EPR study of solid solutions La1 ? 0.33yBa0.33yMnyAl1 ? yO3 (y = 0.02, 0.04, 0.10)

Solid solutions La_{1 − 0.33y} Ba_0.33y Mn _y Al_{1 − y} O₃ (y = 0.02, 0.04, 0.10) prepared using the ceramic technique have been investigated by the EPR method at temperatures of 77 and 300 K. By comparing with the calculated spectra, the experimental spectra have been assigned to Mn²⁺ ions (g = 2.04 and line width ΔH _pp = 64 × 10⁻⁴ T at T = 77K) and Mn⁴⁺ ions (g = 1.97 and ΔH _pp = 76 × 10⁻⁴ T at T = 77 K) and the broad line (ΔH _pp = 500 × 10⁻⁴ T at T = 77 K) has been attributed to clusters. The dilution of manganese ions as a result of the dissolution of La_0.67Ba_0.33MnO₃ in LaAlO₃ has allowed one to trace the cluster formation and the spin dynamics of Mn ions. It has been established that, at room temperature, compared to the system in which the Sr²⁺ ion with a smaller ionic radius is the replacing element, the localized states are more stable at all three manganese concentrations (the EPR lines are more intense). The La_0.67Ba_0.33MnO₃ clusters dissolved in LaAlO₃ retain some properties of a concentrated compound even upon dilution to y = 0.02.     

Insights into the Reactivity of La1?xSrxMnO3 (x?=?0?÷?0.7) in High Temperature N2O Decomposition

Abstract  

In this paper a wide range of La_1−x Sr _x MnO₃ (x = 0–0.7) perovskites was synthesized by Pechini route, characterized by XRD (including high temperature measurements), XPS, differential dissolution phase analysis, TPR H₂, oxygen exchange and tested in N₂O decomposition at 900 °C. At low degree of Sr substitution for La (x ≤ 0.3), high catalytic activity was found for perovskites with hexagonal structure (x = 0.1–0.2) and can be related to fast oxygen mobility caused by the lattice disordering during polymorphic phase transition from the hexagonal to cubic structure. For multiphase samples (x > 0.3) increase of activity and oxygen mobility can be attributed to the formation of the layer-structured perovskite–LaSrMnO₄ on the surface.     

Electrochemical behaviour of FexCo3?xO4 with (x?=?0, 1, 2 and 3) oxides thin film electrodes in alkaline medium

Spinel-type Fe _x Co_3−x O₄ thin films with x = 0, 1, 2 and 3 were prepared, on stainless steel supports, using the thermal decomposition method at 400 °C. The X-ray diffraction patterns show the presence of a spinel-type structure with a low crystallinity. The electrochemical behaviour was investigated in 1 M KOH, using open-circuit-potential measurements and cyclic voltammetry. The studies allowed to observe the redox reactions occurring at the Fe _x Co_3−x O₄ (x = 1 and 2) oxide surface, namely Fe₃O₄/Fe(OH)₂ or Fe₃O₄/Fe₂O₃, Co₃O₄/CoOOH, Co(OH)₂/CoOOH and CoO₂/CoOOH by comparing the experimental data with those obtained for the Co₃O₄ and Fe₃O₄ films as well as with those referred to in the literature. The results show that iron ions play the major role in the solid-state surface redox transitions in the negative potential range, whereas the cobalt ions are the key species in the positive potential range. However, the contribution of each component, although small, has to be considered in both potential regions.     

Glycothermal Synthesis and Catalytic Properties of Nanosized Zn1?xCoxAl2O4 (x?=?0, 0.5, 1.0) Spinels in Phenol Methylation

Abstract  

Zn_1−x Co _x Al₂O₄ (x = 0, 0.5, 1.0) spinels were synthesised under microwave-assisted solvothermal conditions using 1,4-butanediol as reaction medium. The results of XRD and HRTEM have indicated nanocrystallinity of prepared materials (average crystallite size in the range 6–16 nm), and N₂ adsorption–desorption measurements have revealed high feature of their surface area and mesoporous nature. Acid–base properties of prepared materials were determined using TPD-NH₃ method and cyclohexanol test. All studied spinels that underwent examination were active in phenol methylation but Co-substituted zinc aluminate (Zn_0.5Co_0.5Al₂O₄) was found to be the most efficient in the selective formation of ortho-methylated products. It could be ascribed to its dominant basic character and the presence of weak and strong acid centres, and the highest surface area as well.     

