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Kazuyuki Hirao

Publications and source records attributed to Kazuyuki Hirao.

At least 19 recordsLinked to original sources

Seed-mediated growth of palladium nanocrystals on indium tin oxide surfaces and their applicability as modified electrodes.

Palladium nanoparticles (PdNPs) were successfully attached and grown on an indium tin oxide (ITO) surface using a seed-mediated growth method, i.e., via a simple two-step immersion of the ITO substrate into the seed and growth solutions. After the growth treatment for 24 h, PdNPs grew up to 60-80 nm, exhibiting crystal-like appearances and accompanying the formation of short rodlike nanocrystals as a minor product. Thus prepared PdNPs tend to stick each other, so that the dense gathering of PdNPs was observed on the ITO surfaces. Due to the dense attachment, the PdNPs directly attached to the ITO (PdNP/ITO) electrode had a significantly lowered charge-transfer resistivity compared with that of a bare ITO, and the redox reaction of [Fe(CN)6]3-/[Fe(CN)6]4- was observed as reversible in 0.1 M phosphate buffer solution. The electrocatalytic property of PdNPs was confirmed for the reduction of oxygen. In addition, some typical responses were observed in 0.5 M H2SO4 with the PdNP/ITO electrode, reflecting both the characteristics of NPs and the thin layer in nanoscale. The present preparation method of PdNP-attached surfaces would be promising for catalytic applications as well as electrochemical uses.

Journal Article↗

Two-photon-excited fluorescence from silicate glass containing tantalum ions pumped by a near-infrared femtosecond pulsed laser.

We report a novel phenomenon in sodium-calcium-silicate glass doped with Ta(5+). Under irradiation with a 780 nm femtosecond pulsed laser, strong blue emission centered at about 420 nm could be observed. The spectral characteristics are similar to those pumped by ultraviolet photons. The log-log correlation between integrated emission intensity and pump power reveals that a two-photon absorption process is involved in the phenomenon. It is suggested that the presence of localized Ta(5+)5d(0) energy levels is responsible for the appearance of the blue emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into glass hosts.

Journal Article↗

Mutual consistency between simulated and measured pressure drops in silica monoliths based on geometrical parameters obtained by three-dimensional laser scanning confocal microscope observations.

The geometrical properties of co-continuous macroporous silica monoliths have been studied by laser scanning confocal microscopy (LSCM) and a comparison has been made with those obtained by conventional mercury intrusion method. Tetrahedral skeleton model (TMS), which mimics the gel skeleton shape of monoliths, was compared with real monoliths in terms of macropore and porosity using the geometrical parameters extracted from the LSCM observations. Liquid flow behavior through the macroporous silica monoliths was examined in comparison with those simulated using TSM, based on the geometrical properties obtained from LSCM observations. Heterogeneity in macropore topology and connectivity in pores and skeletons are suggested to contribute to the improvement of the model structure for macroporous monoliths.

Microscopy, Confocal↗

Anisotropic siloxane-based monolith prepared in confined spaces.

When bicontinuous gels are prepared via sol-gel method in a 2-dimensionally (2D) confined space, the gel skeletons in the vicinity of interface of a mold are elongated perpendicular to the interface. This phenomenon was attributed to the dynamic wetting of polymerizing siloxane phase onto the interface of the mold under gravity. In this paper, we report the successful preparation of monolithic columns with an oriented pillar structure in a variety of 2D confined spaces. Starting from a solution, which consists of methyltrimethoxysilane (MTMS), the macroporous structure is prepared in situ by a completely spontaneous process. In the oriented pillar structure, bicontinuous siloxane skeletons deformed or disappeared and most pillars are oriented along the direction of gravity. Gel morphologies with the pillar structure were examined by scanning electron microscopy (SEM) and laser scanning confocal microscopy (LSCM). Geometrical information on gel morphologies was numerically derived from the obtained 3D LSCM images.

Acetamides↗

In situ chemical reductive growth of platinum nanoparticles on indium tin oxide surfaces and their electrochemical applications.

