Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Activities in the spinel solid solution, phase equilibria and thermodynamic properties of ternary phases in the system Cu Fe O

A review of the structural and thermodynamic information and phase equilibria in the Cu-Fe-O system suggested that a consistent, quantitative description of the system is hampered by lack of data on activities in the spinel solid solution CuFe2O4-Fe3O4. Therefore the activity of Fe3O4 in this solid solution is derived from measurements of the oxygen potentials established at 1000°C by mixtures containing Fe2O3 and spinel solid solutions of known composition. The oxygen pressures were measured manometrically for solid solutions rich in CuFe2O4, while for Fe3O4-rich compositions the oxygen potentials were obtained by an emf technique. The activities show significant negative deviations from Raoult’s law. The compositions of the spinel solid solutions in equilibrium with CuO + CuFeO2 and Cu + CuFeO2 were obtained from chemical analysis of the solid solution after magnetic separation. The oxygen potential of the three-phase mixture Cu + CuFeO2 + Fe3O4(spinel s.s.) was determined by a solid oxide galvanic cell. From these measurements a complete phase diagram and consistent thermodynamic data on the ternary condensed phases, CuFeO2 and CuFeO2O4, were obtained. An analysis of the free energy of mixing of the spinel solid solution furnished information on the distribution of cations and their valencies between the tetrahedral and octahedral sites of the spinel lattice, which is consistent with X-ray diffraction, magnetic and Seebeck coefficient measurements.

Vacancy wind effect on interdiffusion in a dilute Cu(Sn) solid solution

A study has been conducted on a Cu(Sn) solid solution to examine the role of the vacancy wind effect on interdiffusion. First, the interdiffusion and the intrinsic diffusion coefficients are calculated. The trend of the interdiffusion coefficients is explained with the help of the driving force. Following this, the tracer diffusion coefficients of the species are calculated with and without consideration of the vacancy wind effect. We found that the role of the vacancy wind is negligible on the minor element in a dilute solid solution, which is the faster diffusing species in this system and controls the interdiffusion process. However, consideration of this effect is important to understand the diffusion rate of the major element, which is the slower diffusing species in this system.

Structural and Dielectric-Properties Of A Novel BI2O3-(1-X)WO3-XCUO Solid-Solution

A novel solid solution in the system Bi-W-Cu-O has been synthesized and its structural and dielectric properties studied. The solid solution Bi2O3-(1-x)WO3-xCuO exists up to x = 0.7; the solid solutions up to x = 0.65 are orthorhombic but stabilize in tetragonal structure in a narrow range around x = 0.7. The solid solutions are non-centrosymmetric and exhibit ferroelectric behaviour similar to their parent phase Bi2WO6. The Curie point of the solid solution is found to decrease with increase in x.

Thermodynamics of Al(1-x)Ga(x)N solid solution: Inclination for phase separation and ordering

Although Al(1-x)Ga(x)N semiconductors are used in lighting, displays and high-power amplifiers, there is no experimental thermodynamic information on nitride solid solutions. Thermodynamic data are useful for assessing the intrinsic stability of the solid solution with respect to phase separation and extrinsic stability in relation to other phases such as metallic contacts. The activity of GaN in Al(1-x)Ga(x)N solid solution is determined at 1100 K using a solid-state electrochemical cell: Ga + Al(1-x)Ga(x)N/Fe, Ca(3)N(2)//CaF(2)//Ca(3)N(2), N(2) (0.1 MPa), Fe. The solid-state cell is based on single crystal CaF(2) as the electrolyte and Ca(3)N(2) as the auxiliary electrode to convert the nitrogen chemical potential established by the equilibrium between Ga and Al(1-x)Ga(x)N solid solution into an equivalent fluorine potential. Excess Gibbs free energy of mixing of the solid solution is computed from the results. Results suggest an unusual mixing behavior: a mild tendency for ordering at three discrete compositions (x = 0.25, 0.5 and 0.75) superimposed on predominantly positive deviation from ideality. The lattice parameters exhibit slight deviation from Vegard's law, with the a-parameter showing positive and the c-parameter negative deviation. Although the solid solution is stable in the full range of compositions at growth temperatures, thermodynamic instability is indicated at temperatures below 410 K in the composition range 0.26 <= x <= 0.5. At 355 K, two biphasic regions appear, with terminal solid solutions stable only for 0 <= x <= 0.26 and 0.66 <= x <= 1. The range of terminal solid solubility reduces with decreasing temperature. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Microscopic description of the evolution of the local structure and an evaluation of the chemical pressure concept in a solid solution

Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn1-xCdxS samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S-4 and Cd-S-4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.

Activities in the $FeTiO_{3}-NiTiO_{3}$ Solid Solution from Alloy-Oxide Equilibria at 1273 K

Nine tie-lines between Fe-Ni alloys and FeTiO3-NiTiO3 solid solutions were determined at 1273 K. Samples were equilibrated in evacuated quartz ampoules for periods up to 10 days. Compositions of the alloy and oxide phases at equilibrium were determined by energy-dispersive x-ray spectroscopy. X-ray powder diffraction was used to confirm the results. Attainment of equilibrium was verified by the conventional tie-line rotation technique and by thermodynamic analysis of the results. The tie-lines are skewed toward the FeTiO3 corner. From the tie-line data and activities in the Fe-Ni alloy phase available in the literature, activities of FeTiO3 and NiTiO3 in the ilmenite solid solution were derived using the modified Gibbs-Duhem technique of Jacob and Jeffes [K.T. Jacob and J.H.E. Jeffes, An Improved Method for Calculating Activities from Distribution Equilibria, High Temp. High Press., 1972, 4, p 177-182]. The components of the oxide solid solution exhibit moderate positive deviations from Raoult's law. Within experimental error, excess Gibbs energy of mixing for the FeTiO3-NiTiO3 solid solution at 1273 K is a symmetric function of composition and can be represented as: Delta G(E) = 8590 (+/- 200) X-FeTiO3 X-NiTiO3 J/mol Full spectrum of tie-lines and oxygen potentials for the three-phase equilibrium involving Fe-Ni alloys, FeTiO3-NiTiO3 solid solutions, and TiO2 at 1273 K were computed using results obtained in this study and data available in the literature.

X-ray and IR characterisation of Nasicon solid solution, Na1+xZr2SixP3−xO12

X-ray and IR studies on Nasicon solid solutions, Na1+xZr2SixP3−xO12, are carried out as a function of composition x. X-ray diffraction studies show that the unit cell volume increases as x increases and exhibits a maximum at x ≈ 2. On further increase in x the unit cell volume decreases. The infrared absorption peak positions and the splitting of these absorption peaks suggest a distortion of the PO4 and SiO4 tetrahedra. But the distortion is not large enough to change the local symmetry around the phosphorus or silicon ion from Td to C3v.

Electrical transport in the perovskite solid solution LaNi1-xCoxO3

We have studied the resistivity and thermopower of the solid solution LaNi1-xCoxO3 in the temperature range 1.4K-300K. Effect of interaction and localization are seen in the low temperature transport data for x<0.55. A negative anomaly in the thermopower has been observed at low temperature for 0.1

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Thermodynamic activities in the Pb(Zr1-XTiX)O-3 solid solution at 1373 K

Although Pb(Zr1-XTiX)O-3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1-XTiX)O-3 solid solution with cubic perovskite structure and (Zr1-YTiY)O-2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs-Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1-YTiY)02 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model: Delta G(E.M) (J mol(-1)) = X-PbTiO3 X-PbZrO3(5280X(PbTiO3) - 1980X(PbZrO3)) where Delta G(E.M) is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution. (C) 2007 Elsevier B.V. All rights reserved.