Structure and superconducting properties of layered perovskite-like compounds Y1 ? 2xCaxPrxBa2Cu3Oy and Y1 ? xBa2PrxCu3 ? xZnxOy

The conditions of preparation of Y_{1 − x} Pr _x Ba₂Cu_{3 − x} Zn _x O _y and Y_{1 − 2x} Ca _x Pr _x Ba₂Cu₃O _y solid solutions with an Y-123-type structure in the orthorhombic crystal system by the method of solid-phase chemical reactions have been determined. The concentration dependences of the unit cell parameters for these solid solutions have been established. The temperature dependences of the resistivity of the synthesized compounds have been investigated, the critical temperatures of the superconducting transition have been determined, and their variation as a function of the type and content of the introduced dopants has been analyzed. It has been demonstrated that, in the Y_{1 − x} Pr _x Ba₂Cu_{3 − x} Zn _x O _y samples, individual dopants have a combined effect on the suppression of the superconducting properties, whereas in the Y_{1 − 2x} Ca _x Pr _x Ba₂Cu₃O _y samples, calcium and praseodymium ions interact with each other when they are simultaneously introduced into the yttrium sublattice.     

Scanning Tunneling Microscopy Study of H6+xP2Mo18?xVxO62 (x?=?0–3) Wells–Dawson Heteropolyacid Catalysts: Correlation of NDR Peak Voltage with Reduction Potential and Oxidation Catalysis

Abstract  

Scanning tunneling microscopy (STM) and tunneling spectroscopy studies were carried out to examine the redox properties of vanadium-containing H_6+x P₂Mo_18−x V _x O₆₂ (x = 0, 1, 2, 3) Wells–Dawson heteropolyacid (HPA) catalysts. The HPAs formed two-dimensional well-ordered monolayer arrays on a graphite surface and exhibited a distinctive current–voltage behavior called negative differential resistance (NDR). The NDR peak voltages of H_6+x P₂Mo_18−x V _x O₆₂ HPAs were correlated with reduction potentials determined by temperature-programmed reduction and with catalytic activity for oxidative dehydrogenation of isobutyraldehyde to methacrolein. The NDR peak voltage of H_6+x P₂Mo_18−x V _x O₆₂ appeared at less negative voltage with increasing reduction potential and oxidation catalysis.     

Structural and dielectric behavior of yNi1 ? xCdxFe2O4 + (1 ? y)Ba0.8Sr0.2TiO3 magnetoelectric composites prepared through SHS route

The structural and dielectric properties of SHS-produced yNi_{1 − x} Cd _x Fe₂O₄ + (1 − y)Ba_0.8Sr_0.2TiO₃ (x = 0.2, 0.4, 0.6; y = 15, 30, 45%) magnetoelectric composites were characterized by XRD, SEM, and resistivity/dielectric measurements. SEM images reveal that SHS reaction can produce two pure phases simultaneously. The grown Cd-substituted nickel ferrite grains were well dispersed in a BST matrix. A decrease in resistivity with temperature shows the semiconducting nature of synthesized samples. The dielectric results demonstrated an attractive response of dielectric constant to frequency and temperature. The Curie temperature of about 480°C was observed in the Ni_0.4Cd_0.6Fe₂O₄ + Ba_0.8Sr_0.2TiO₃ composite.     

A study of the formation of Ln2 + xMe2 ? xO7 ? x/2 (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals

It has been established that the process of producing the Ln_{2 + x} Me_{2 − x} O_{7 − x/2} (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals by calcination of hydroxides, which, in turn, have been produced by coprecipitation of metal salts, includes several stages. At the beginning, the X-ray amorphous structure of the precursors remains unchanged during dehydration; during subsequent heating to 600–700°C, nanocrystals with a disordered fluorite structure begin to be formed. An increase in the temperature above 700°C leads to an increase in the size of crystallites (coherent scattering regions). This process is accompanied by changes occurring in their local structure. In the nanocrystalline powders of Cd₂Hf₂O₇ and Gd₂Zr₂O₇ synthesized at 1200°C (6 h), the pyrochlore-type superstructure with the lattice parameters doubled relative to fluorite has been revealed. It has also been found that, possibly, the Dy₂HfO₅ sample at 1600°C (3 h) has a modulated structure.     

