Evidence of Nonelectrochemical Shift Reaction on a CO-Tolerant High-Entropy State Pt-Ru Anode Catalyst for Reliable and Efficient Residential Fuel Cell Systems

A randomly mixed monodispersed nanosized Pt-Ru catalyst, an ultimate catalyst for CO oxidation reaction, was prepared by the rapid quenching method. The mechanism of CO oxidation reaction on the Pt-Ru anode catalyst was elucidated by investigating the relation between the rate of CO oxidation reaction and the current density. The rate of CO oxidation reaction increased with an increase in unoccupied sites kinetically formed by hydrogen oxidation reaction, and the rate was independent of anode potential. Results of extended X-ray absorption fine structure spectroscopy showed the combination of N(Pt-Ru)/(N(Pt-Ru) + N(Pt-Pt)) ? M(Ru)/(M(Pt) + M(Ru)) and N(Ru-Pt)/(N(Ru-Pt) + N(Ru-Ru)) ? M(Pt)/(M(Ru) + M(Pt)), where N(Pt-Ru)(N(Ru-Pt)), N(Pt-Pt)(N(Ru-Ru)), M(Pt), and M(Ru) are the coordination numbers from Pt(Ru) to Ru(Pt) and Pt (Ru) to Pt (Ru) and the molar ratios of Pt and Ru, respectively. This indicates that Pt and Ru were mixed with a completely random distribution. A high-entropy state of dispersion of Pt and Ru could be maintained by rapid quenching from a high temperature. It is concluded that a nonelectrochemical shift reaction on a randomly mixed Pt-Ru catalyst is important to enhance the efficiency of residential fuel cell systems under operation conditions.     

Theory of particle transport phenomena during fatigue and time-dependent fracture of materials based on mesoscale dynamics and their practical applications

In this work, the mesoscale mechanics of metals, which links their microscopic physics and macroscopic mechanics, was established. For practical applications, the laws for quantitatively predicting life of cycle and time-dependent fracture behavior such as fatigue, hydrogen embrittlement, and high-temperature creep were derived using particle transport phenomena theories such as dislocation group dynamics, hydrogen diffusion, and vacancy diffusion. Furthermore, these concepts were also applied for estimating the degree of viscoelastic deterioration of blood vessel walls, which is dominated by a time-dependent mechanism, and for the diagnosis of aneurysm accompanied by the viscoelastic deterioration of the blood vessel wall. In these theories, new mechanical indexes were derived as dominant factors for predicting the life of fatigue crack growth and the time-dependent fracture of notched specimens of materials such as hydrogen embrittlement and high-temperature creep. Furthermore, as an example of a practical application, these theories were applied to estimate the degree of viscoelastic deterioration and chaotic motions of blood vessel walls, which are closely related to blood vessel diseases such as atherosclerosis and aneurysm. Moreover, new indexes to diagnose them were also proposed for clinical applications.     

Novel stability condition for delayed fractional-order composite systems based on vector Lyapunov function

Nonlinear Dynamics - This paper proposes a novel stability condition for delayed fractional-order composite systems. First, we extend the vector Lyapunov function to the fractional-order systems to...     

Presence of β-Turn Structure in Recombinant Spider Silk Dissolved in Formic Acid Revealed with NMR

Spider dragline silk is a biopolymer with excellent mechanical properties. The development of recombinant spider silk protein (RSP)-based materials with these properties is desirable. Formic acid (FA) is a spinning solvent for regenerated Bombyx mori silk fiber with excellent mechanical properties. To use FA as a spinning solvent for RSP with the sequence of major ampullate spider silk protein from Araneus diadematus, we determined the conformation of RSP in FA using solution NMR to determine the role of FA as a spinning solvent. We assigned ¹H, ¹³C, and ¹⁵N chemical shifts to 32-residue repetitive sequences, including polyAla and Gly-rich regions of RSP. Chemical shift evaluation revealed that RSP is in mainly random coil conformation with partially type II β-turn structure in the Gly-Pro-Gly-X motifs of the Gly-rich region in FA, which was confirmed by the ¹⁵N NOE data. In addition, formylation at the Ser OH groups occurred in FA. Furthermore, we evaluated the conformation of the as-cast film of RSP dissolved in FA using solid-state NMR and found that β-sheet structure was predominantly formed.     

