Study of Au/SnO x –Al2O3 catalysts used in CO oxidation by in situ Mössbauer spectroscopy

The active catalytic components in tin oxide containing alumina-supported gold catalyst were examined by comparing and analysing the in situ Mössbauer spectra of the SnO _x –Al₂O₃ support and the 3 wt.% Au/SnO _x –Al₂O₃ catalyst (1.1 wt.% Sn, Au/Sn = 3:2 atomic ratio). Samples were prepared by using organometallic precursor of ¹¹⁹SnMe₄ (enriched). First tin was grafted to the alumina surface from the organometallic precursor compound. In the next step the grafted complexes were decomposed in flowing oxygen. Gold was deposited onto the SnO _x –Al₂O₃ support in the subsequent step. Analysis of in situ spectra shows that in Au/SnO _x –Al₂O₃ catalyst after activation in hydrogen at 620 K tin may occur in three different oxidation states [Sn (IV), Sn(II) and Sn(0)] simultaneously. The metallic tin is a component of the bimetallic AuSn alloy phase. Data presented provide the first evidence for the formation of alloy-type supported Sn–Au catalyst on alumina. Furthermore, from the spectra recorded at different temperatures, values of the Debye temperatures and recoilless fractions were also determined for the various species. The results show that in catalytic oxidation of carbon monoxide at room temperature the dominant part of Sn(II) and the AuSn alloy is oxidized.     

Pure and Sb-doped SnO 2 nanoparticles studied by photoelectron spectroscopy

We describe photoemission results from pure and Sb-doped SnO₂ nanoparticles deposited on gold substrates. Photoelectron spectra with synchrotron radiation were recorded for Sn 3d, Sb 3d and O 1s core levels and valence bands in the 500-1200 eV energy range. For pure SnO₂ nanoparticles the surface is terminated by an oxygen rich layer with no obvious surface environment for Sn. When doped n-type with 9.1% or 16.7% Sb, dopant atoms are concentrated near the surface of the nanoparticles. The valence state of the dopant atoms is predominantly Sb^V. Plasmon satellite features are also observed in core level photoemission spectra and their intensity relative to the main peak increases with increasing photon energy. Received 30 November 2000     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

XPS depth profiling studies of L-CVD SnO2 thin films

In this paper we present the results of the XPS atomic depth profile analysis, using ion beam sputtering, of L-CVD SnO₂ thin films grown on an atomically clean SiO₂ substrate after annealing at 400 °C in dry atmospheric air. From the evolution of the Sn 3d_5/2, O 1s, Si 2p and C 1s core level peaks our experiments allowed the determination of the in depth atomic concentration of the main components of the SnO₂/SiO₂ interface. Thin (few nm) nearly stoichiometric SnO₂ films are present at the topmost layer of the thin films, and progressive intermixing with SnO and silicon oxide is observed at deeper layer. The interface between the Sn and the Si oxide layers (i.e. the effective Sn oxide thickness) is measured at 13 nm.     

Characterization of tin phosphate coatings by CEMS

The structure and chemical state of tin in converted tin phosphate coatings, obtained by a treatment of Zn and Mn phosphate in SnCl₂ solution, were characterized by CEMS. Converted Sn(II) phosphate and adsorbed SnO₂ species were main products in the ≈1/3 top layers of Mn and Zn phosphate coationgs, and metallic tin was occasionally recognized in deeper layers. Tin phosphate layers, coated directly on a steel substrate by RF sputtering of Ar ions, were composed of two kinds of Sn(IV) species.     

Observation of resonance recombination lines in electron excited auger spectra of Gd

Combined measurements of electron excited N_4,5 Auger spectra and photoelectron emission on clean and oxidized Gd lead to a distinction between Auger lines originating from 4d → continuum and 4d → 4? resonance excitations. Several Auger structures are identified as due to the direct recombination of 4d⁹4?⁸ states with the 4f and valence electrons. The shape of the most prominent Auger line for oxidized Gd agrees perfectly with the Fano profile of the 4? photoemission intensity.     

Facile preparation of SnC2O4 nanowires for anode materials of a Li ion battery

A simple method of creating densely-packed nanostructures of functional metal oxides is attractive, but it has always been a challenge. Here, we synthesize well-distributed nanostructures of Sn complexes (SnC₂O₄ and SnO₂) via a simple chemical anodization technique followed by annealing. Chemical anodization of Sn surface in oxalic acid, using various organic solvents, provides one-dimensional nanostructures of SnC₂O₄. Length and packing density were precisely controlled by several parameters: solubility of oxalic acid, dielectric constant of organic solvents, and the ion transfer of proton and oxalate anion. Further thermal decomposition converts the SnC₂O₄ nanowires into SnO₂ nanowires, maintaining the nanostructure form in the process. In addition, we expect that the mixture of SnC₂O₄ and SnO₂ nanowires synthesized by this approach might be potential alternative anode materials for prompt charging and discharging Li ion batteries.     

Modification of the electronic structure and formation of an accumulation layer in ultrathin Ba/n-GaN and Ba/n-AlGaN interfaces

The electronic structure of the n-GaN(0001) and Al _x Ga_{1 ? x} N(0001) (x = 0.16, 0.42) surfaces and the Ba/n-GaN and Ba/AlGaN interfaces is subjected to in situ photoemission investigations in the submonolayer Ba coverage range. The photoemission spectra of the valence band and the spectra of the surface states and the core 3d level of Ga, the 2p level of Al, and the 4d and 5p levels of Ba are studied during synchrotron excitation in the photon energy range 50–400 eV. A spectrum of the surface states in Al _x Ga_{1 ? x} N (x = 0.16, 0.42) is found. The electronic structure of the surface and the near-surface region is found to undergo substantial changes during the formation of the Ba/n-GaN and Ba/AlGaN interfaces. The effect of narrowing the photoemission spectrum in the valence band region from 10 to 2 eV is detected, and surface eigenstates are suppressed. The Ba adsorption is found to induce the appearance of a new photoemission peak in the bandgap at the Fermi level in the Ba/n-GaN and Ba/n-Al_0.16Ga_0.84N interfaces. The nature of this peak is found to be related to the creation of an accumulation layer due to a change in the near-surface potential and enriching band bending. The energy parameters of the potential well of the accumulation layer are shown to be controlled by the Ba coverage.     

Sn and SnO2-graphene composites as anode materials for lithium-ion batteries

Sn and SnO₂-graphene composites were synthesized using hydrothermal process, followed by annealing in Ar/H₂ atmosphere, and characterized using x-ray diffraction, scanning electron microscopy, and transition electron microscopy. The results indicated that the polycrystalline metallic Sn forms nanospheres with a diameter of 100?～?300 nm, while the SnO₂ nanoparticles are much smaller with a size below 15 nm, which adsorb tightly on the surface of graphene sheets. The Sn and SnO₂-gaphene composites showed good electrochemical performance. After 55 charging/discharging cycles, the capacity remains above 440 mAh/g at a cycling rate of 400 mA/g and the coulombic efficiency is 99.1 %. The good electrochemical properties of the composites are partially contributed to the graphene component with good mechanical flexibility and electrical conductivity, which is an excellent carbon matrix for dispersing the Sn and SnO₂ nanostructures and provides the electron transport pathways as well.     

Growth of SnO2 nanoparticles via thermal evaporation method

Tin oxide (SnO₂) nanoparticles were fabricated by evaporation of Sn powers at 1000 °C in air pressure. The as-deposited SnO₂ particles were single crystal structure, which were mostly spherical shape, the diameter of particles was ranging from 200 to 600 nm. The photoluminescence (PL) spectrum showed that a sharp emission peak at around 393 nm with the excitation wavelength at 325 nm, which suggested possible applications in nanoscaled optoelectronic devices. It was also found that the holding time affects the morphology of the products. The formation mechanism of SnO₂ particles was discussed.     

