In situ XPS and MS study of methanol decomposition and oxidation on Pd(111) under millibar pressure range

The methanol decomposition and oxidation on a Pd(111) single crystal have been investigated in situ using ambient-pressure X-ray photoelectron spectroscopy (XPS) and mass-spectrometry (MS) in the temperature range of 300–600 K. It was found that even in the oxygen presence the methanol decomposition on palladium proceeds through two competitive routes: fast dehydrogenation to CO and H₂, and slow decomposition of methanol via the C–O bond scission. The rate of the second route is significant even in the millibar pressure range, which leads to a blocking of the palladium surface by carbon and to a prevention of the further methanol conversion. As a result, no gas phase products of methanol decomposition were detected by mass-spectrometry at 0.1 mbar CH₃OH in the whole temperature range. The methanol C–O bond scission produces CH_x species, which fast dehydrogenate to atomic carbon even at room temperature and further partially dissolve in the palladium bulk at 400 K with the formation of the PdC_x phase. According to in situ XPS data, the PdC_x phase forms even in the oxygen excess. The application of an in situ XPS–MS technique unambiguously shows a good correlation between a decrease in the surface concentration of all carbon-containing species and the rate of methanol conversion. Since these carbon species have a high reactivity towards oxygen, heating of Pd(111) above 450 K in a methanol–oxygen mixture yields CO, CO₂, and water. The product distribution indicates that the main route of methanol conversion is the dehydrogenation of methanol to CO and hydrogen. However, under the experimental conditions used, hydrogen is completely oxidized to water, while CO is partially oxidized to CO₂. No palladium oxide was detected by XPS in these conditions.     

Density functional theory study into the adsorption of CO2, H and CHx (x = 0-3) as well as C2H4 on α-Mo2C(0 0 0 1)

The structures and energetics of the chemisorbed CO₂, CH_x species and H as well as C₂H₄ on the α-Mo₂C(0 0 0 1) surface have been computed at the GGA-RPBE level of density functional theory. It is found that CO₂ adsorbs dissociately into CO and O, in agreement with the experimental finding. The adsorbed O, CH_x and H species prefer the site of three surface molybdenum atoms over a second layer carbon atom (V_C site). On the basis of the calculated adsorption energies of CH_x and H, the sequential dehydrogenation of CH₄ and the C/C coupling reaction of CH_x have been discussed.     

Attrition of lignite char under fluidized bed gasification conditions: The effect of carbon conversion

The effect of carbon conversion on the attrition of lignite char particles during fluidized bed gasification by CO₂ was studied in a lab-scale apparatus. The influence of bed temperature and inlet CO₂ concentration on carbon conversion and, consequently, on attrition was studied. The mechanical resistance of the char particles was also characterized at different stages of char conversion by specific attrition experiments. A predictive kinetic model for CO₂ gasification of the lignite char was developed from the experimental results, that was able to correctly predict the evolution of carbon conversion versus time. On this basis a semi-empirical model was developed in order to simulate the evolution of carbon elutriation rate with carbon conversion degree, i.e. the gasification-assisted attrition enhancement effect.     

Experimental study of influence of temperature on fuel-N conversion and recycle NO reduction in oxyfuel combustion

Coal combustion in O₂/CO₂ environment was examined with a bituminous coal in which the gas-phase and char combustion stages were considered separately. The effects of temperature (1000–1300 °C) and the excess oxygen ratio λ (0.6–1.4) on the conversion of volatile-N and char-N to NOx were studied. Also, the reduction of recycle NOx by fuel-N was investigated under various conditions. The results show that fuel-N conversion to NO in O₂/CO₂ is lower than that in O₂/N₂. In O₂/CO₂ atmosphere, the volatile-N conversion ratios vary from 1–7% to 15–24% under fuel-rich and fuel-lean conditions, respectively. The char-N conversion ratios are 11–28% and 30–50% under fuel-rich and fuel-lean conditions, respectively. The influences of temperature on the conversion of volatile-N to NO under fuel-rich and fuel-lean conditions are contrary. A significant difference for char-N conversion in fuel-rich and fuel-lean conditions is observed. The experimental data of recycle NO reduction indicate that the reduction of recycle NO by gas-phase reaction can be enhanced by volatile-N addition in fuel-lean condition at high temperature, while in fuel-rich condition, the volatile-N influence cancelled out and the overall impact is small. NO/char reaction competes with the conversion of fuel-N to NO at higher temperatures.     

