

ESR spectroscopy of FeIII ions in sodium silicate glasses

The state of Fe^III ions doped in sodium silicate glasses of the composition (100 ? x)Na₂O-xSiO_2?y Fe₂O₃ (x = 75, 81 mol.%; y = 0.05?13 wt.%) was studied by electron spin resonance (ESR). X-band ESR spectra exhibited three resonance signals at g ≈ 2.0, 4.3, and 6. The computer simulation of ESR spectra was performed on the basis of spin-Hamiltonian of rhombic symmetry. The nature of observed signals was interpreted as a combination of five types of Fe^III complexes. Three of them were clustered iron ions and two other were isolated paramagnetic ones. The ratio of observed forms was found for different glass compositions and various total amounts of Fe^III ions in a matrix containing 0.55, 2.5, 4, 7, and 13 wt.% of Fe₂O₃.     

Gas‐Phase Reactions of Cationic Vanadium‐Phosphorus Oxide Clusters with C2Hx (x=4, 6): A DFT‐Based Analysis of Reactivity Patterns

The reactivities of the adamantane‐like heteronuclear vanadium‐phosphorus oxygen cluster ions [V_xP_4?xO₁₀]^.+ (x=0, 2–4) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas‐phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT‐based calculations; homolytic C? H bond activation constitutes the initial step, and for all systems the P? O^. unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen‐atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e^? reduction of the cationic clusters.     

Determination of pH value of isoelectric solution and identification of passive iron surface phases using immersion method

Using the method of phase modeling, the pH values of solutions corresponding to the uncharged surface of passive iron and ferric oxide γ-Fe₂O₃ (pH₀) are compared. According to the theory of connected places, the charge of metal oxide surface is determined by the adsorption or desorption of hydrogen ions leading to a change in the potential drop at the oxide/solution interface. Preliminarily passivated iron electrode was washed with twice-distilled water and placed into 0.5 M NaNO₃ solution with various pH values; the variation in the potential (ΔE) with time was studied. The pH₀ value for passive electrode under the open-circuit conditions was determined by the dependence of ΔE on the pH value (pH₀ 6.2 ± 0.1). The pH₀ value was close to that for γ-Fe₂O₃ (pH₀ 6.2), which was determined by the method of potentiometrical titration of oxide suspension in the nitrate solution. The introduction of surface-active ions Ba²⁺ and Cl^? changes the charge of passive iron surface: Ba²⁺ ions increase the electrode potential, while Cl^? ions decrease it. Comparing the pH₀ values for passive electrode and metal oxides, one can identify the composition of passive electrode surface.     

Preparation of nanostructured thin films of yttrium iron garnet (Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript>) by sol–gel technology

The synthesis of hydrolytically active heteroligand coordination compounds [M(C₅H₇O₂)_3?x(C₅H₁₁Oⁱ)_x] (M = Fe³⁺ and Y³⁺) using iron and yttrium acetylacetonates has been studied. The gel formation kinetics in solutions of these compounds upon hydrolysis and polycondensation has also been studied. Thin films of a solution of these precursors have been applied to polished sapphire substrates by dip coating technology. The crystallization of nanostructured yttrium iron garnet (Y₃Fe₅O₁₂) films during heat treatment of xerogel coatings under various conditions has been studied. How the phase composition, microstructure, and particle size depend on the synthesis parameters has been recognized.     

Thermal decomposition of zinc and cadmium zirconyl oxalates

The enthalpy of formation at 298.15 K of the polymer Al₁₃O₄(OH)₂₈(H₂O)³⁺₈ and an amorphous aluminium trihydroxide gel was studied using an original differential calorimetric method, already developed for adsorption experiments, and aluminium-27 NMR spectroscopy data. ΔH_f “Al₁₃” (298.15 K) = ? 602 ± 60.2 kJ mole^?1 and ΔH_f Al(OH)₃ (298.15 K) = ? 51 ± 5 kJ mole^?1. Using theoretical values of ΔG_R “Al₁₃” and ΔG_R Al(OH)₃, we calculated ΔG_f “Al₁₃” (298.15 K) = ? 13282 kJ mole^?1; ΔS_f “Al₁₃” (298.15 K) = + 42.2 kJ mole^?1; ΔG_f Al(OH)₃ (298.15 K) = ? 782.5 kJ mole^?1; and ΔS_f Al(OH)₃ (298.15 K) = + 2.4 kJ mole^?1.     

Electronic State of Vanadium Ions in Li1+xV3O8 According to EPR Spectroscopy

EPR spectroscopy is used to study the electronic state of vanadium ions in HT- and LT-Li_1+xV₃O₈. It is shown that in both cases the EPR spectra observed are attributed to vanadyl VO²⁺ ions (localized electron centers) with weak exchange interaction. The other type of registered electrons is characterized by larger mobility through a few V⁵⁺ ions, i.e., by a higher degree of delocalization (electron gas). Based on the analysis of the temperature dependence of the EPR line width, it is stated that the exchange interaction between localized electron centers proceeds through electron gas (C-S-C relaxation). It is found that HT-Li_1+xV₃O₈ differs from LT-Li_1+xV₃O₈ by the sloping form of its spectrum at g_∥ range connected with two types of VO²⁺ ions different in the direction of the crystal field axis corresponding to a short V=O²⁺ bond.     

Crystal chemistry of the (Ta6Si4O26)6− and (Ta14Si4O47)8− frameworks

The range of chemical flexibilities of the hexagonal frameworks (Ta₆Si₄O₂₆)^6? and (Ta₁₄Si₄O₄₇)^8? have been partially explored. This has been done with high-temperature preparations as in general ionic mobilities in these frameworks are too low to permit low-temperature ion exchange. Ionic site potential calculations indicate that preferential site-occupancy factors as well as geometric constraints are responsible for the absence of ionic motion. New phases K_6?xNa_xTa₆Si₄O₂₆ (x ? 4), K_8?xNa_xTa₁₄Si₄O₄₇ (x ? 5), and impure Ba_3?xNa_2xTa₆Si₄O₂₆ have been prepared. Introduction of up to 2 moles of Li⁺ and 1 mole of Mg²⁺ ions per formula unit into sites of the framework not normally occupied has been demonstrated as well as the possibility of partially substituting Zr⁴⁺ for Ta⁵⁺ ions. Substitutions designed to introduce large tunnel vacancies in the presence of only monovalent K⁺ or Na⁺ ions (P for Si, W for Ta and F for O) generally proved unsuccessful. Competitive phases also frustrated attempts to substitute either the larger Rb⁺ or the smaller Li⁺ ions into the large-tunnel sites. A large area of solid solution was discovered in the BaONa₂OTa₂O₅ phase diagram; it has a (TaO₃)-framework with the structure of tetragonal potassium tungsten bronze.