Highly durable Pd metal catalysts for the oxygen reduction reaction in fuel cells; coverage of Pd metal with silica

Pd cathode catalysts for polymer electrolyte fuel cells have been covered with silica layers a few nanometres thick. The silica-coated Pd catalysts showed high activity and excellent durability for the oxygen reduction under the severe cathode conditions of PEFCs, while Pd catalysts without silica-coating were seriously deactivated under the same conditions. The coverage of Pd metal with silica prevents the diffusion of Pd species out of the silica layers.     

Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.     

Determination of 13C concentration in biological materials using infrared absorption method

Tracer experiments on the transfer of carbon from culture solution to Daphnia magna through phytoplankton have been carried out using ¹³C and infrared absorption method. The purpose of this experiment is to investigate the experimental systems for the use of ¹³C in aquatic system. Daphnia magna was cultured in a 100 ml of solution containing phytoplankton and 20 mg of NaH¹³CO₃ for 24 hours in the light and dark conditions (2000 lux, 14 hour light and 10 hours dark at 25 C). The concentration of ¹³C in Daphnia magna under light condition was about 2.0% (atom% excess), while in the dark condition ¹³C tracer was not detected. The concentration of ¹³C in phytoplankton under light condition was around 20%. It was suggested that ¹³C added as carbonate in the culture solution was photosynthetically assimilated by phytoplankton and then transferred to Daphnia magna. Using this system, the effect of UV-B exposure on the ¹³C uptake of Daphnia magna has been examined. The UV-B intensity was 95 mW/cm² and exposure time was 15, 30, and 60 minutes. The concentration of ¹³C in Daphnia magna decreased with increasing exposure time. The Daphnia magna exposed to UV-B for 15 minutes intakes phytoplankton as much as control, while 30 minutes and 60 minutes exposures were lower than control. The lower concentrations of ¹³C observed in Daphnia magna were due to less intake of phytoplankton caused by the UV-B exposure.     

Short communication: An alternative and effective catalyst for the silastannation of arylacetylenes with Me3SiSnBu3 at room temperature

The palladium‐catalyzed silastannation of acetylenes with tributyl(trimethylsilyl)stannane in the presence of triethylphosphite is reported for the first time. The reaction occurs at room temperature to give (Z)‐silyl(stannyl)ethenes in high yields. The protodemetallation of the resulting adducts with HCl–tetraethylammonium chloride is described first, which demonstrates that the reaction is governed only by the stability of a carbonium ion arising from the protonation to (Z)‐silyl(stannyl)ethenes rather than the hard and soft acid and base principle, i.e. the β‐cation stabilization effect (σ–π stabilization one) of a stannyl group in the carbonium ion is rather significant. Copyright © 2004 John Wiley & Sons, Ltd.     

On the volume and surface area of hyperbolic polyhedra

A truncated tetrahedron is a building block of hyperbolic 3-manifolds with totally geodesic boundary. We study the relation between the volume of a truncated tetrahedron and the area of its faces which form the boundary of manifolds.     

Determination of diltiazem hydrochloride enantiomers in dog plasma using chiral stationary-phase liquid chromatography

The separation and determination of d- and l-diltiazem hydrochloride in dog plasma by a two-column high-performance liquid chromatographic technique are described. Diltiazem hydrochloride and its metabolites were extracted from dog plasma and analyzed on a conventional column (Nucleosil 5C18) with a volatile buffer system. The column effluent of diltiazem hydrochloride was collected and evaporated. The enantiomeric ratio of the collected diltiazem was determined using a chiral column (Chiralcel OC). The method was accurate and sensitive.     

Effect of Comatic Aberration on the Propagation Characteristics of Laguerre--Gaussian Beams

Seidel comatic aberration is an important cause of deformation for a Laguerre--Gaussian (LG) beam. In addition, mono-axial comatic aberration, whose phase modulation depends only on one transverse coordinate, is also an important cause of beam deformation. Deformation of an LG beam by such aberrations is analyzed through numerical simulation based on the angular spectrum method. It is also shown that for holographically generated LG beams quadratic spatial variation of grating pitch can produce seidel and mono-axial comatic aberrations. An example of an experimentally generated LG beam with mono-axial comatic aberration is reported.     

Weak coupling in the upper part of thesd-shell and α-clustering in38Ar

It is suggested that weak coupling picture for theα-cluster states holds not only in the⁴⁴Ti～⁴⁰Ca region but also in the upper part of thesd-shell region. To confirm this experimentally, theα-clustering aspects of³⁸Ar is investigated.