新型水溶性配体-负载金属氢甲酰化催化剂:TPPTS-Rh/SiO2

考察了几种硅胶负载贵金属催化剂和HRhCO(TPP) 3 催化剂的 1 己烯氢甲酰化反应 ,对Rh/SiO2 、HRhCO(TPPTS) 3 /SiO2 和TPPTS Rh/SiO2 上的 1 己烯氢甲酰化结果进行了比较 .结果表明 ,TPPTS Rh/SiO2 催化剂的醛的选择性和醛的正异比n/b接近HRhCO(TPPTS) 3 /SiO2 的相应的催化性能 ,而远高于Rh/SiO2 的相应的催化性能 ,7.0MPa高压下TPPTS Rh/SiO2 催化剂的活性大幅度增加 ,达到 0 .0 6 92S-1.实验排除了其他可能 ,认为是含有孤对电子的TPPTS和Rh/SiO2 中高度分散的Rh粒子产生了化学键的作用 ,形成了具有匀相性能的支撑水膜多相催化剂 :TPPTS Rh/SiO2 .     

Self-assembly of β-Ga2O3 nanobelts

Self-assembly of β-Ga₂O₃ (beta-gallium oxide) nanobelts with diameters of 50–100 nm and lengths of tens to hundreds of microns have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). Under appropriate conditions such as nanobelts concentration, controlled solvent evaporation, β-Ga₂O₃ nanobelts assemble into a fan-like structure on the substrate. A tendency of these nanobelts to align parallel to each other was also observed. The mechanism behind the formation of self-assembly of β-Ga₂O₃ nanobelts has been proposed on the basis of lateral capillary forces.     

Change of the surface induced optical anisotropy of the clean Si(110) surface by oxidation

Normal incidence ellipsometry has been used to measure the change in the complex anisotropic reflectance ratio γ upon oxidation of the clean Si(110)16 × 2 surface. The spectroscopic change in the amplitude of γ (tan(Ψ)) shows a broad maximum of height 1.4 × 10⁻³ in the high energy region above 2.5 eV. No phase shift difference for the reflectance coefficients belonging to the surface principal optical axes has been measured. A Kramers-Kronig transformation of the amplitude ratio showed that a change in the phase is not expected. The change in tan(Ψ) indicates that the change in reflection upon oxidation in the optical region ismainly in the ( 10) direction.     

Computer simulations of ion scattering and recoiling blocking patterns for surface structure analysis

A three-dimensional classical ion trajectory simulation code has been developed and applied to ion scattering and recoiling patterns on a large-area detector. The test systems used for the patterns were as follows: (1) Pt{110})-(1 × 2) and −(1 × 3) as an example of a reconstructed metal surface; (2) Ni{100}, {110}, and {111} surfaces as an example of different crystal faces: and (3) Ni{110}−(2 × 1)−O as an example of adsorbate recoiling. The optimum experimental configurations for collecting data for structural analysis have been considered. Three configurations have been identified; these include collection of both in- and out-of-plane scattering and recoiling data. The anisotropic patterns obtained for the scattered I_S, and recoiled I_R flux in azimuthal δ and exit β angle space are produced by blocking cones and are unique for the specific substrate and adsorbate structures. Critical exit β_c and azimuthal δ_c angles can be identified from these patterns. The interatomic spacings d along specific azimuths are determined from measurements of β_c and δ_c. Simulated patterns for the three test systems listed above are presented and their features are analyzed in terms of the surface structures. The advantages and new features available through the use of large-area detectors are described and compared to conventional ion scattering spectrometry (ISS). In the case of Pt, for which comparable experimental scattering data are available, the agreement between simulations and experimental results is good.     

