V. V. Kriventsov

Cocatalytic effect of palladium and zinc in the condensation of alcohol carbon backbones into hydrocarbons

The results of the direct conversion of ethanol and its mixture with glycerol into a C4–C10+ alkane and olefin fraction in the presence of Pd-, Zn-, and Pd-Zn-containing catalysts, which were prepared by supporting homo- and heterometallic acetate complexes onto the surface of γ-Al2O3, are reported. It was found that, in the presence of mono- and bicomponent Pd-ZnO (Pd; ZnO)/γ-Al2O3 systems, selectivity in the formation of alkanes, olefins, or their mixtures in the target fraction can be controlled as a result of the cocatalytic effect of active components that are responsible for the catalyst activity in condensation and hydrogenation reactions. The structures of the active components were studied and the genesis of the catalytic systems was characterized using XAFS, XPS, and XRD analysis. It was found that the addition of glycerol considerably increased the yield of the target hydrocarbon fraction.

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.

Modified Ceria-Zirconia Fluorite-Like Catalysts for the Combustion of Methane

Abstract For dispersed ceria-zirconia-based solid solutions prepared via the polymerized complex method and annealed at 700 °, effects of bulk doping by Ca, Mn, Co, Bi or Nb cations and surface modification by Mn and Pt on their structural features, surface/bulk oxygen reactivity and catalytic activity in methane combustion are considered. With up to 20 mol% doping, a structural type of homogeneous solid solutions of anion-deficient fluorite with disordered anion vacancies is formed. Doping by transition metal cations or Pt increases the mobility and reactivity of the surface/bulk oxygen. A broad variation in specific rates of methane combustion for the studied systems was observed, suggesting structural sensitivity of this reaction. In general, there is no universal relationship between the oxygen mobility, the reactivity and the catalytic activity in methane combustion, which is explained by the factor of specific methane activation on surface active sites. For the Pt-promoted samples, Pt efficiency in methane activation depends on the Pt-support interaction, and the most favorable ones being mixed Pt/MnOx and Pt/NbOx clusters on the surface of the supports that exhibit high lattice oxygen mobilities.

Structure of nanosize bimetals Fe-Co and Fe-Ni

The phase composition and structural features of nano-size powders of Fe-Co and Fe-Ni systems synthesized by reducing the metal salts from strongly alkaline aqueous solutions are investigated by XAFS (XANES/EXAFS) and X-ray diffraction methods by using the synchrotron radiation (EXAFS spectrometer and diffractometer of Siberian SR Center) in combination with ordinary X-ray diffraction methods by using DRON-3.0 and Bruker D8 Advance diffractometers.

Doped Nanocrystalline Pt-Promoted Ceria-Zirconia as Anode Catalysts for IT SOFC: Synthesis and Properties

Ceria-zirconia samples doped with Gd, Pr, Sm, or La cations were prepared via Pechini route and promoted by Pt. Effect of their real structure and surface properties (characterized by neutronography, EXAFS, XPS, FTIRS of adsorbed CO) on the mobility and reactivity of the lattice oxygen (by oxygen isotope exchange and CH 4 TPR) was analyzed. For the reaction of CH 4 steam reforming (SR), catalytic performance is determined both by Pt dispersion and lattice oxygen mobility. Ni-YSZ anodes promoted by these catalysts possess a stable and efficient performance in CH 4 SR in the 600-800°C range in stoichiometric feeds without coking.

Spectroscopy of Homogeneous Deuterated Hydrocarbon Films Redeposited from a T-10 Tokamak Plasma Discharge

Homogeneous deuterated hydrocarbon films redeposited from a deuterium plasma discharge inside the T-10 tokamak vacuum chamber are studied using photoluminescence methods; EXAFS, EPR, and IR spectroscopies; and temperature measurements. The photoluminescence excitation spectra of sp3-sp2 nanostructures of tokamak films are compared with those of sp2 nanostructures of C60 fullerite films. The effect of defect states on photoluminescence and its temperature quenching is discussed. It is concluded that the model of temperature luminescence quenching for homogeneous deuterated tokamak films is similar to that for amorphous a-C:H films.

Phase separation in La1−xSrxCoO3 solid solutions with a perovskite structure

The properties of La1−xSrxCoO3 (x = 0, 0.15, 0.20, 0.30) solid solutions are investigated using neutron diffraction, positive-muon spin relaxation (precession) measurements, and extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy. The results obtained are interpreted within the model of phase separation into ferromagnetic regions enriched with Sr2+ ions and nonmagnetic regions similar in composition to the LaCoO3 compound.

Structure of HfO2 films and binary oxides on its base

The chemical composition and structure of HfO2 films and binary oxides formed by their doping with aluminum and scandium are analyzed. It is shown that aluminum doping of HfO2 causes film amorphization: at the Al concentration above 30 at.% the film becomes amorphous. Scandium doping of HfO2 modifies the monoclinic structure, and in the Sc concentration range from ∼9 at.% to ∼14 at.% Sc under non-equilibrium conditions of the CVD process at 600°C a solid solution film of the orthorhombic structure forms.

The effect of supports (Al2O3, Al2O3-CeO2 and Al2O3-CeZrO2) on the nature of gold-species in supported gold catalysts

This work is concerned with the study of Au specimens produced by gold deposition on nanosized mixed oxides (alumina, ceria, zirconia) prepared by the sol-gel method using organometallic precursors. According to X-ray absorption near edge structure, extended X-ray absorption fine structure, transmission electron microscopy data, and ultraviolet-visible and X-ray photoelectron spectroscopy measurements, mixed Al-Ce-Zr oxides are quite effective for stabilization of different gold specimens. The samples pre- treated in hydrogen at 150°C are characterized by the presence of gold Au3+ cations located on the surface in slightly disordered octahedral oxygen coordination. Metallic gold nanoparticles with a size of about 2 nm and gold clusters were found in the samples treated in hydrogen at 300°C.

Specificity of the Local Structure of Nanocrystalline Doped Ceria Solid Electrolytes

This work presents results of studies of the structural features of nanocrystalline doped Ce1xMexO2-y samples (Me = Sm, Bi, Gd; x = 0-0.5) prepared via the polymerised precursor (Pechini) route by using a combination of diffraction (XRD, TEM, WAXS on SR) and spectroscopic (EXAFS, Raman, FTIRS of lattice modes, XPS, SIMS) methods.