Quasi in situ Ni K‐edge EXAFS investigation of the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant

Ni species on the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant were studied by Ni K‐edge EXAFS and TEM measurement without contact of the catalysts with air. The Ni–Mo coordination shell related to the Ni–Mo–S phase was observed in the spent catalyst by quasi in situ Ni K‐edge EXAFS measurement with a newly constructed high‐pressure chamber. The coordination number of this shell was almost identical to that obtained by in situ Ni K‐edge EXAFS measurement of the fresh catalyst sulfided at 1.1 MPa. On the other hand, large agglomerates of Ni₃S₂ were observed only in the spent catalyst by quasi in situ TEM/EDX measurement. MoS₂‐like slabs were sintered slightly on the spent catalyst, where they were destacked to form monolayer slabs. These results suggest that the Ni–Mo–S phase is preserved on the spent catalyst and Ni₃S₂ agglomerates are formed by sintering of Ni₃S₂ species originally present on the fresh catalyst.     

The molecular symmetry group of the CO dimer and the assignments of the intermolecular vibrations

Vibrational assignments for some of the lowest energy levels of the CO dimer have been derived purely spectroscopically on the basis of the molecular symmetry, nuclear spin statistics, observed selection rules, and sequence of the transition doublets. Most of the previous assignments of Surin et al. [L.A. Surin, D.N. Fourzikov, T.F. Giesen, S. Schlemmer, G. Winnewisser, V.A. Panfilov, B.S. Dumesh, G.W.M. Vissers, A. van der Avoird, J. Phys. Chem. A 111 (2007) 12238-12247] are confirmed in the present work, and are supported by much clear evidences. One significant revision of that analysis in the present work is identification of the torsional (out-of-plane) excited state, which had been assigned previously to an excited state of the geared (in plane) internal rotation.     

High-precision sample stage for photoemission microscopy of organic films

A high-precision sample stage for photoemission microscopy has been constructed to translate the sample by ±3 mm with accuracy better than 100 nm. The stage is actuated by step motors settled outside the vacuum. The accuracies of the translations were measured by observing a standard patterned sample with a photoemission electron microscope (PEEM) of 50 nm resolution. The accuracy was nearly independent of the distance of each translation step and the error was not accumulated by repeated steps. After round-trip translations up to 0.2 mm, the sample came back to the original position with accuracy of ±50 nm. The performance of the stage was demonstrated by observing growth processes of lead phthalocyanine (PbPc) films formed on graphite.     

Numerical analysis on auto-ignition of a high pressure hydrogen jet spouting from a tube

In this study, a direct numerical simulation based on compressible flow dynamics has been applied to the autoignition and extinction of a high-pressure hydrogen jet spouting from a tube. The diameter of the tube is 4.8 mm. The length of the tube is 71 mm. At the inlet, pressure is set at 3.6, 5.3 and 21.1 MPa, and temperature is set at 300 K for all cases. To explore the autoignition of hydrogen jet, two-dimensional axisymmetric Navier–Stokes equations with a detailed chemical kinetics and rigorous transport properties have been employed. The hydrogen jet through the tube is choked. The numerical results show that the high-pressure hydrogen jet produces a semi-spherical shock wave in the ambient air at the early time of jetting. The shock wave heats up the air to a high temperature and causes the autoignition of the hydrogen and air mixture in the tube as well as at the tube exit.     

Electrical properties and memory effect in the field effect transistor based on organic ferroelectric insulator and pentacene

We have fabricated a field effect transistor (FET) based on an organic ferroelectric insulator and molecular conductor, and investigated the electrical properties and memory effects on the PEN-FET. We have observed a drastic change in the drain current at around the coercive electric fieldE _c of the organic ferroelectric insulator in not only a FET (PEN-FET) based on a pentacene (PEN) film but also a FET (IPEN-FET) based on an iodine doped PEN film. The magnitude of the change of the drain current for the IPEN-FET is 200 times larger than that for the PEN-FET. It is expected from these results that the PEN-FET (especially the IPEN-FET) is an improvement in such devices, since it operates at a low gate electric field accompanied by the appearance of the spontaneous polarization in the organic ferroelectric insulator. In addition, we have found that the drain current for the PEN-FET does not return to the initial drain current ofE _G =0 V/cm for more than one week, even if the gate electric field is changed to 0 V/cm from 500 V/cm(>E _c ). From these results, it is suggested that the PEN-FET becomes a memory device.     

Quasi-distribution of tunneling time

Using real time Feynman histories, a quasi-distribution of tunneling time Q(τ) is introduced. For the tunneling time of resident time type, an explicit expression for Q is shown for square barriers. Q becomes oscillatory as the barrier becomes opaque. Some well-known tunneling times fall within the range of τ where Q takes non-negligible values. The formal “average” and the “variance” of the tunneling time are found to be related to known tunneling times. It is thus demonstrated that the quasi-distribution extracts the temporal information about tunneling from real time Feynman histories.     

CEMS Study on Fe Films Deposited by Laser Ablation

Iron thin films deposited on Al foil by pulsed laser ablation were characterized by conversion electron Mössbauer spectrometry (CEMS). The hyperfine fields became large and the isomer shift was closed to that of bulk α-Fe with increasing the thickness of deposited films. The small grains are so reactive that small particles of Fe^III oxides were produced in thin deposited layers. The magnetic orientation of the deposited films became from parallel to in-plane to at random. The small grains were considered to grow by aggregating with ablation time.

     

Instrumental Requirements for Non-Invasive Blood Glucose Measurement Using NIR Spectroscopy

The magnitude of spectral change in blood glucose measurements with diffuse reflectance spectroscopy is investigated. Spectral change is estimated by simulation of light propagation in skin tissue and measurements of absorbance spectra of aqueous glucose solution. Required sensitivity of spectrophotometers for monitoring change in the blood glucose concentration as small as 10 mg/dL has been obtained using the estimated change in the absorbance spectrum and mean pathlength of light in tissue.     

Photoinduced intramolecular electron-transfer reactions in carbazole-fullerene and phenothiazine-fullerene linked compounds in benzene and benzonitrile as studied by fluorescence, transient absorption, time-resolved EPR, and magnetic field effects

Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C₆₀) (Cz(8)C₆₀) and phenothiazine (Ph)-C₆₀ (Ph(n)C₆₀ (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C₆₀ (¹C₆₀ ^*) occurred in Cz(8)C₆₀, but not to the triplet excited state (³C₆₀ ^*), while the intramolecular electron-transfer to both¹C₆₀ ^* and³C₆₀ ^* occurred in Ph(n)C₆₀ (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both¹C₆₀ ^* and³C₆₀ ^* took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents.