V. V. Kaichev

The Nature of Electrophilic and Nucleophilic Oxygen Adsorbed on Silver

Results of a spectroscopic study of two forms of adsorbed atomic oxygen on a silver surface, which participate in ethylene epoxidation reaction, are presented. The possibility of the combined use of the methods of photoelectron spectroscopy and X-ray absorption for a detailed analysis of adsorbate electron structure on solid surfaces is demonstrated. It is found that a significant difference in the position of O 1s lines for nucleophilic (528.3 eV) and electrophilic (530.4 eV) oxygen is determined by the effects of the initial state, that is, by the difference in the charge state of oxygen anions. The use of the well-know correlation of the Auger line splitting with a Pauling charge at an oxygen atom showed a substantial difference (∼1 electron charge unit) in charge transfer from metal to the nucleophilic or electrophilic adsorbed oxygen atom. Based on the X-ray absorption data of the oxygen K-edge, it is found that there is a substantial overlap of the 4d- and 5sp orbitals of silver with oxygen 2p orbitals in the nucleophilic state in the formation of an Ag–O bond and there is only an overlap of 5sp orbitals of silver with oxygen 2p orbitals in the electrophilic state. Structural models of the adsorption site are presented for both states. The conclusion is drawn that the charge state of oxygen in oxide systems may depend substantially on its binding to metal atoms.

Composition and structure of hafnia films on silicon

Ellipsometry, electron microscopy, and x-ray photoelectron spectroscopy data indicate that, during HfO2 deposition onto silicon, the native oxide reacts with the HfO2 deposit to form an amorphous intermediate layer which differs in refractive index (≃1.6) from both HfO2 (1.9–2.0) and SiO2 (1.46). Thermodynamic analysis of the Si-SiO2-HfO2-Hf system shows that Si is in equilibrium with Si/HfO2 − y only at low oxygen pressures. Starting at a certain oxygen pressure (equivalent to the formation of a native oxide layer), the equilibrium phase assemblage is Si/HfSiO4/HfO2 − y.

Catalysts Based on Fiberglass Supports: III. Properties of Supported Metals (Pt and Pd) According to Electron-Microscopic and XPS Data

Under various preparation conditions, metals supported on leached borosilicate and soda–silica fiberglass form three types of particles. First, these are metal particles in sizes from tens to hundreds of angstrom distributed over the outer surface of fibers. Second, in the presence of mesopores in fiberglass supports (borosilicate glasses), metal particles of commensurable sizes (15–100 Å) are localized in the cavities. Third, dispersed (<10 Å) particles are present in the bulk of fiberglass; these particles are intercalated into the bulk of leached glasses as deep as several hundreds of angstrom. The amount of a metal and the depth of penetration into the bulk of fiberglass can be controlled by preparation conditions and by the addition of cointercalates, which are responsible for pillaring effects.

In Situ Study of the Selective Oxidation of Methanol to Formaldehyde on Copper

Combined use of X-ray photoelectron spectroscopy (XPS) and in situ mass spectrometry made it possible to simultaneously obtain the O1s spectra and the mass spectrometric signal of formaldehyde (m/z = 30) in the course of heating (420–670 K) of polycrystalline foil in a flow of the reaction mixture of methanol and oxygen (with a total pressure of 0.1 mbar and a ratio of 3/1). It is shown that the O1s spectra contain two lines with Eb = 530.1 and 531.2 eV, whose relative intensities depend on the sample temperature. At a low temperature (420 K) the line with a lower binding energy dominates, whereas sample heating leads to a drastic decrease in its intensity and its replacement by a line with a higher value of Eb. A decrease in the intensity of the latter line occurs at T > 550 K, in the same temperature range as a drastic increase in the intensity of the formaldehyde signal. These lines were assigned on the basis of literature data and data obtained by the authors for the known forms of oxygen on copper and for the intermediate species of the reaction, such as methoxy and formate. The O1s line with Eb = 530.1 eV was assigned to methoxy groups, and the line with Eb = 531.2 eV was assigned to suboxide oxygen. The correlation of the intensity of the XPS signal of suboxide oxygen with the yield of formaldehyde was supported by stationary experiments using in situ XPS that prove its participation in the key step of the selective oxidation of methanol to formaldehyde.

Chemical Composition of Boron Carbonitride Films Grown by Plasma-Enhanced Chemical Vapor Deposition from Trimethylamineborane

Boron carbonitride and boron nitride films were grown by plasma-enhanced chemical vapor deposition using trimethylamineborane and its mixtures with ammonia, hydrogen, or helium. The effects of the starting-mixture composition and substrate temperature on the chemical composition of the deposits was studied by ellipsometry, scanning microscopy, IR spectroscopy, Raman scattering, and x-ray photoelectron spectroscopy. The results indicate that the initial composition of the gas mixture, the nature of the activation gas, and substrate temperature play a key role in determining the deposition kinetics and the physicochemical properties of the deposits. Depending on these process parameters, one can obtain h-BN, h-BN + B4C, or BCxNy films.