Platinum nanoparticles directly attached to indium tin oxide (PtNP/ITO) were successfully fabricated by using an in situ chemical reductive growth method. In this method, PtNPs could be grown on the ITO surface via the one-step immersion into the growth solution containing PtCl4(2-) and ascorbic acid. The attached and grown PtNPs were spherical having an agglomerated nanostructure composed of small nanoclusters. From the morphological changes depending on the growth time, which were observed with an FE-SEM, PtNPs were found to be grown via the progressive nucleation mechanism. As the characteristics of the PtNP/ITO were those of a working electrode, it was found that the charge transfer resisivity was significantly lowered due to the grown PtNPs. Hence, for a typical redox system of [Fe(CN)6]3-/[Fe(CN)6]4-, the PtNP/ITO electrode exhibited the electrochemical responses similar to those of the bulk Pt electrode. Furthermore, it was clarified that the PtNP/ITO electrode had significant electrocatalytic properties for the oxygen reduction and methanol oxidation. The present PtNPs that had the agglomerated nanostructure may be promising for a new type of electrode material.

Journal Article↗

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity.

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.

Journal Article↗

Fabrication of photonic crystals in ZnS-doped glass.

Three-dimensional photonic crystals were fabricated in a ZnS-doped silicate glass by use of a femtosecond pulsed laser. Woodpile structures consisting of 36 layers were produced by focusing with a 100x (1.35-numerical-aperture) objective. Attenuations of approximately 3-8 dB arising from a photonic bandgap were observed in the visible and the near-infrared regions.

Journal Article↗

Fabrication of high-efficiency diffraction gratings in glass.

We investigated a microfabrication process for optical gratings with periods of micrometer order that use ultrafast laser pulses in semiconductor-doped glass. ZnS- or PbS-doped SiO2-A12O3-B2O3-CaO-ZnO-Na2O-K2O glass was prepared by a melting method. Glass transmission diffraction gratings with a high refractive-index difference were fabricated with femtosecond laser pulses. The first-order diffraction efficiencies of these gratings were approximately 80%, and the first-order diffraction angles of these gratings were 8 degrees at telecommunication wavelengths.

Journal Article↗

Silver-nanoparticle-attached indium tin oxide surfaces fabricated by a seed-mediated growth approach.

By applying a seed-mediated growth method that had been reported for the chemical synthesis of Ag nanorods and nanowires in aqueous solution, we successfully attached Ag nanosphere and nanorod particles to indium tin oxide (ITO) surfaces. In this method, it is characteristic that the attachment can be performed without using bridging reagents, such as 3-mercaptopropyltrimethoxysilane, but rather through a two-step immersion into the seed solution first and then into the growth solution containing AgNO(3), cetyltrimethylammonium bromide, and ascorbic acid. It was found that the formed nanostructures were very sensitive to the amount of ascorbic acid in the growth solution. Whereas Ag nanoparticles grew on the ITO surface with a moderate dispersion when the concentration of ascorbic acid in the growth solution was 0.64 mM, the formation of nanorods and nanowires was observed when the ascorbic acid concentration was increased to 0.86 mM. The attachment of Ag nanoparticles onto the ITO surfaces was strong enough for further use, e.g., as a working electrode. From electrochemical measurements, it was confirmed that the outer spheres of the Ag nanoparticles involved in the redox reaction show the typical oxidation and reduction waves of Ag. In addition, the redox behavior of [Fe(CN)(6)](3-)/[Fe(CN)(6)](4-) was improved on the Ag-nanoparticle-attached ITO (AgNP/ITO) electrode, reflecting the low electron-transfer resistivity, which is a remarkable advantage of the present fabrication without using bridging reagents. This result indicated that the Ag nanoparticles promote the electron-transfer reactions by being present on the conducting ITO surface. The AgNP/ITO electrode was examined for the reduction of the methyl viologen dication in order to discuss some features of the present fabrication.

Electrochemistry↗

Ultrasmall demultiplexer by use of one-dimensional photonic crystal.

Silica-based one-dimensional photonic crystal (1D-PC) is fabricated by use of a high-spatial-frequency grating with input and output surfaces tilted with respect to its periodic direction. An incident beam is coupled with the first photonic band in the second Brillouin zone of the 1D-PC. The output beam angle changes 3 degrees with a wavelength change of 1%. A prototype of an ultrasmall demultiplexer is demonstrated by use of a silica slab waveguide with 1D-PC.

Journal Article↗

Periodic nanovoid structures via femtosecond laser irradiation.

