Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques

There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation.     

Effects of ionic dissociation of membrane polymer on pervaporation performance

Pervaporation of a water/alcohol mixture through a membrane which has ion-exchange capacity has been investigated. Theoretical equations are introduced which relate the degree of ionic dissociation of the polymer to quantities of water and alcohol dissolved in the polymer. From these equations, an equation for selective dissolution R is derived which does not contain an explicit term for ionic dissociation. Dissociation affects selective dissolution only by changing the degree of swelling of the polymer. Reformulating R asymptotically obtains a reciprocal relationship between permselectivity and permeability for a water-selective membrane. Experiments to check the validity of the relationship have been carried out using chitosan membranes neutralized by several acids. The effect of degree of neutralization also has been investigated. Results can be well understood on the supposition that ionic dissociation depends upon the water/alcohol composition, the kind of acid, and the degree of neutralization. Experimental results indicate that the reciprocal relationship is maintained over an appropriate range of feed compositions which confirm the validity of the theoretical equations for the swelling equilibrium of an ionic membrane. © 1994 John Wiley & Sons, Inc.     

Electrical and optical properties of chalcogenide amorphous semiconductors modified with Ni

The electrical and optical properties of the chalcogenide semiconductor (Se₃₂Te₃₂As₄Ge₃₂)_100?xNixitx have been studied. As the Ni concentration is increased the electrical dc conductivity is drastically increased and variable range hopping conduction becomes dominant even above room temperature. The optical energy gap decreases with the Ni concentration from 1.18–0.95 eV. Ni-atoms in the chalcogenide semiconductor donate free electrons which occupy the gap state. This occupation causes the shift of the Fermi level toward the conduction band. It is an effect of this shift that the thermal activation energy is decreased. The decrease in optical energy gap is independent of the shift of the Fermi level and is ascribable to the appearance of the additional level located at 0.95 eV above the top of the valence band. This level originates from the 3d-level of the Ni-atom.     

Layer-by-layer electrodeposition of copper in the presence of o-phenanthroline, caused by a new type of hidden NDR oscillation with the effective electrode surface area as the key variable

Electrochemical deposition of copper (Cu) from aqueous acidic Cu2+ solutions with o-phenanthroline (o-phen) shows both potential and current oscillations, together with a (partially hidden) N-shaped negative differential resistance (N-NDR), indicating that the oscillations are classified into hidden N-NDR (or HN-NDR) oscillations. The color and the surface morphology of Cu deposits oscillate in synchronization with the potential and current oscillations. Microscopic inspection has shown that dense round Cu leaflets, which look gray, grow in the positive side of the potential oscillation or in the high-current state of the current oscillation, whereas thin Cu leaflets, which look black, grow in the opposite-side stages of the potential and current oscillations, thus finally resulting in a layered Cu deposit with the layer thickness of about 5 microm. The appearance of the NDR is explained to be due to adsorption of the reduced form of a [Cu(II)(o-phen)2]2+ complex, which suppresses the Cu electrodeposition. The increase in the effective electrode surface area by growth of thin Cu leaflets, on the other hand, causes a current increase that can hide the NDR. This NDR-hiding mechanism is of a new type and the present oscillation is regarded as a new-type of HN-NDR oscillator.     

Efficient synthesis of poly(phenylazomethine) dendrons allowing access to higher generation dendrimers

We have developed a novel synthetic method of phenylazomethine dendrons that uses 4,4'-methylenedianiline instead of 4,4'-diaminobenzophenone to synthesize the precursor of the phenylazomethine dendron and then oxidized the precursor to the next-generation dendron. For this method, the productivity of the dendrons has been significantly increased. Furthermore, as the synthesis of high-generation dendrons becomes easier, synthesis of DPA G5 was achieved. [structure--see text]