Investigation on the arrangement of lithium ions in LixLa(1/3)NbO3 with perovskite structure

The relationship between the Li arrangement and the electrochemical behavior has been examined as a function of composition x in electrochemically lithiated A-site deficient perovskite, Li(x)()La(1/3)NbO(3). The cell potential diagram and powder X-ray diffraction (XRD) study indicated that the Li ions are inserted into the vacant Perovskite A-site with an electrochemical reaction. In addition, the derivatives of the cell potential diagram showed three cathodic peaks, indicating a stepwise Li insertion mechanism takes place. Such a stepwise behavior would be ascribed to the changes in arrangement of inserted Li ions in the Perovskite lattice, since the XRD patterns of pristine La(1/3)NbO(3) showed that the La arrangement in La(1/3)NbO(3) was ordered along the c-axis, causing two kinds of A-site vacancies. To reveal the changes in the arrangement of Li ions, the entropy measurement of the reaction was performed by both the electrochemical and the calorimetric techniques. Moreover, the formation energy of the Perovskite structure with various Li arrangements was compared by using an ab initio calculation. The results of experiment and computation suggested that the electrochemical reaction proceeded via two kinds of superstructures of Li(1/6)La(1/3)NbO(3) and Li(1/2)La(1/3)NbO(3) due to the ordered arrangement of Li ions.     

Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate-loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic-absorption spectrometry

A rapid column-adsorption method has been developed for concentrating traces of copper, cadmium, and lead in water prior to their determinations by graphite-furnace atomic-absorption spectrometry. The adsorbent used was prepared by loading a strongly basic anion-exchanger QAE-Sephadex A-25 (50 mg) with thiacalix[4]arenetetrasulfonate (20 mol). Two-hundredfold preconcentration of the analyte elements was achieved by passing 100 mL of sample solution (pH 8.0) through a column packed with the adsorbent (6 mm i.d.×7 mm high) at a flow rate of 10 mL min^–1 and by the subsequent elution with 500 L of aqueous nitric acid solution (1 mol L^–1). The practical applicability of the proposed method was evaluated by analyzing certified reference seawater samples.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

The effect of iron spin transition on electrical conductivity of (Mg,Fe)O magnesiowüstite

We measured the electrical conductivity of Mg_0.81Fe_0.19O magnesiowüstite, one of the important minerals comprising Earth’s lower mantle, at high pressures up to 135 GPa and 300 K in a diamond-anvil cell (DAC). The results demonstrate that the electrical conductivity increases with increasing pressure to about 60 GPa and exhibits anomalous behavior at higher pressures; it conversely decreases to around 80 GPa and again increases very mildly with pressure. These observed changes may be explained by the high-spin to low-spin transition of iron in magnesiowüstite that was previously reported to occur in a similar pressure range. A very small pressure effect on the electrical conductivity above 80 GPa suggests that a dominant conduction mechanism changes by this electronic spin transition. The electrical conductivity below 2000-km depth in the mantle may be much smaller than previously thought, since the spin transition takes place also in (Mg,Fe)SiO₃ perovskite.     

Effects of atomic-scale contacts on transport properties through single molecules - ab initio study

Using the RTM/NEGF method, which is a first-principles calculation tool for the quantum transport through nanostructures between electrodes, we study the effects of atomic-scale contacts on the transport properties through single molecules. Electronic states and current-voltage (I-V) characteristics are investigated in various contact conditions with and without single molecules between electrodes. We find that similar nonlinear behaviors appear in the I-V characteristics. Such nonlinear behaviors are determined not only by the HOMO-LUMO electronic states of single molecules between electrodes, but also by the atomic-scale contact conditions. We show that the transitions from tunneling to ballistic regimes affect the I-V characteristics significantly.     

Time-dependent wave-packet approach to the quantum transport of carbon nanotubes with vacancies

We investigate the vacancy effect on the electronic transport properties of the (5,5)-metallic and (5,0)-semiconducting carbon nanotubes using the time-dependent wave-packet approach based on the Kubo-Greenwood formula within the tight-binding approximation. We found that the metallic and semiconducting carbon nanotubes show different electronic transport properties for the states created by vacancies.     

Ellipsometry characterization of a-Si:H layers for thin-film solar cells

In order to determine microscopic structures of hydrogenated amorphous silicon (a-Si:H) layers incorporated in a-Si:H-based thin-film solar cells, the spectroscopic ellipsometry (SE) analysis of a-Si:H layers prepared by plasma-enhanced chemical vapor deposition has been performed. In particular, we have characterized the a-Si:H layers by applying a new dielectric function model that allows the evaluation of the SiH₂ bond densities in a-Si:H networks. This model is based on our finding that the a-Si:H dielectric functions in the visible/ultraviolet region vary systematically with the formation of SiH₂-clustered microvoids. We have applied this model to estimate the SiH₂ content in a-Si:H layers fabricated on glass substrates, on which the characterization of the SiH₂ bonding is generally difficult. The validity of the SE analysis has been confirmed from the direct characterization of the SiH_n local structures using infrared ellipsometry.