Varistor and dielectric properties of Cr2O3 doped SnO2–Zn2SnO4 composite ceramics

Cr₂O₃ doped SnO₂–Zn₂SnO₄ composite ceramics were prepared by traditional ceramic processing and the varistor, dielectric properties were investigated. With increasing Cr₂O₃ content, the breakdown electrical field E_B increases from 11 to 92 V/mm and the relative dielectric constant ε_r measured at 1 kHz, 50 °C decreases from 11,028 to 3412, respectively. The barrier height ?_B about 0.8–0.84 eV and the decreasing of SnO₂ grain size suggest that the varistor behavior with high ε_r is originated from SnO₂–SnO₂ or SnO₂–Zn₂SnO₄ grain boundary. In the dielectric spectra lower than 1 kHz, a dielectric peak is presented and depressed with increasing bias voltage. Similarly, at high temperature, the dielectric constant also presents a dielectric peak in the temperature spectra and the peak becomes faint with increasing frequency. The exhibition of the dielectric peak is thought to be attributed to the conduction of grain boundary since it is accompanied by the sharp increase of dielectric loss. In addition, a dielectric relaxation with the activation energy about 0.4–0.5 eV was observed in the temperature range of 20–100 °C. Based on the results, the formation mechanism of Schottky barriers at grain boundaries and the varistor behavior with high dielectric constant are well understood.     

Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

H2 reactivity on the surfaces of In and Sn at 298 K

The reactivity of H₂ gas with the In and Sn surfaces was quantitatively measured by a volumetric method at pressures ranging from 10⁻⁷ to 10⁻² Pa at 298 K. Significant enhancement of H₂ reactivity was observed when O₂ or H₂O preadsorbed on the surface of In and Sn before H₂ exposure. The formation of the oxygen deficient SnO_2−x and In₂O_3−z in the surface layers is proposed as a reason for such a facilitating the H₂ dissociation and resulting in the enhancement of the H₂ reactivity at 298 K.     

Resonant photoemission in DyNi2Mn x rare-earth intermetallides

The electronic structure of the DyNi₂Mn _x rare-earth (RE) intermetallides whose cubic structure is similar to the structure of RT₂ compounds is studied. Resonant photoemission and X-ray absorption methods are used in the vicinity of the 2p- and 3p-excitation thresholds of transition elements and the 3p-, 3d-, and 4d-thresholds of RE metals to find the Ni, Mn 3d-, and R 4f-partial densities of the states in the valent band. The use of resonant photoemission allows us to establish features of the interaction between the unfinished 4f-shells of ions of RE metals with ions of the transition 3d-elements in RNi₂Mn _x compounds. The contributions from atoms of various elements to the structure of the valent band are separated, and the basic regularities of band formation during the introduction of manganese atoms are found.     

Low temperature CEMS of Sn-implanted SiO2

Conversion electron Mössbauer spectroscopy (CEMS) at room and low temperature has been used to study thin SiO₂ films implanted with Sn atoms and annealed at 900°C. This work focuses on the determination of the Debye temperature (θ _D) and Debye–Waller factors (f) of the Sn oxidized phases formed in this system. The Sn²⁺ oxidation state is the predominant one, even if a small percentage of the Sn atoms is in the Sn⁴⁺ oxidation state. The real Sn-oxides fractions are calculated by normalizing the resonant areas to the f values, as calculated from the temperature dependence of the related resonant areas within a Debye model. The Sn⁴⁺ oxidation state, possibly related to Sn atoms close to the SiO₂ surface, represents less than 20% of the Sn atoms. For the Sn²⁺ oxidation state, two different electronics configurations a and b, having different Debye temperature and hyperfine parameters are identified. The component a, with a lower θ _D (137 K), is the predominant one and might be related to small (2–3 nm) amorphous SnO _x clusters in the SiO₂ matrix. The component b could be related to substitutional Sn atoms in the SiO₂ network forming a local Sn environment similar to the SnO amorphous compound.     

