V. P. Ivanov

Pt-Supported Nanocrystalline Ceria-Zirconia Doped with La, Pr or Gd: Factors Controlling Syngas Generation in Partial Oxidation/Autothermal Reforming of Methane or Oxygenates

Nanocrystalline CeO2-ZrO2 (Ce:Zr 1:1) samples doped with La, Pr or Gd cations (containing up to 30 at.%) were prepared via the Pechini route. Pt (1.4 wt.%) was supported via impregnation with H2PtCl6 solution followed by drying and calcination. The samples’ surface features were studied by SIMS and FTIRS of adsorbed CO. The oxygen mobility was characterized by the dynamic oxygen isotope exchange and H2 TPR. Catalytic activity was studied in the flow installation using diluted feeds (0.7% CH4 +0.5% O2 or 1% C3H6O + 0.5% O2 +0.5% H2O in He). In the selective oxidation of methane (POM), the catalytic activity correlates with Pt dispersion controlled by the oxidized sample’s ability to stabilize Pt2+ cations as precursors of small reactive Pt clusters formed under reaction conditions. This is favoured by a larger doping cation (La) and a developed network of nanodomain boundaries. At comparable Pt dispersion, the highest performance was demonstrated by a La-doped system, which correlates with the highest surface/near-surface oxygen mobility controlled by the strength of Ce-O bonds in the surface layer. In the autothermal reforming of acetone, the activity trends differ from those in POM because of the more prominent role of the oxygen mobility required to prevent surface coking.

Mechanochemical Synthesis and Catalytic Properties of the Calcium Ferrite Ca2Fe2O5

The formation of the real structure of calcium ferrite prepared by the calcination of a mechanochemically activated hydroxide mixture at 600–1100°C was studied by X-ray diffraction analysis, electron microscopy, thermal analysis, Moessbauer spectroscopy, IR spectroscopy, small-angle X-ray scattering, and secondary-ion mass spectrometry. It was found that low-temperature calcium ferrite is an anion-modified oxide, in which the ordering of oxygen vacancies was incomplete. Regions with a disordered structure were detected on the surface of crystallites. As the calcination temperature was increased, the brownmillerite crystal structure was improved and the intercrystalline boundaries were formed and then annealed. At the surface, these processes were accompanied by a change in the predominant form of adsorbed NO from nitrosyl to dinitrosyl species. An increase in the specific catalytic activity of samples with calcination temperature can be associated with the perfection of the brownmillerite structure and with a change in the state of adsorption centers.

Physicochemical and catalytic properties of La1-xCax FeO3-0.5x perovskites

The phase analysis of La1-xCaxFeO3-0.5x perovskites prepared by a ceramic process from oxides is studied by X-ray diffraction and differential dissolution methods. Atx < 0.5, the system does not form a continuous series of homogeneous solid solutions and does not consist of the members of a homological series. Atx < 0.5, the system contains two phases and calcium ferrite nanoparticles located on the surface of lanthanum ferrite. Atx > 0.5, the formation of the structures of a brownmillerite-based homological series is found. The catalytic activity of perovskites depends nonmonotonically on thex value and reaches the maximum atx = 0.6.

Real structure and catalytic activity of La1−xCaxMnO3+δ perovskites

Abstract Calcium-substituted lanthanum manganites La 1− x Ca x MnO 3+ δ (0≤ x ≤1) were synthesized from the solid oxide precursors using two routes: a traditional ceramic method and the mechanical activation of the mixture of oxides in high power planetary ball mills, followed by the product annealing at different temperatures. The samples structure was studied by XPD and TEM methods, while their surface composition was characterized by the differential dissolution method. A pronounced effect of the preparation method on samples bulk and surface properties, reflected in their reactivity characterized by the rate of CO catalytic oxidation, was observed. For samples prepared via the ceramic route by sintering at 1100°C, continuous solid solutions are formed. In the case of mechanical activation route, by annealing of activated mixture of oxides at 700–100°C, solid solutions are formed only at the Ca content within 0≤ x ≤0.4 range. At higher Ca content, microheterogeneous composites are formed, in which the nucleus of particles is formed by the perovskite phase with x ≤0.4, while the surface layer is enriched by Ca. The catalytic activity in CO oxidation appears to correlate with the density of extended defects, being decreased when Ca is segregated in the surface layer.

Effect of structural disorder on the catalytic activity of mixed La−Sr−Co−Fr−O perovskites

For a perovskite system La0.7Sr0.3Co1-xFexO3, the effect of partial substitution of Co by Fe on the particle microstructure and chemical composition of the surface layer has been studied. Iron incorporation was found to cause a structure rearrangement from the hexagonal (at x<0.05) to the cubic (atx>0.05) type, which was not accompanied by any appreciable variation of the surface layer composition. A transient sample with x=0.05 was characterized by a high degree of misorientation of microblocks and had the highest activity in the CO catalytic oxidation.