The structure of n-alkane binary mixtures adsorbed on graphite

The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A_1−xB_x try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations.     

Solid-state NMR and EPR analysis of carbon-doped titanium dioxide photocatalysts (TiO2−xCx)

Carbon-doped TiO₂ have received attention recently because of their potential for environmental photocatalysis and solar hydrogen conversion applications. Three different carbon-doped TiO₂ nanoparticle materials were synthesized via sol–gel and hydrothermal procedures, and analyzed by ¹³C solid-state nuclear magnetic resonance (SSNMR) and other methods to characterize the environment of the doping species. UV/vis spectra and powder X-ray diffraction (XRD) patterns showed that the synthesized materials absorbed visible light and their crystal structures corresponded to anatase. ¹³C SSNMR analyses of TiO_2?xC_x displayed signals corresponding to carbonate-type or sp²-type carbon species. Variable contact CP-MAS and dipolar dephasing analyses gave evidence for the presence and proximity of H atoms near these carbonate species. Electron paramagnetic resonance (EPR) spectroscopy showed that the thermally oxidized TiO_2?xC_x displayed a complex mixture of point defects, electron and hole trapping centers, all attributable to the incorporation of carbon, while the XPS data ruled out the presence of carbide species.     

Oxidation process of SiGe on SOI substrates

The oxidation of SiGe film epitaxial grown on top of SOI wafers has been studied. These SiGe/SOI samples were oxidized at 700, 900, 1100 °C. Germanium atoms were rejected from SiGe film to SOI layer. A new Si_1−xGe_x (x is minimal) layer formed at SiGe/Si interface. As the germanium atoms diffused, the new Si_1−xGe_x (x is minimal) layer moved to Si/SiO₂ interface. Propagation of threading dislocation in SiGe film to SOI substrate was hindered by the new SiGe/Si interface. Strain in SOI substrate transferred from SiGe film was released through dislocation nucleation and propagation inner. The relaxation of SiGe film could be described as: strain relaxed through strain equalization and transfer process between SiGe film and SOI substrates. Raman spectroscopy was used to characterize the strain of SiGe film. Microstructure of SiGe/SOI was observed by transmission electron microscope (TEM).     

155Gd Mössbauer spectroscopy measurements on Gd2T17C x,with T=Fe,Co, Ni andx varying from 0.6 to 1.2

¹⁵⁵Gd Mössbauer measurements were performed on Gd₂T₁₇C _x with T=Fe, Co, and Ni andx varying from 0.6 to 1.2. The crystal structures of these compounds are either the Th₂Zn₁₇ or the Th₂Ni₁₇ structure type. There is only partial occupation of the site available to the carbon atoms, leading to several crystallographically non-equivalent gadolinium surroundings. These various Gd sites show different quadrupole interactions. Doping with carbon causes an increased Curie temperature for the Gd₂Fe₁₇C _x compounds. The randomness of the occupation by carbon has been studied.     

Simulations of structures of amorphous SixC1−x films

Amorphous Si_xC_1−x films possess the potential to improve wear performance in humid atmospheres and at higher temperatures. But some experimental work on the films showed that silicon contents greatly influenced their microstructures and mechanical properties. Therefore, simulations of molecular dynamics were carried out to predict structures of the Si_xC_1−x films at different silicon contents. The results show that the sp³/sp² ratio of all the films increases, but the stiffness of the films is decreasing with an increase in silicon contents. Moreover, silicon atoms are almost surrounded by carbon atoms, which is in agreement with the experiments.     

Burning carbon monoxide in the settling chamber of a hotshot wind tunnel for obtaining the CO<Subscript>2</Subscript> test gas

A method of formation and heating of CO₂ as a test gas in the settling chamber of a hotshot wind tunnel is considered. To form and heat CO₂, the chamber is filled with a source gas mixture of CO, O₂, and CO₂, and after initiation, these substances participate in an exothermic chemical reaction in accordance with the formula CO + 0.5 O₂ + xCO₂ = (1 + x)CO₂. A stoichiometric ratio of the concentrations of carbon monoxide CO and oxygen is used. Variation of the number of moles x of ballast CO₂ in the left part of the chemical formula allows changing the temperature of the resultant test gas in a wide range. Experiments in the IT-302M hotshot wind tunnel carried out at ITAM SB RAS have shown that a pressure increase during an isochoric process in the settling chamber due to the joint effect of heat released in the reaction CO + 0.5 O₂ and an electric charge provides the completeness of CO combustion almost equal to unity. The time of reaction completion at its initiation by an electric arc is no more than several milliseconds.     

