E. M. Pazhetnov

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.

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.

Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries

Classical Li-ion battery technology is based on the insertion of lithium ions into cathode materials involving metal (cationic) redox reactions. However, this vision is now being reconsidered, as many new-generation electrode materials with enhanced reversible capacities operate through combined cationic and anionic (non-metal) reversible redox processes or even exclusively through anionic redox transformations. Anionic participation in the redox reactions is observed in materials with more pronounced covalency, which is less typical for oxides, but quite common for phosphides or chalcogenides. In this Concept, we would like to draw the readers attention to this new idea, especially, as it applies to transition-metal polychalcogenides, such as FeS2 , VS4 , TiS3 , NbS3 , TiS4 , MoS3 , etc., in which the key role is played by the (S-S)2- /2 S2- redox reaction. The exploration and better understanding of the anion-driven chemistry is important for designing advanced materials for battery and other energy-related applications.

X-ray emission and X-ray photoelectron spectroscopic studies of fullerene fluoride C60F24

The structure of the fullerence fluoride C60F24 of the Th symmetry contains two types of chemically different carbon atoms, namely, atoms of isolated double bonds and atoms of CF groups. X-ray photoelectron and x-ray emission spectroscopic studies of C60F24 revealed a difference in the widths of the x-ray bands corresponding to these types of atoms. Nonempirical quantum-chemical calculations performed for C59NF24+ ions with a hole in the C 1s core level of the fullerence fluoride showed that the difference in the bandwidths may be due to the fact that the vibrational states of the system are different when 1s electrons are removed from chemically nonequivalent atoms.

Fluorination of multiwall nitrogen-doped carbon nanotubes

A film of oriented nitrogen-doped multiwall carbon nanotubes was grown on a silicon substrate as a result of the thermolysis of an acetonitrile + ferrocene mixture. The fluorination of the film by BrF3 vapor at room temperature removed the substrate; however, the vertical orientation of the nanotubes was not destroyed. Analysis of micrographs of a fluorinated sample obtained with a high-resolution transmission electron micro-scope showed that only the surface walls of the nanotubes were fluorinated. The fluorine concentration of the product as determined from X-ray photoelectron spectroscopy was about 16%. A comparison of the N1s spectra of the starting and fluorinated samples showed that the nitrogen atoms of CNx nanotubes changed their electronic state as a result of fluorination. Matching of the X-ray photoelectron spectroscopic data with the results of quantum-chemical calculations for fragments of fluorinated nitrogen-doped nanotubes showed that fluorine atoms preferred to attach to pyridine-like nitrogen atoms or to carbon atoms in the ortho or meta positions relative to a nitrogen atom.

Fluorination of CNx Nanotubes

Abstract Multiwall CN x nanotubes have been prepared by thermal decomposition of acetonitrile over Co/Ni catalytic particles. The fluorination of nanotubes was performed at room temperature by using a gaseous mixture of BrF3 and Br2. Transmission electron microscopy (TEM) and x‐ray diffraction (XRD) indicated that only the outer shells of CN x nanotubes were fluorinated, whereas the inner shells remained intact. X‐ray photoelectron spectroscopy (XPS) showed an oxidation of pyridinic‐type nitrogen with tube fluorination.

Formation Mechanism and Structure of Monatomic Carbon Films in Ethylene Decomposition on the Pt(111) Surface According to XPS Data

The interaction of ethylene with a Pt(111) single-crystal surface was studied using X-ray photoelectron spectroscopy. It was found that both two-dimensional flat graphite islands and curved fullerene-like carbon structures or nanotubes can be formed depending on the reaction temperature of ethylene and the presence of dissolved carbon in the bulk of the crystal. It was assumed that the size and curvature of the islands depend on the size of terraces on the single-crystal surface.

Fluorine Effect on the Binding Energy of Nitrogen Atoms Incorporated into Multiwall CNx Nanotubes

Fluorination of multiwall CNx nanotubes has been shown to change the N 1s line of X‐ray photoelectron spectrum (XPS). Ab initio Hartree‐Fock calculations on various models of fluorinated nitrogen‐doped graphite fragments were performed to reveal fluorine effect on the binding energy of N 1s core level. Comparison between experimental and theoretical data indicated that the most probable sites for fluorine attachment are (1) carbon atoms bonded to three‐coordinated nitrogen, (2) pyridinic nitrogen atoms, and (3) carbon atoms located para and ortho to the pyridinic nitrogen.