properties of Na2O in Nasicon solid solution, Na1+xZr2SixP3-xO12

The thermodynamic activity of sodium oxide (Na2O) in the Nasicon solid solution series, Na1+xZr2SixO12, has been measured in the temperature range 700–1100 K using solid state galvanic cells: Pt|CO2 + O2|Na2CO3?Na1+xZr2SixP3-xO12?(Y2O3)ZrO2?In + In2O3|Ta, Pt for 1 = ? = 2.5, and Pt?CO2 + O2?Na2CO3?ß-alumina?Na1+xZr2SixP3-xO12?Ar + O2?Pt for x = 0, 0.5, 2.5, and 3. The former cell, where the Nasicon solid solution is used as an electrolyte along with yttria-stabilized zirconia, is well suited for Nasicon compositions with high ionic conductivity. In the latter cell, ß-alumina is used as an electrolyte and the Nasicon solid solution forms an electrode. The chemical potential of Na2O is found to increase monotonically with x at constant temperature. The partial entropy of Na2O decreases continuously with x. However, the partial enthalpy exhibits a maximum at x = 2. This suggests that the binding energy is minimum at the composition where ionic conductivity and cell volume have maximum values.

Crystal chemistry of a new solid solution in the BaO-Bi2O3-Nb2O5 system: Ba-5x/2-Bi(1-x)5/3Nb5O15

A solid solution of the type Ba5x/2Bi(1-x)5/3Nb5O15 has been identified in the BaO-Bi2O3-Nb2O5 system for the first time. The limits of the solid solution are within the range 0.52 <= x <= 0.80. The compositions x = 0.52, 0.60, 0.72, 0.77, 0.78, and 0.80 were synthesized by the solid-state technique from the starting materials in stoichiometric quantities. The powder X-ray patterns of all the phases in the domain indicate a structural similarity to tetragonal tungsten bronzes (TTBs). The compositions below x = 0.52 and those above x = 0.80 exhibit barium niobate and bismuth niobate impurities, respectively. Single crystals of the composition x = 0.77 were obtained by the melt cooling technique. The crystal structure of Ba3.85/2Bi1.15/3Nb5O15 (x = 0.77) was solved in the tetragonal space group P4bm (No. 100) with a = 12.4938 (14) angstrom, c = 3.9519 (2) A, V = 616.87 (10) angstrom(3), and Z = 2 and was refined to an R index of 0.034. Dielectric measurements on all the phases indicate a typical relaxor behavior with a broad phase transition at T-m approximate to 300 K.

Thermodynamic partial properties of Na2O in Nasicon solid solution, Na1+xZr2SixP3-xO12

The thermodynamic activity of sodium oxide (Na2O) in the Nasicon solid solution series, Na1+xZr2SixO12, has been measured in the temperature range 700�1100 K using solid state galvanic cells: Pt|CO2 + O2|Na2CO3?Na1+xZr2SixP3-xO12?(Y2O3)ZrO2?In + In2O3|Ta, Pt for 1 = ? = 2.5, and Pt?CO2 + O2?Na2CO3?ß-alumina?Na1+xZr2SixP3-xO12?Ar + O2?Pt for x = 0, 0.5, 2.5, and 3. The former cell, where the Nasicon solid solution is used as an electrolyte along with yttria-stabilized zirconia, is well suited for Nasicon compositions with high ionic conductivity. In the latter cell, ß-alumina is used as an electrolyte and the Nasicon solid solution forms an electrode. The chemical potential of Na2O is found to increase monotonically with x at constant temperature. The partial entropy of Na2O decreases continuously with x. However, the partial enthalpy exhibits a maximum at x = 2. This suggests that the binding energy is minimum at the composition where ionic conductivity and cell volume have maximum values.

Interdiffusion study on Co(W) solid solution and topological close-packed mu phase in Co-W system

An interdiffusion study is conducted on the Co-W system by a diffusion couple technique. The interdiffusion coefficient of the Co(W) solid solution and the Co7W6 mu phase is determined. The activation energy is found to increase with the W content of the Co(W) solid solution. (C) 2010 Elsevier Ltd. All rights reserved.