Potassium adsorption on graphite(0001)

Potassium adsorption on graphite has been studied with emphasis on the two-dimensional K adlayer below one monolayer. Data are presented for the work function versus coverage, high-resolution electron energy loss spectroscopy (HREELS) vibrational spectra of K-adlayers, low energy electron diffraction and ultraviolet photoemission spectroscopy (UPS) spectra at different coverages. The data provide information regarding the vibrational properties of the K-adlayer, the metallization of the adlayer at submonolayer coverages, and the charge transfer from the K adatoms to the graphite substrate. Analysis of the work function, HREELS, and UPS data provides a qualitatively consistent picture of the charge state of the K adatoms, where at low coverages, below a critical coverage θ_c (θ_c=0.2–0.3), the K adatoms are dispersed and (partially) ionized, whereas at θ>θ_c islands of a metallic 2×2 K phase develops that coexist with the dispersed a K adatoms up to θ=1. We show that it is possible to understand the variation of the work function data based on a two-phase model without invoking a depolarization mechanism of adjacent dipoles, as is normally done for alkali-metal adsorption on metal surfaces. Similarly, the intensity variation as a function of coverage of the energy loss peak at 17 meV observed in HREELS, and the photoemission peak at E_b=0.5 eV seen in UPS can be understood from a two-phase model. A tentative explanation is presented that connects apparent discrepancies in the literature concerning the electronic structure of the K adlayer. In particular, a new assignment of the K-induced states near the Fermi level is proposed.     

The Fermi matrix elements inferred from β-γ(CP) correlation measurements in Fe decay

Measurements have been made of the β-γ circular-polarization correlation paramter A for the 273 keV β-branch in the decay of ⁵⁹Fe. It has recently been established that each of the principal β-branches of ⁵⁹Fe involves ΔJ=0 and thus has a possible non-zero Fermi matrix element M_F which can be determined from the ƒt value and A. Previous β-γ (_CP) measurements on this nucleide have all employed the usual γ-ray scattering technique. This method is suitable for the 475 keV β-branch but does not produce an accurate measurement of the lower energy branch because of energy discrimination difficulties. A transmission polarimeter with γ-discrimination has been used in the present work to obtain clean data on the 273 keV β-1.29 MeV γ-cascade. Calibration with ⁶⁰Co (1.33 MeV) and ²⁸Al (1.79 MeV) yielded A = −0.154±0.023. This gives for the isospin impurity coefficient and the effective Coulomb matrix element of the 1.29 MeV state (1.1±1.4) × 10⁻³ and 9±11 keV, respectively.     

Effect of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge

Single-walled carbon nanotubes (SWCNTs) have been synthesized in high yield by the dc arc discharge technique under heat-pretreatment of the graphite rod conditions. Before executing arc discharge, the graphite rods containing the catalysts were heat treated at 600, 700, 800 and 900 °C for 1–3 h, respectively. Effects of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge were investigated. The heat-treatment temperature and time were found to be crucial for a high yield of high-purity SWCNTs. Optimum parameter was found to be at the heat-treatment temperature of 800 °C for 2 h. The SWCNTs synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.9 V/μm and the threshold field where current density reaches 10 mA/cm² is 3.9 V/μm.     

Final-state hyperon-nucleon interaction in the inclusive K photoproduction from the deuteron

We calculate d(γ, K⁺) inclusive cross sections with the full inclusion of the final ΛN - ΣN interaction. Modern hyperon-nucleon forces and a recently updated production operator for the γ + N → K⁺ + Y process are used. Significant effects of the hyperon-nucleon final-state interaction have been found especially around the K⁺ΣN threshold.     

