A New Supramolecular Tetraruthenated Cobalt (II) Porphyrazine Displaying Outstanding Electrocatalytical Performance in Oxygen Evolution Reaction

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)₂Cl]⁺ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O₂ evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.     

Observation of spatial distribution of laser-induced refractive index change in dye-doped liquid crystals

Spatial distributions of photothermal refractive index changes in dye-doped liquid crystals were determined by an optical interferometric method. The refractive index change of the order of 10^-1, including spatial distribution, was estimated by the described experimental technique. The absolute value of the refractive index change was proportional to the pump beam power, and the diameter of the index distribution was slightly larger than that of the pump laser beam due to heat conduction.     

Controlled assembly of silica microspheres in spherically confined polymer particles by using self-organized precipitation (SORP) method

Assembly of submicron-sized microspheres has received much attention due to its high potential for wide variety of applications. We have developed a preparation method of polymer particles by simple mixing of a poor solvent into the polymer solution followed by evaporation of a good solvent. By using this technique, silica nanoparticles and polymer composite particles were prepared. Preparation of three-dimensional assemblies of silica particles in polymer particles and composite Janus particles are shown.     

The resonant secondary emission of the F center in alkali halides

The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states.     

Nickel metallisation of Si by dynamic ion-beam mixing

Abstract

Thin Ni films were prepared at room temperature by Ni metal vapour deposition and simultaneous irradiation by Ar ions with an energy of 2–20 keV. The reaction of Ni with Si during dynamic ion-beam mixing was studied. The fluences of the ion beam were 4.7 × 10¹⁷ and 8.9 × 10¹⁷ cm^?2, and arrival rate ratios Ni/Ar were 9.7 and 5.1. Concentration profiles of Ni, Si, C, and O were analysed with Auger electron spectroscopy; the surface morphology and the crystalline structure were investigated with a cross-sectional scanning electron microscope and X-ray diffractometry. The theoretical profiles were calculated with the dynamic Monte Carlo simulation T-DYN for comparison with the experimentally obtained profiles. It was possible to observe the ballistic mixing effects and also thermally activated formation of nickel silicide.     

Resistivity control of sputtered amorphous-silicon by ion-implantation

The resistivity of a hydrogenated sputtered amorphous-silicon is controlled by using room temperature implantation of P⁺. It is found that the defects produced by implantation can be minimized by annealing at 300°C in an H₂ atmosphere, and also found that there is a threshold implanted dose, beyond which the resistivity begins to be controlled by changing the dose.     

Spontaneous ignition temperature for the compacted mixture of Ni–Al system: Experiment,theory, and comparisons

Spontaneous ignition of compacted mixture has been examined not only experimentally but also theoretically, relevant to materials synthesis for Ni–Al system. Spontaneous ignition temperature, determined from the inflection-point of the temporal variation of surface temperature, is found to decrease at first, reach the minimum, and then increase gradually, with increasing size ratio, being defined as the ratio of compact and particle diameters and reported to be useful in correlating experimental results. The lowest temperature observed is as low as that, more than 200 K below the melting point 934 K of Al, at the size ratio of c.a. 700. While its decrease is attributed to the increase in the particle surface per unit spatial volume of compacted mixture, as reported in the literature, its increase found in the course of the present study can fairly be correlated to an enhancement of heat loss from each particle in the compacted mixture, by conducting a theoretical consideration. As for the dependence of spontaneous ignition temperature on the mixture ratio, a shifting occurs from a decreasing trend with increasing mixture ratio at small size ratios, less than about 700, to an insensitive trend to the mixture ratio, had not been reported in the literature. In addition, a fair degree of agreement, shown in experimental comparisons with theoretical results, indicates that the present formulation has captured the essential features of the spontaneous ignition of compacted mixture, especially for size ratios with large values. Since this kind of particle size effects, relevant to the spontaneous ignition of the compacted mixtures, has not been captured in the previous studies, its elucidation can be considered not only notable but also useful, in manipulating combustion process in materials synthesis, especially, in choosing a specific condition for the lowest spontaneous ignition temperature by varying the size ratio.