Ceria-Zirconia Nanoparticles Doped with La or Gd: Effect of the Doping Cation on the Real Structure

The real structure of nanocrystalline CeO2-ZrO2 (Ce:Zr=1:1) systems prepared via the polymerized polyester precursor (Pechini) route and doped with La3+ or Gd3+ cations, up to 30 at.%, was studied by X-ray powder diffraction, EXAFS and Raman spectroscopy and the surface features characterized by XPS and SIMS. Undoped CeO2-ZrO2 system revealed nanoscale heterogeneity, perhaps due to the co-existence of Zr- or Ce-enriched domains. With large La3+ dopant the system remains bi-phasic within the studied ranges of composition, incorporation of the smaller Gd3+ cation stabilizes the single-phase solid solution. For both systems, the increase of dopant content was accompanied by a decline of domain size and an increase of the average lattice parameter of fluorite-like phases. Depletion of the surface layer by smaller Zr4+ cations was observed, while the surface content of a doping cation is either, close to that in the bulk (La) or below it (Gd). Such a spatial distribution of components results in some ordering of cations within the lattice. It is reflected in different modes of rearrangement of oxygen coordination polyhedra with the Gd or La content (distances and coordination numbers by EXAFS), and specificity of XRD patterns not conforming to a simple model with statistical distribution of oxygen vacancies.

CATION/ANION MODIFIED CERIA-ZIRCONIA SOLID SOLUTIONS PROMOTED BY Pt AS CATALYSTS OF METHANE OXIDATION INTO SYNGAS BY WATER IN REVERSIBLE REDOX CYCLES

Ca and/or F-modified fluorite-like Ce-Zr-mixed oxides have been prepared by Pechinis method. The bulk structure of samples was characterized by XRD, EXAFS and FTIRS of the lattice modes. The surface properties were studied by SIMS and FTIRS of adsorbed CO and surface hydroxyls. The specific reactivity of the surface oxygen, its amount, coefficients of bulk and near-surface diffusion, as dependent upon the sample composition and temperature, were estimated using sample reduction by CO in the pulse/flow mode. Insertion of fluorine into the lattice results in decreasing the degree of oxygen polyhedra distortion, thus decreasing the amount of reactive oxygen and diffusion coefficients. Calcium and Pt addition counteracts this effect. At 500oC for Pt-supported Ce-Zr-O samples including those modified by Ca and F, the lattice oxygen is easily removed by methane generating CO and hydrogen with high selectivity. Reoxidation of reduced samples by water or carbon dioxide at the same temperature restores the oxygen capacity producing more hydrogen or carbon monoxide.

Physicochemical and catalytic properties of La1-xCaxFeO3-0.5x perovskites prepared using mechanochemical activation

The phase composition of La1 – xCaxFeO3 – 0.5x perovskites synthesized from preactivated oxides was studied by powder X-ray diffraction analysis and differential dissolution. The system does not form a continuous series of homogeneous solid solutions. No intermediate samples from this series are monophasic. It was found that the synthesis under nonequilibrium conditions (mechanical activation + calcination at 900°С for 4 h) resulted in nonequilibrium microheterogeneous solid solutions with degrees of calcium substitution for lanthanum of no higher than 0.5. A longer calcination (for 16 h) or an increase in the calcination temperature of solutions up to 1100 °С decreased the calcium content of the samples down to x ∼ 0.2 because of the formation of a brownmillerite phase. The catalytic activity of the test samples in the oxidation of CO changed nonmonotonically with x, and it was maximum at x = 0.5–0.6, which correlates with the maximum density of interphase boundaries in these samples.

Porous Al2O3/Al metal ceramics prepared by the oxidation of aluminum powder under hydrothermal conditions followed by thermal dehydration: III. The reactivity of aluminum, the reaction mechanism of its oxidation with water vapor, and the microtexture of cermets

The macrokinetics of aluminum oxidation under hydrothermal conditions at 150–250°C and water vapor pressures of ∼0.5–4.5 MPa was studied. The apparent kinetic characteristics of the process were determined. The diffusion of water through the layer of a hydrated product was found to be a rate-limiting step. It was found that diffusion coefficients for various aluminum samples differed by almost two orders of magnitude; the main reaction steps were revealed. Changes in the texture of aluminum oxide in cermets in the course of the hydrothermal oxidation reaction were analyzed. This texture was found to depend on the ratio between the specific rate of the oxidation reaction and the rate of aging of the oxidation products under hydrothermal conditions.

Conductivity of the nanostructured ceramic material Zr0.88Sc0.1Ce0.01Y0.01O1.955 prepared from mechanically activated powders

The structure of the Zr0.88 Sc0.1Ce0.01Y0.01O1.955 solid solution, a candidate for the use as a solid electrolyte in fuel cells with a low temperature, has been investigated using x-ray powder diffraction and Raman spectroscopy. Single-phase ceramic materials have been produced from powders prepared by the mechanochemical synthesis from ZrO2 nanoprecursors purified of the impurities introduced during grinding of commercial zirconia. The solid solution has a rhombohedral structure at room temperature owing to the partial ordering of oxygen vacancies. The electrical conductivity of the ceramic materials sintered at temperatures below 1570 K exhibits a hysteresis due to the delay of the martensitic transition from the cubic phase to the rhombohedral phase upon cooling of the sample. The nanostructured ceramic materials are characterized by a high mechanical strength and unusually close values of the activation energies for bulk and grain-boundary electrical conduction.