Intergranular properties of YBCO and BSCCO ceramic superconductors at low fields

Isothermal low-field AC susceptibility measurements have been used to analyze the intergranular critical current density J_c(T) on sintered, non-oriented YBa₂Cu₃O_7−δ and Bi₂Sr₂CaCu₂O_8+δ ceramic samples at zero field. Below the critical temperature, potential variations, J_c(T) ≈ (1−t_j)^m with t_j = T/T_j, have been found, T_j being the onset of grain's coherence, but with different exponents, supporting that different mechanisms limit the intergranular J_c values. Moreover, the effect of texture has been also considered on Bi₂Sr₂CaCu₂O_8+δ ceramics grown by the laser floating zone method, which have stronger intergranular junctions. Their high-temperature behaviour is limited by intrinsic effects, while at low temperatures the quality of the junctions is the limiting factor. The temperature dependence of the χ′(h₀) extrapolation at zero filed has also been correlated with the evolution of the intergranular penetration depth, λ_J(T).     

Energy levels of Kr populated by Br decay

The γ-rays following the β-decay of ⁸²Br have been investigated using a 220 mm³ Ge(Li) detector, an anti-Compton NaI(Tl) spectrometer and a two-dimensional coincidence arrangement. The ⁸²Br was produced by thermal neutron activation of ammonium bromide. The presence of eight, well-known and 11 weak γ-rays has been established. It has been shown through half-life measurements that the newly identified γ-rays belong to ⁸²Br decay and that the high-energy peaks are not to summing effects. All the reported transitions have been incorporated in a level scheme of ⁸²Kr by introducing levels at 0, 776, 1474, 1820, 1953, 2093, 2426, 2554, 2647 and 2828 keV. Limits on probable spin and parity values for the newly-introduced levels have been established. The level introduced at 2828 keV on the basis of a 1008–1043 keV γγ-coincidence must be fed by a weak β-branch of ⁸²Br with an end-point energy of 263 keV and log ft of approximately 6.1.     

Coherent and incoherent η-photoproduction from nuclei

Elastic and inelastic η-photoproduction from complex nuclei is studied in a distorted-wave impulse approximation (DWIA) framework. The elementary operator is obtained by using a dynamical model which employs the reactions πN→πN, πN→ππN and π⁻p→ηn to fix the hadronic vertex as well as the isobar propagators and the process γN→πN to constrain the electromagnetic vertex. The nuclear structure input for the inelastic transitions has been extracted from electron-scattering form factors. The η final-state interaction has been included via a simple optical potential using the ηN t-matrix as an input. We find that coherent η-production is dominated by the D₁₃(1520) isobar while spin-flip transitions to excited nuclear states are sensitive to the S₁₁(1535) resonance. Predictions are given for coherent production on ⁴He, ¹²C and ⁴⁰Ca, as well as incoherent production on ⁶Li, ¹⁰B and ¹²C.     

Magnetic moment of the Δ (1232) resonance

The reaction γp → π^°γ′p has been measured with the TAPS BaF₂ calorimeter at the Mainz Microtron accelerator facility MAMI for energies between √2 = 1221–1331 MeV. Cross sections differential in angle and energy have been determined for the photon γ′ in three bins of the excitation energy. This reaction channel provides access to the magnetic dipole moment of the Δ⁺(1232) resonance and, for the first time, a value of μ_Δ+ = (2.7^+1.0_−1.3(stat) ± 1.5(syst) ± (theor)) π_N has been extracted.     

Interaction between CO and NH3 coadsorbed on Ru(001): its effects on the ordering in mixed adlayers and the ammonia dissociation