Solid solutions Na1 - xKxB3O5 (0.5 < x ≤ 1.0)

The phase relations in the NaB₃O₅-KB₃O₅ pseudobinary system are investigated using high-temperature X-ray powder diffraction, differential scanning calorimetry, and the annealing and quenching techniques. Solid solutions Na_{1 - x}K_xB₃O₅ (0.5 < x 1.0) based on the KB₃O₅ phase are found in the system at temperatures below 650–670°C. The replacement of potassium atoms by sodium atoms is accompanied by the contraction of the structure along the a and c axes. The parameter b (the direction of channels in the structure) is insensitive to the substitution of sodium atoms for potassium atoms. No isomorphic miscibility on the basis of NaB₃O₅ is revealed in the system. In the region from 0 to 50 mol % KB₃O₅, there exist two phases, namely, Na_{1 - x}K_xB₃O₅ (x 0.5) and -NaB₃O₅.Original Russian Text Copyright © 2004 by Fizika i Khimiya Stekla, Bubnova, Georgievskaya, Filatov, Ugolkov.     

New anode materials of Li1+xV1?xO2 (0?≤?x?≤?0.1) for secondary lithium batteries: correlation between structures and properties

Li_1+x V_1−x O₂ (0 ≤ x ≤ 0.1) compounds were studied as the anode materials for a lithium-ion battery. The crystal and electronic structures of the prepared materials were correlated with electrical conductivities and electrochemical properties. The electrochemical behaviors were significantly dependent on the composition of Li_1+x V_1−x O₂, and these were resulted from the perturbation of the local electronic structure arising from the increase in lithium contents in Li_1+x V_1−x O₂ rather than from the slight distortion in the crystal structure. The electrical conductivities of Li_1+x V_1−x O₂ increased with the increase in lithium contents in the compounds. Li_1.1V_0.9O₂ and Li_1.075V_0.925O₂ samples exhibit the first discharge capacities of 250 and 241 mAh g⁻¹ at 0.2 C-rate, respectively.     

On the local structure of Cd3+ centers in (BaGeO3)1 ? x ? y (Al2O3) x (0.45CaF2 · 0.55MgF2) y glasses

A correlation between the ¹⁵⁵Gd M?ssbauer spectra of the GdAlO₃ and Gd₃Al₅O₁₂ compounds and Gd³⁺-doped glasses in the (BaGeO₃)_{1 − x − y} (Al₂O₃) _x (0.45CaF₂ · 0.55MgF₂) _y system is revealed. The conclusion is drawn that, in the structure of the glasses under investigation, trivalent gadolinium atoms form structural units characteristic of mixed gadolinium and aluminum oxides. Original Russian Text ? S.A. Nemov, A.V. Marchenko, P.P. Seregin, 2008, published in Fizika i Khimiya Stekla.     

Ionic conductivity of (As2Se3)1 ? x(AgHal)x (Hal = I, Br) nanocomposites

Nanocomposites based on chalcogenide glasses have been synthesized. A differential thermal analysis of (As₂Se₃)_{1 − x} (AgI) _x and (As₂Se₃)_{1 − x} (AgBr)x (0 ≤ x ≤ 0.5) samples has been performed. The size of nanofragments that undergo elementary structural transformations has been evaluated. The data obtained are in agreement with the evaluated sizes of X-ray coherent scattering regions. The electrical properties of the glasses under consideration have been studied using impedance spectroscopy in the temperature range 293–393 K. It has been demonstrated that the ionic component of the electrical conductivity dominates in glasses with a high content of silver halide.     

Characterization of MgMnxFe2?xO4 as a possible cathode material for electrochemical reduction of NOx

Spinel-type oxides of MgMn _x Fe_2−x O₄, x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, were synthesized as a solid state reaction and characterized with dilatometry and resistivity measurements up to 1000 °C. Results showed a general decrease of the linear expansion and an increase in conductivity as a function of the Mn content. Point electrodes were analyzed from 300 to 600 °C in a pseudo-three-electrode setup in 1% NO, 1% NO₂, and 10% O₂ using cyclic voltammetry. The activities in O₂ were in general very low whereas the activities in NO were slightly higher. The activities in NO₂ were for all materials much higher than the activities in O₂. Even though Mn tends to decrease the activity of the materials, current ratios of I_NOx/I_O2I_{{\rm NO}_{x}}/I_{{\rm O}_2} have relatively high values in both NO and NO₂.     