Volume of precursor solution effect on the properties of SnO<Subscript>2</Subscript> thin films prepared by nebulized spray pyrolysis technique

Undoped SnO₂ thin films have been deposited on amorphous glass substrates with different precursor solution volume (10, 15, 20 and 25 ml) using simple and cost-effective nebulized spray pyrolysis technique. The influence of precursor solution on structural, optical, photoluminescence and electrical properties had been studied. The X-ray diffraction spectra prove the polycrystalline nature of SnO₂ with tetragonal structure. All the films show a preferred growth orientation along (110) diffraction plane. The average transmittance of SnO₂ thin films varied between 82 and 75% in the visible as well as IR region. The band gap energy decreases from 3.74 to 3.64 eV corresponding to direct transitions with the precursor solution volume had increased from 10 to 20 ml and then increased as 3.72 eV for 25 ml. SEM pictures demonstrated polyhedrons like grains. EDX confirmed the existence of Sn and O elements in all the prepared SnO₂ thin films. Photoluminescence spectra at room temperature revealed that the four emission bands in all the samples such as sharp dominant peak at 361 nm with shoulder peak at 377 nm (UV region), a broad and low intensity peak at 492 nm (blue region) and 519 nm (green region). The electrical parameters were examined by Hall effect measurements, which demonstrated that the film prepared at 20 ml precursor solution volume possess minimum resistivity 2.76?×?10^?3 Ω-cm with activation energy 0.10 eV and maximum figure of merit 1.54?×?10^?2 (Ω/sq)^?1.     

Electric quadrupole interactions in nano-structured SnO 2 as measured with PAC spectroscopy

Measurements of the electric quadrupole interaction were used to characterize pure and cobalt-doped samples of SnO₂ prepared by the sol-gel method. Perturbed gamma–gamma angular correlation (PAC) spectroscopy using ¹¹¹In–¹¹¹Cd probe nuclei was employed for these measurements. A methodology was developed for sample preparation that were prepared by sol-gel method from pure metallic Sn (99.9999%) and Co (99.9998%) as starting materials. Carrier-free ¹¹¹In was added to the precursor sol-gel solution prior to the formation of gel. PAC measurements were carried out to follow the formation of the SnO₂. PAC measurements were carried out in the temperature range from 10 k to 1123 K and the results show that the electric quadrupole frequency depends on the annealing temperature.     

Electric field gradient in nanostructured SnO2 studied by means of PAC spectroscopy using 111Cd or 181Ta as probe nuclei

Electric quadrupole interactions were studied in pure and Mn-doped powder samples and thin films of SnO₂ using perturbed γγ angular correlation spectroscopy (PAC). The powder samples were prepared by Sol gel method and the thin film were prepared on the Si (100) substrate by sputtering technique using Sn in the oxygen atmosphere. The samples were characterized by x-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy. The thickness of the film was 100 nm. The average particle size of the SnO₂ powder samples was determined to be smaller than 60 nm. The radioactive ¹¹¹In and ¹⁸¹Hf tracers were introduced in the powder samples during the sol gel chemical process. Radioactive ¹¹¹In was implanted on the SnO₂ thin films using the University of Bonn ion implanter (BONIS). PAC measurements were carried out in a four BaF₂ detector spectrometer in the temperature range of 77–973 K for samples annealed at different temperatures. The PAC results for both nuclear probes show the presence of two electric quadrupole interactions. The major fractions in both cases correspond to the substitutional sites in the rutile phase of SnO₂. The results are compared with previous PAC measurements.     

Fe/SnO2非晶多层膜的磁特性

研究了高频溅射制备的Fe/SnO₂非晶多层膜的磁特性.当SnO₂层厚度d_s固定为5nm时，样品的饱和磁化强度M_s随Fe层厚度d_m的减小而降低，这主要受样品的死层效应和维度效应的影响.另外，在d_m很小时，样品呈现准二维磁性.样品居里温度T_C随d_m的减小单调下降.样品矫顽力H_c随d_m的变化呈现 关键词：     

Photoemission of adsorbed CO and H2O on Pt: Valence band studies

In this paper, using monochromatic He and Ne discharge lines, we report the ultraviolet photoemission results for CO and H₂O adsorbed on a Pt crystal. For chemisorbed CO, we use the energy dependence of the photoionization cross section to deduce that the 5σ?1π splitting is approximately 1 eV and that the 5σ is located at about ?8.1 eV while the 1π is at ?9.1 eV. The distribution of metal electrons changes in two ways upon CO chemisorption: a d character peak is found at ?4 to ?5 eV and emission at E_f is strongly depleted. For the weakly adsorbed water molecule, we find preferential attenuation of Pt states near E_f that has heretofore been observed for strongly chemisorbed systems.