The coadsorption of CO and ammonia on Ru(001) has been investigated by low-energy electron diffraction (LEED), temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). The main focus has been on the interaction between different admolecules on the surface and its important role in surface reaction. Exposing CO-precovered Ru(001) to ammonia at 100 K leads to the formation of mixed ordered layers with a (2 × 2) periodicity. It was found that two types of (2 × 2) structures are formed depending on the CO precoverage. One of the (2 × 2) structures (-phase) contains one CO and two ammonia molecules per (2 × 2) unit cell and the other (β-phase) contains two CO and one ammonia. Structure models for the two phases are proposed based on vibrational spectra measured for the coadsorbed phases of CO and ammonia (¹⁵NH₃ or ND₃). TPD results suggest that the ammonia dissociation takes place on clean and CO-precovered Ru(001). The amount of dissociated ammonia decreased initially with increasing CO precoverage, passed a minimum at θ_CO = 0.25, increased with a further increase of CO coverage, and eventually reached a saturation value above θ_CO = 0.5. The dissociation of ammonia in the β−(2 × 2) structure was found to be enhanced by a factor of 4–6 as compared with the dissociation in the −(2 × 2) structure. The HREEL spectra indicated that the C_3v molecular axis of ammonia is tilted in the coadsorbed layers, the tilting being most pronounced in the β−(2 × 2) phase with a high CO partial coverage. This observation suggests that the tilting of ammonia due to the interaction with CO facilitates electron donation from Ru 4d to LUMO of ammonia, leading to the N-H bond dissociation. The microscopic model for the CO-NH₃ interaction on metal surfaces is presented.     

The interaction of oxygen and potassium on the Ru(001) surface

The interaction of oxygen and different coverages of potassium on Ru(001) has been investigated by thermal desorption spectroscopy (TDS), metastable quenching spectroscopy (MQS), electron stimulated desorption spectroscopy (ESD), and work-function change measurements. The results show that this is a complex surface system with several different oxides forming, depending on the surface stoichiometry and temperature. While we cannot uniquely identify all the surface species, our interpretation of the present data combined with previous information is as follows. For potassium coverages up to about three monolayers (θ_K ≈ 1), exposure to oxygen initially gives oxygen atoms on the surface. Further exposure produces some surface monoxide ions O²⁻, which are converted with additional exposure to Superoxide ions O⁻₂ and possibly peroxide ions O²⁻₂. Thermal annealing causes strong changes in the surface oxide composition, and with potassium multilayers (θ_K ≈ 10) all the oxides diffuse beneath the K surface layer with annealing to only 300 K. K₂O and K₂O₂ are found to desorb together in the 600–700 K region.     

Study of the interfacial structure and chemistry of CVD κ-Al2O3/TiC multilayer coatings

This article describes the interfacial regions in CVD grown TiC/κ-Al₂O₃ multilayers. A number of microanalytical techniques were used including HREM, EDX and EELS. Occasionally, the first 50 nm of the alumina layers deposited on the intermediate TiC layers grew as a cubic alumina, heavily faulted, containing small amounts of sulphur (S), maybe as a stabiliser. The presence of slightly rounded TiC (111) facets may act as preferred nucleation sites for the cubic Al₂O₃ phase, with a ‘cube on cube’ orientation relationship. In this way the nucleation of κ-Al₂O₃ is less favourable. After some tens of nanometres the cubic phase cannot be stabilised any longer and the layer continues to grow as κ-Al₂O₃. A number of observations point towards the reaction zone (RZ) being η- and/or γ-Al₂O₃. The diffraction work and the FFT analysis of the HREM images show that the RZ is an fcc phase with a=7.9 Å, which matches with η- and γ-Al₂O₃. The EELS Al fine structure indicate more tetrahedral Al ions than in κ-Al₂O₃, as in η- and γ-Al₂O₃. The RZ contains small amounts of S, as has been reported for γ-Al₂O₃. Due to the structural similarities between η- and γ-Al₂O₃ it was not possible to determine which of these cubic phases is present in the RZ.     

Experimental study and calculations of nitric oxide absorption in the γ(0,0) and γ(1,0) bands for strong temperature conditions

Absorption spectra of nitric oxide in the γ(0,0) and γ(1,0) bands have been measured for hard temperature conditions up to 1700 K in order to validate a model for the simulation of these two bands. The good agreement between experiments and calculations (relative errors of 2–5% for the γ(0,0) band and 10–15% for the γ(1,0) band) consolidates the two important assumptions concerning the intermediate Hund's case between (a) and (b) for the X²Π state of the γ(0,0) and γ(1,0) absorption bands and the use of collisional broadening parameters of γ(0,0) to simulate the γ(1,0) band. Using this simulation, a study of the Beer–Lambert law behavior at high temperature has been carried out. With the instrument resolution used for these experiments, it was shown that a correction of the Beer–Lambert law is necessary. To apply this technique for the measurements of NO concentrations inside the combustion chamber of an optical SI engine, a new formulation of the Beer–Lambert law has been introduced, since the modified form proposed in the literature is no longer applicable in the total column range of interest.     