Electrochemical properties of Li1?z(Ni1?yFey)1+zO2 synthesized by the combustion method in an air atmosphere

For the syntheses of LiNi_1−y Fe _y O₂ (0.000 ≤ y ≤ 0.300), mixtures of the starting materials with the desired compositions were preheated in an air atmosphere at 400 °C for 30 min and calcined in air at 700 °C for 48 h. The phases appearing in the intermediate reaction steps for the formation of lithium nickel oxide are deduced from the DTA analysis. XRD analysis, FE-SEM observation, FTIR analysis and electrochemical measurement were performed for the synthesized Li_1−z (Ni_1−y Fe _y )_1+z O₂ (0.000 ≤ y ≤ 0.300) samples. The samples of Li_1−z (Ni_1−y Fe _y )_1+z O₂ with y = 0.025 and 0.050 have higher first discharge capacities than Li_1−z (Ni_1−y Fe _y )_1+z O₂ with y = 0.000 and better or similar cycling performance at the 0.1 C rate in the voltage range of 2.7–4.2 V. Similar results have not previously been reported except for Co-substituted LiNiO₂. The sample Li_1−z (Ni_0.975Fe_0.025)_1+z O₂ has the highest first discharge capacity (176.5 mAh g⁻¹). Rietveld refinement of the XRD patterns of LiNi_1−y Fe _y O₂ (0.000 < y ≤ 0.100) from a starting structure model [Li,Ni]_3b[Li,Ni,Fe]_3a[O₂]_6c showed that cation disordering occurred in the samples.     

CO Oxidation Kinetics over a Nanostructured Cu0.1Ce0.9O2?y Catalyst: A CO/O2 Concentration Cycling Study

Feed composition cycling as a transient kinetic technique provides detailed information about elementary steps in CO oxidation over a nanostructured Cu_0.1Ce_0.9O_2–y catalyst. This catalyst has a great potential as a future PROX reactor catalyst since it has great oxygen storage capacity as well as high reoxidation rate under oxygen rich conditions.     

XPS studies on the oxygen species of LaMn1−xCuxO3+λ

The electronic states of LaMn_1−xCu_xO_3+λ (x=0–0.4) have been studied with X-ray photoelectron spectroscopy (XPS). The valence states of substituted copper ions were Cu²⁺ and the manganese ions were a highly mixed state of Mn³⁺ and Mn⁴⁺. The nonstoichiometry and electronic state of lattice oxygen have been studied. The samples at x=0 and 0.1 had an excess of lattice oxygen but those at x=0.2–0.4 had lattice oxygen deficiency. A modified Auger parameter (Δ′) was used to evaluate the electronic states of oxygen ions. The Δ′ of lattice oxygen increased with increasing substitute quantity. This increase of Δ′ reflected the decrease of ionic bond character of lattice oxygen. The adsorbed oxygen species on LaMn_1−xCu_xO_3+λ was assigned mainly as O⁻ from the peak positions of spectra for the O 1s and O KLL levels, and the Δ′ of this O⁻ decreased with x. This decrease, i.e., the increase of ionic bond character of adsorbed oxygen was correlated well with the value of nonstoichiometry of lattice oxygen.

The rate of CO oxidation at 448 K was increased by the substitution till x=0.4. We consider that this enhancement of reactivity comes from the change of electronic state of adsorbed oxygen, O⁻ itself, i.e., a weak interaction between O⁻ and low coordinated metal site brings about a high reactivity.     