We have observed periodically aligned nanovoid structures inside a conventional borosilicate glass induced by a single femtosecond (fs) laser beam for the first time, to our knowledge. The spherical voids of nanosized diameter were aligned spontaneously with a period along the propagation direction of the laser beam. The period, the number of voids, and the whole length of the aligned void structure were controlled by changing the laser power, the pulse number, and the position of the focal point.

Crystallization↗

Controllable photoinduced optical attenuation in a single-mode optical fiber by irradiation of a femtosecond pulse laser.

Novel optical attenuation fibers were fabricated by the irradiation of a focused infrared femtosecond pulsed laser onto the core of a silica glass single-mode optical fiber. Optical attenuation at a wavelength of 1.55 microm proportionally increased with increasing numbers of irradiation points and was controllable under laser irradiation conditions. The single-mode property of the waveguide and the mode-field diameter of the optical fiber were maintained after irradiation of the femtosecond laser. It is suggested that the attenuation results from optical scattering at photoinduced spots formed inside the fiber core.

Journal Article↗

Compact and monolithic coarse wavelength-division multiplexer-demultiplexer fabricated by use of a high-spatial-frequency transmission grating buried in a slab waveguide.

A compact and monolithic four-channel demultiplexer with 20-nm spacing was fabricated by use of a high-spatial-frequency transmission grating buried in a silica waveguide. The grating was successfully buried in a silica slab waveguide by overcladding by plasma-enhanced chemical-vapor deposition. The device's size was approximately 5.1 mm x 9.2 mm. The average insertion loss was 13 dB. The average cross talk was -15 dB for adjacent channels and -19 dB for nonadjacent channels. The polarization-dependent loss was estimated to be as low as 0.7 dB.

Journal Article↗

Optical properties of structurally modified glasses doped with gold ions.

We report on the optical properties of a structurally modified silicate glass doped with Au ions. The area in the vicinity of the focal point of an 800-nm femtosecond laser in a glass sample became gray as a result of the formation of color centers after laser irradiation and turned red because of precipitation of Au nanoparticles after further annealing at 550 degrees C for 30 min. When the glass was excited by UV light at 365 nm, yellowish-white and orange-yellow emissions were observed in the laser-irradiated and the Au-nanoparticle-precipitated area, respectively. An optical Kerr shutter experiment showed that the Au nanoparticle-precipitated glass had an ultrafast nonlinear optical response, and the third-order nonlinear susceptibility was estimated to be approximately 10(-11) esu.

Journal Article↗

Structural formation of hybrid siloxane-based polymer monolith in confined spaces.

Structural deformation of phase-separated methylsiloxane gel under the influence of a surface has been studied. Competitive wetting of siloxane gel phase on a surface during phase formation is found to significantly affect the final morphology in a confined space. When the spinodal wavelength is sufficiently shorter than the size of the available space, a uniform bicontinuous structure forms in confined geometry. However, gel skeletons in the vicinity of a surface are elongated with decreasing size of the space, and finally when the size of the space becomes shorter than the spinodal wavelength, all the gel phase wets on a surface, showing a "wetting transition". Homogeneous bicontinuous methylsiloxane gels were successfully prepared, avoiding such structural deformation, in a long cylindrical fused silica capillary and used for capillary HPLC. The capillary gels exhibited excellent separation efficiency of nitrobenzenes and it was found that the surface character can be altered by incorporating surfactants, which will enable more advanced and extended control of surface character, depending on the analytes.

Chromatography↗

Photoinduced birefringence of azodye-doped materials by a femtosecond laser.

Birefringence in azodye-doped polymethylmethacrylate and azodye-doped silica hybrid materials was induced by the two-photon excitation of a femtosecond laser. The growth and the relaxation characteristics of the photoinduced birefringence in the two types of material were investigated, and the probe transmittance for the induced birefringence was estimated to be 92%. Furthermore, an optical image storage based on this photoinduced birefringence was demonstrated.

Journal Article↗

Room-temperature grating-based morphological hole burning in Sm2+-doped glass powders.

We have observed grating-based morphological hole burning in Sm2+-doped glass powders at room temperature. When photobleaching on the 4f(6)-4f(5)5d transition of Sm2+ is combined with multiple light scattering, holes are produced in frequency and wave-vector domains. The hole profile depends on the amount of light absorption of Sm2+; it sharpens as the absorption decreases. The variation of the hole shape is explained theoretically based on a diffusion approximation.

Journal Article↗