Imaging benzene on nickel and copper {110} surfaces with low temperature STM:: the adsorption site

Single benzene molecules have been imaged on the {110} surfaces of both copper and nickel with an Eigler-type low temperature scanning tunnelling microscope. Conditions were chosen such that the molecule and the lattice atoms could be resolved at the same time within one image frame. On Ni{110} benzene was found to adsorb in the hollow site between the close-packed rows. For the more weakly bound molecule on Cu{110} the imaging conditions had to be changed since, for the tunnelling conditions under which the lattice atoms are resolved, a strong interaction between the tip and the benzene takes place. This results in the molecule being “dragged” along the surface. By changing the tunnelling conditions within one image frame, however, it is possible via extrapolation of the substrate lattice to show that the molecule adsorbs in the long-bridge site. The shapes of the images of individual molecules are discussed.     

Intensified dissolution of uranium from graphite substrate using ultrasound

Decontamination of graphite structural elements and recovery of uranium is crucial for waste minimization and recycle of nuclear fuel elements. Feasibility of intensified dissolution of uranium-impregnated graphite substrate using ultrasound has been studied with objective of establishing the effect of operating parameters and the kinetics of sonocatalytic dissolution of uranium in nitric acid. The effect of operating frequency and acoustic intensity as well as the acid concentration and temperature on the dissolution of metal has been elucidated. It was observed that at lower acid concentrations (6 M–8 M), the dissolution ratio increases by 15% on increasing the bath temperature from 45 to 70 °C. At higher acid concentration (>10 M), the increase was only around 5–7% for a similar change in temperature. With 12 M HNO₃, pitting was also observed on the graphite surface along with erosion due to high local reaction rates in the presence of ultrasound. For higher frequency of applied ultrasound, lower dissolution rate of uranium was observed though it also leads to high rates of erosion of the substrate. It was thus established that suitable optimization of frequency is required based on the nature of the substrate and the choice of recycling it. The dissolution rate was also demonstrated to increase with acoustic intensity till it reaches to the maximum at the observed optimum (1.2 W/cm² at 33 kHz). Comparison with silent conditions revealed that enhanced rate was obtained due to the use of ultrasound under optimum conditions. The work has demonstrated the effective application of ultrasound for intensifying the extent of dissolution of metal.     

Band structures of Se and Se

Band structures of ⁷⁶Se and ⁷⁸Se have been studied with the ^74,76Ge(, 2nγ)^76,78Se reactions by using a variety of in-beam γ-techniques : γ-ray singles spectra, γ-ray excitation functions, γ-γ-t coincidences, γ-ray angular distributions and γ-ray linear polarizations.

Spins and parities have been assigned uniquely for many new levels in ⁷⁶Se and ⁷⁸Se and four bands have been identified in both nuclei: (i) the ground-state band, (ii) a positive-parity ΔJ = 1 band built on the second 2⁺ state (γ-vibrational band), (iii) a negative-parity Δ J = 2 band built on the 3⁻ state (octupole band) and (iv) a ΔJ = 2 band built on the high-lying J = 4 state. In addition, the second 8 ⁺ and 10⁺ states, which are possibly the lowest members of a band, have been found in both nuclei.

Systematics of the band structures obtained are discussed. Level energies of the band members and B(E2) ratios for some of the inter-band transitions between γ- and ground-state bands have been calculated with the proton-neutron interacting boson model IBM-2 and a reasonable agreement with the present data has been obtained.