Synthesis of LiFe0.4Mn0.6?xNixPO4/C by co-precipitation method and its electrochemical performances

LiFe_0.4Mn_0.6−x Ni _x PO₄/C(x = 0, 0.05, 0.1, and 0.2) composite cathode materials for lithium ion batteries have been prepared by the co-precipitation method using oxalic acid as a precipitator. The structure and morphology of precursors and products have been investigated. Electrochemical tests demonstrate that LiFe_0.4Mn_0.55Ni_0.05PO₄ can deliver a specific capacity of 142 mAh g⁻¹ at 0.1 C, and retains 133 mAh g⁻¹ after 60 cycles. The rate performance of LiFe_0.4Mn_0.6PO₄ is obviously improved by doping Ni. The capacity of LiFe_0.4Mn_0.55Ni_0.05PO₄ at 2 C is 110 mAh g⁻¹.     

Phase separation and crystallization in glasses of the lithium silicate system xLi2O · (100 ? x)SiO2 (x = 23.4, 26.0, 33.5)

The phase separation in ultimately homogenized glasses of the lithium silicate system xLi₂O · (100 − x)SiO₂ (where x = 23.4, 26.0, and 33.5 mol % Li₂O) has been investigated. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which provide the maximum dehydration and the removal of bubbles from the glass melt. The parameters of nucleation and growth of phase_separated inhomogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates I _st of lithium disilicate crystals in the 23.4Li₂O · 76.6SiO₂ and 26Li₂O · 74SiO₂ glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates I _st for the glass of the stoichiometric lithium disilicate composition. It has been established that the crystal growth rate have a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low-temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li₂O-SiO₂ system is compared with that in the glass of the stoichiometric lithium disilicate composition. The inference has been made that the phase separation weakly affects the nucleation parameters of lithium disilicate and has a strong effect on the crystal growth.     

Effect of Sm content on the properties and electrochemical performance of SmxSr1 − xCoO3 − δ (0.2 ≤ x ≤ 0.8) as an oxygen reduction electrodes on doped ceria electrolytes

Sm_xSr_{1 − x}CoO_{3 − δ} (SSCx) materials are promising cathodes for IT-SOFCs. The influence of Sm content in SSCx (0.2 ≤ x ≤ 0.8) oxides on their oxygen nonstoichiometry, oxygen desorption, thermal expansion behavior, electrical conductivity and electrochemical activity for oxygen reduction is systematically studied by iodometric titration, oxygen-temperature programmed desorption (O₂-TPD), dilatometer, four-probe DC conductivity, electrochemical impedance spectroscopy (EIS) and three-electrode polarization test, respectively. Iodometric titration experiments demonstrate that the electrical charge neutrality compensation in SSCx proceeds preferably through the oxidation of cobalt ion for high Sm³⁺ contents (x ≥ 0.6). However, it proceeds mainly through the creation of oxygen vacancies at x ≤ 0.5. O₂-TPD shows SSC5 possesses the highest oxygen desorption ability among the range of SSCx materials tested. The thermal expansion coefficients (TECs) are high between the transition temperature and 900 °C, showing values typically larger than 20 × 10⁻⁶ K⁻¹. All dense materials show high electrical conductivity with a maximum value of ∼1885 S cm⁻¹ for SSC6 in air, while SSC5 has the highest electrical conductivity in nitrogen. EIS analysis of porous electrodes demonstrates that SSC5 has the lowest area specific resistance (ASR) value (0.42 Ω cm²) at 600 °C. Cathodic overpotential testing demonstrates that SSC5 also has the largest exchange current density of 60 mA cm⁻² at 600 °C in air.     

Transformation of the crystal structure in the series of K1 ? xCsxBSi2O6 borosilicate solid solutions

The transformation of the crystal structure by isomorphous K⁺-Cs⁺ substitutions in the non-tetrahedral positions leading to the phase transition has been studied in the series of K_{1 − x} Cs _x BSi₂O₆ solid solutions. The samples have been crystallized from the glass at 850°C for 10 h. According to the data on the crystal structures refined by the Rietveld method, the compositions with 0 ≤ x ≤ 0.35 crystallize in space group I[`4]3dI\bar 43d, structural type KBSi<sub>2</sub>O<sub>6</sub>, and those with 0.37 ≤ x ≤ 1.0, crystallize in Ia[`3]dIa\bar 3d, structural type CsBSi₂O₆. The reversible cubic-cubic phase transition I[`4]3d \rightleftarrows Ia[`3]dI\bar 43d \rightleftarrows Ia\bar 3d occurs in the composition range x = 0.35–0.37.