Electronic structure of rutile simultaneously doped with carbon and nitrogen atoms in the coherent potential approximation

The coherent potential method has been used for calculating the electronic structure and magnetic properties of rutile with a disordered arrangement of impurity carbon and nitrogen atoms in the oxygen sublattice: TiO_{2 ? x ? y} C _x N _y , x(y) = 0, 0.03, and 0.06. The tendencies to changes in the magnetic moment and photocatalytic activity with variations in the carbon-nitrogen composition of codoped rutile have been analyzed using the obtained data.     

Reduction of FeO/Pt(1 1 1) thin films by exposure to atomic hydrogen

Using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS) and density functional theory (DFT) calculations we have studied the reduction of ultra-thin films of FeO(1 1 1) grown on Pt(1 1 1) after exposure to atomic hydrogen at room temperature. A number of new ordered, partly-reduced FeO_x structures are identified and as a general trend we reveal that all the reduced FeO_x structures incorporate 2-fold coordinated Fe atoms as opposed to the original 3-fold coordinated Fe atoms in the FeO film. We find that when all the Fe atoms are 2-fold O-coordinated the FeO_x surface structure is resistant to further reduction at room temperature. We observe that water easily dissociates on the most heavily reduced FeO_x, structure in contrast to the initially inert FeO film, and reveal that it is possible to partially re-oxidize the FeO_x film by heating the surface slightly in the presence of water.     

Growth of Y-junction bamboo-shaped CNx nanotubes on GaAs substrate using single feedstock

Nitrogen-doped Y-junction bamboo-shaped carbon nanotubes were synthesized by chemical vapor deposition of monoethanolamine/ferrocene mixture on GaAs substrate at 950 °C. The use of monoethanolamine as the C/N feedstock simplifies the experimental arrangement by producing ammonia during the growth process. The structure, morphology and graphitization of as-grown nitrogen-doped carbon nanotubes (CN_x) were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy analysis. TEM analysis indicates that nanotubes have a bamboo-like structure. The nitrogen concentration on as-grown CN_x nanotube was found to be 7.8 at.% by X-ray photoelectron spectroscopy (XPS) analysis. XPS analysis also indicated that there are two different types of nitrogen atoms (pyridinic and graphitic) in these materials. The possible growth mechanism of formation of Y-junction CN_x nanotubes was briefly discussed. Field emission measurement suggested that as-grown CN_x nanotubes are excellent emitters with turn-on and threshold fields of 1.6 and 2.63 V/μm, respectively. The result indicated that monoethanolamine proves to be an advantageous precursor to synthesize Y-junction nitrogen-doped carbon nanotubes and such nanotubes might be an effective material to fabricate various field emission devices.     

Carbon concentration dependence of the superconducting transition temperature and structure of MgCxNi3

The crystal structure of the superconductor MgC_xNi₃ is reported as a function of carbon concentration determined by powder neutron diffraction. The single-phase perovskite structure was found in only a narrow range of carbon content, 0.88<x<1.0. The superconducting transition temperature was found to decrease systematically with decreasing carbon concentration. The introduction of carbon vacancies has a significant effect on the positions of the Ni atoms. No evidence for long-range magnetic ordering was seen by neutron diffraction for carbon stoichiometries within the perovskite phase stability range.     

Atomic-vacancy ordering in the carbide phase ζ-Ta4C3t-x

The structure of the nonstoichiometric trigonal (rhombohedral) carbide ζ-Ta₄C_3t-x forming in the tantalum-carbon system is studied by neutron diffraction, x-ray diffraction, and metallography. The unit cell parameters of the trigonal (space group R-3m) carbide ζ-Ta₄C_3?x (TaC_0.67) are found to be a _h = 0.3123 nm and c _h = 3.0053 nm. It is shown that the metallic close-packed sublattice of the ζ-Ta₄C_3?x phase consists of alternating blocks in which the metallic atoms are arranged in the same manner as on the fcc sublattice of the cubic carbide TaC_y and the hcp sublattice of the hexagonal carbide Ta₂C, respectively, and that the former sublattice is intermediate between the latter two sublattices. We are the first to establish experimentally that the distribution of carbon atoms and structural vacancies in the ζ-Ta₄C_3?x carbide is ordered and to calculate the distribution function of carbon atoms over the nonmetallic-sublattice sites involved in the ordering. The results obtained for the ζ-Ta₄C_3?x phase are used to refine the phase diagram of the Ta-C system.     