Variation of the speckle contrast in a graded-index fibre by misalignment of the incident beam

The speckle pattern observed at the output end of a multimode fibre is closely related to the modal noise. In this paper, the average contrast of the speckle pattern is studied as a function of the radial position in the output end plane for three kinds of misalignment of the incident beam, i.e. defocusing, axial misalignment and angular misalignment. It is found that a variation of the speckle contrast is very sensitive to all kinds of misalignment of the incident beam and that its varying form strongly depends on the kind of misalignment of the incident beam. The speckle contrast at the centre of the output end plane is also examined as a function of the magnitude of misalignment. It is found that the contrast increases from a minimum value in the correct alignment to a certain saturated value with an increase of misalignment.     

13C NMR spectra of tricyclo[4.2.1.02,5]nonanes and tetracyclo[5.4.1.02,6.08,11]dodecanes

The ¹³C NMR spectra of tricyclo[4.2.1.0^2,5]nonanes and tetracyclo[5.4.1.0^2,6.0^8,11]dodecanes and their dimethyl derivatives were measured to demonstrate the four-membered ring annelation effects on the bicyclo[2.2.1]heptane skeleton, and the steric δ-syn effects of the methyl groups attached to the four-membered ring on the bridge carbons in these systems.     

Measurements of the velocity gradient using a laser Doppler phenomenon

This paper reports on a method for measuring the velocity gradient using a laser Doppler phenomenon. The velocity gradient is determined from the velocity difference between two different points of the probing object and is actually obtained from the optical heterodyning of two differently Doppler-shifted scattered light fields from two points of the object having different velocities. The properties of output beat signals are theoretically investigated from their spectral broadening including the effect of the detecting aperture. The preliminary experiment was performed by using a rotating glass disk whose velocity is different from its center to the outside. The experimental results shows the usefulness of the present method for measurements of the velocity gradient.     

Anomalous photoluminescence and raman scattering behavior in heavily Mg+ ion-implanted InP

Mg⁺ ions were implanted into highly pure InP grown by the liquid encapsulated Czochralski (LEC) method in which the Mg concentration [Mg] was varied between 1×10¹⁵ cm^–3 and 3×10²⁰ cm^–3. Two annealing methods were used: furnace annealing (FA) up to 740° C and flash lamp annealing (rapid thermal annealing, RTA) up to 900° C. For characterization, photoluminescence (PL) spectra were measured between 2K and room temperature together with Raman scattering measurements at room temperature. An emission designated by g, which was attributed to a novel energy state of an isolated acceptor, was found to be produced for a rather low value of [Mg]. In addition, a broad emission denoted by [g–g], which was ascribed to acceptor-acceptor pairs, was observed below bound exciton emissions for moderate values of [Mg]. These features were quite similar to those previously observed in acceptor-doped GaAs when the background concentration of donors is extremely low. Two additional novel emissions located far below the band-to-acceptor emission were also obtained, and each showed a remarkable energy shift towards lower energy with increasing [Mg]. The binding energies of these emissions were estimated from the temperature dependence of PL spectra and the results suggest that they are complex-type radiative recombination centers, presumably donor-acceptor-type centers. A strong broad emission centered near the band-to-acceptor emission was observed for [Mg]=3×10²⁰ cm^–3. This observation indicates a formation of a new material between In, P and Mg, which was also attested by the appearance of a new TO-like Raman signal for [Mg] greater than 1×10¹⁹ cm^–3. A substantial difference of PL and Raman spectra was revealed for the two annealing methods, suggesting that the annealing behaviour of ion-implanted InP should be investigated more extensively in order to establish reliable annealing procedures.Dedicated to H.-J. Queisser on the occasion of his 60th birthday