LiMn2O4 and LiCoO2 composite cathode materials obtained by mechanical activation

New composite cathode materials xLiMn2O4/(1 − x) LiCoO2(x = 0.7, 0.6, 0.5 и 0.4) were obtained by mechanical activation. According to scanning electron microscopy data, the process was accompanied by pronounced dispersion and fine mixing of the initial components. In the course of the preparation and electrochemical cycling of the composites, LiMn2O4 and LiCoO2 partially reacted, leading to the replacement of manganese with cobalt in the structure of spinel, which was detected by powder X-ray diffraction (XRD), IR and X-ray photoelectron spectroscopy (XPS), and cyclic chronopotentiometry. The specific discharge capacity of composites was ∼100 mAh/g.

Effect of the Ni/Cu ratio on the composition and catalytic properties of nickel-copper alloy in anisole hydrodeoxygenation

The activity of NiCu-SiO2 catalysts with a metal content of 90% and different Ni/Cu ratios has been investigated in the hydrodeoxygenation of anisole, a model compound of bio-oil, at 280°C and 6 MPa. A homogeneous phase composition of the active component has been synthesized by the co-decomposition of nickel and copper nitrates followed by the introduction of SiO2 as a stabilizer. The resulting catalysts have been characterized by temperature-programmed reduction, X-ray powder diffraction, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy combined with energy-dispersive microanalysis. The bulk and surface composition of active-component particles has been determined by XPS and X-ray diffraction. In all of the catalysts containing 15–85 wt % Ni, there are two types of solid solutions. One has a constant composition, Cu0.95Ni0.05, which is independent of the Ni/Cu ratio in the catalyst; in the other, the nickel stoichiometry increases with an increasing Ni content of the active component. A correlation has been established between the Ni/Cu ratio and the rate constants of the reaction examined and between the Ni/Cu ratio and the degree of hydrodeoxygenation for all samples. The most active catalyst is Ni85Cu5-SiO2.

Origin of temperature oscillations of nickel catalyst occurring in methane oxidation

The catalytic oxidation of methane over a nickel foil has been investigated in a wide range of methane: oxygen molar ratios at a constant reactor temperature of 680°C. Under oxygen-deficient conditions, the reaction takes place in the self-oscillating mode. Stable self-sustained oscillations of the methane oxidation rate are observed in the CH4: O2 molar ratio range from 2: 1 to 19: 1. This process is accompanied by catalyst temperature oscillations, whose amplitude reaches 80°C. It has been demonstrated by scanning electron microscopy that the origination of the self-sustained oscillations is accompanied by morphological changes in the catalyst surface. Under the action of the reaction medium, a porous layer 5–10 µm in thickness forms on the nickel foil surface. The mechanism of methane oxidation over nickel that accounts for the onset of the self-sustained oscillations is discussed. This mechanism is based on periodical nickel oxidation and reduction. When nickel is in the high-activity state, it is mainly in metallic form, and the passage of nickel into its low-activity state is accompanied by the formation of a nickel oxide layer on the foil surface. The reduction of this nickel oxide causes a periodic decrease in the catalyst temperature. The total and partial oxidations of methane on the reduced surface of the nickel foil raise the catalyst temperature. Under oxygen-deficient conditions, a carbon deposit builds up on the catalyst surface, and the combustion of this deposit complicates the catalyst temperature oscillation profile.

Mathematical simulation of self-oscillations in methane oxidation on nickel: An isothermal model

The dynamics of methane oxidation on nickel was studied by mathematical modeling within the framework of an 18-step microkinetic scheme. The model examined predicts the appearance of self-oscillations caused by the periodic oxidation-reduction of nickel in the reaction proceeding under isothermal conditions.

Plasma-chemical deposition of SiCN films from volatile N-bromhexamethyldisilazane

Process of silicon-carbonitride (SiCN) film production from a new volatile organosilicon, N-bromhexamethyldisilazane, is developed. The use of this chemical comprising the relatively week N-Br bond makes it possible to increase the film growth velocity in the plasma-chemical process with remote plasma in comparison with the processed in which hexamethyldisilazane and hexamethylcyclotrisilazane are used. The chemical composition of the films is determined using a complex of spectroscopic methods. It is found that inorganic SiCN films containing Si-N, Si-C, and C-N bonds are deposited at temperatures 570–870 K. The C-N bonds are formed already at a temperature of about 470 K. It is shown that the use of this volatile organosilicon material makes it possible to synthesize silicon carbonitrides with various ratios of the Si-C, Si-C, and C-N bonds. This enriches the possibilities of producing films and coatings with various functional parameters. The nanohardness of 100-nm films prepared at T > 770 K is 17 GPa.