CO2 sensing properties of semiconducting copper oxide and spinel ferrite nanocomposite thin film

A new active layer for CO₂ sensing based on semiconducting CuO-Cu_xFe_3−xO₄ (with 0 ≤ x ≤ 1) nanocomposite was prepared by radiofrequency sputtering from a delafossite CuFeO₂ target using a specific in situ reduction method followed by post annealing treatment in air. The tenorite-spinel ferrite nanocomposite layer was deposited on a simplified test device and the response in a carbon dioxide atmosphere was measured by varying the concentration up to 5000 ppm, at different working temperatures (130-475 °C) and frequencies (0.5-250 kHz). The results showed a high response of 50% (Rair/RCO₂=1.9) at 250 °C and 700 Hz for a CO₂ concentration of 5000 ppm.     

New approach to the growth of SiOx nanowire bunch using Au catalyst and SiNx film on Si substrate

SiO_x nanowire bunches were fabricated on a SiN_x film with Au catalytic metal in the presence of an Ar flow of 50 sccm at 1150 °C. The resulting samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. A SiN_x film serves as a barrier to the diffusion of Si atoms from the Si substrate to the catalytic Au metal, where a substrate is a Si source material for SiO_x nanowire (NW) growth. Using this process, we could temporally control the initial growth step of SiO_x NWs and easily grow the NW bunch.     

Magnetic characterisation of the ternary carbide ThFe11C x (1.5≤x≤2) by57Fe Mössbauer spectroscopy

A⁵⁷Fe Mössbauer spectroscopy analysis of the ternary carbide ThFe₁₁C _x withx=1.5 and 1.8 has permitted to clearly identify the three different Fe sublattices from their relative abundance. Moreover, direct bonds exist between carbon atoms and iron atoms of one of the three sublattices, yielding a relatively large decrease of the local magnetic moment. A spin reorientation phenomenon (SR), taking place at low temperature, is shown to be of first order type. Both the exchange interactions and magnetocrystalline anisotropy parameters are very sensitive to the carbon stoichiometry. They are analysed for their role on the shifts inT _c andT _SR respectively.     

Possibilities of C 1s XPS and N(E) C KVV Auger spectroscopy for identification of inherent peculiarities of diamond growth

The interaction of C-atoms and CH_n-radicals with uncleaned and argon cleaned silicon substrate and with diamond surface after H-treatment have been studied in situ by XPS and Auger spectroscopy. It was found the formation of a new chemical surface state of carbon atoms in the case of carbon atoms and radicals interaction with cleaned silicon. The same chemical state was revealed on the H-treated diamond surface. Graphite-like structure of carbon atoms was observed on the surface of unlearned silicon and H-treated diamond after interaction with carbon atoms and radicals. N(E) C KVV Auger spectrum for the new chemical state of carbon atoms significantly differs from typical spectra for sp²- and sp³-bonded carbon materials. The high energy part of this spectrum was interpreted under the hypothesis of sp³-bonded carbon atoms but with shifted fermi level position.     

Effect of Co substitution for Fe in Sr2FeMoO6 on electrocatalytic properties for oxygen reduction in alkaline medium

Double perovskites Sr₂Fe_1???x Co _x MoO₆ (x?=?0, 0.25, 0.5, 0.75 and 1) have been investigated as cathode material for oxygen reduction reaction (ORR) in 0.5 M NaOH at 25 °C using the rotating disk electrode. The electrocatalytic powders were prepared by a solid-state process and characterised by X-Ray powder diffraction, scanning electron microscopy and infrared spectroscopy. The electrochemical techniques considered are linear voltammetry, steady-state polarization and impedance spectroscopy. The electrocatalysts Sr₂Fe_1???x Co _x MoO₆/C consisting of the double perovskite oxides and carbon (Vulcan XC-72) were mixed and spread out into a thin layer on a glassy carbon substrate. The electrocatalytic activity was strongly influenced by the Co substitution at room temperature. The relation between catalytic performance and the degree of Co content was examined. The Co-containing catalysts exhibited lower activity attributed to their high resistivity, and the highest activity toward oxygen reduction was observed for Sr₂CoMoO₆.