Hiroaki Noma

Effect of functional group on photochemical properties and photosensitization of TiO2 electrode sensitized by porphyrin derivatives

A series of porphyrin derivatives containing carboxylic-, sulfo- and hydro- groups, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP), 5,10,15,20-tetrakis(4-sulfophenyl)porphyrin (TSPP) and 5,10,15,20-tetraphenyl-porphyrin (TPP), were examined as sensitizers for porous nanocrystalline TiO2. The difference in the adsorption behavior on the TiO2 electrode surface was discussed. The interaction between the porphyrins and the TiO2 surface was determined and compared using UV–Vis spectra and X-ray photoelectron spectroscopy (XPS). The luminescence spectra of the porphyrins in DMF solution and adsorbed onto TiO2 electrodes were measured. The ionization potentials of the porphyrins in the solid state and adsorbed onto TiO 2 electrodes were determined by a new approach using an apparatus for measuring the emission yield under atmospheric conditions. The importance of the binding states between the dye and TiO2 surface was discussed by comparison of the energy conversion efficiency in a dye-sensitized solar cell. The results indicate that the binding state and the amount of adsorbed dye are important factors affecting the properties of the dye-sensitized solar cell.

Preparation and properties of nanostructured TiO2 electrode by a polymer organic-medium screen-printing technique

An organic-medium screen-printing technique was developed for making porous TiO2 electrodes. The TiO2 pastes were prepared by mixing only 100% polyalkylene glycol and commercial nanocrystalline TiO2 powders. The obtained paste is highly printable and hard to evaporate during printing. The TiO2 electrodes have a very porous structure with large cavities. The dye-sensitized solar cell based on these meso-macroporous TiO2 electrodes exhibits high overall conversion efficiency of 4.3–5.8%, which is comparable to those of prepared by water or terpineol medium.

Photoelectrochemical properties of TiO2 electrodes sensitized by porphyrin derivatives with different numbers of carboxyl groups

Abstract The photochemical and photoelectrochemical properties of two porphyrin derivatives with different numbers of carboxyl groups were investigated. The two porphyrin derivatives are 5-(4-carboxyphenyl)-10,15,20-tritolylporphyrin (H2TC1PP) and 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (H2TC4PP). The interaction between the porphyrin and TiO2 is determined by the UV–vis spectra. Differences in adsorption behavior of the two porphyrin derivatives on the TiO2 electrode surface were observed. The IR data suggest that both of the porphyrins adsorb by bridging or bidentate chelate coordination on the TiO2 surface. Comparing the luminescence spectra of the two porphyrins in solution and the solid state, no spectral difference was observed. However, we found that the variation in the number of carboxyl groups has an influence on the fluorescence spectra of the adsorbed TiO2 electrode. Furthermore, we measured and compared the incident photon-to-current conversion efficiency (IPCE) and the light-to-electrical conversion efficiency of the porphyrin-sensitized solar cell. These results revealed that the number of functional groups influenced the photoelectrochemical properties of the cell.

NATURAL 1.1 AND 1.4 NM TOBERMORITES FROM FUKA, OKAYAMA, JAPAN: CHEMICAL ANALYSIS, CELL DIMENSIONS, 29SI NMR AND THERMAL BEHAVIOR

Tobermorite is both a natural mineral and a main constituent of autoclaved calcium silicate products. In this study, a natural specimen of tobermorite from Japan, which contained both 1.1 and 1.4 nm phases, was studied by optical microscopy, X-ray powder diffractometry (XRD), electron probe microanalysis, analytical electron microscopy, 29Si nuclear magnetic resonance (NMR) spectroscopy and thermo-gravimetric/differential thermal analyzer. These results were compared with those for a specimen from Crestmore, California. The first sample, occurring as a vein in contact with metamorphic rocks, could be divided into three zones. In two of the zones containing only the 1.1 nm phase, about 10% of the Si were substituted by Al. The third zone was an intergrowth of 1.1 and 1.4 nm tobermorites and contained almost no Al. The basal spacings of the 1.1 and 1.4 nm tobermorites were changed mainly to 0.9 nm by heating at 300 deg C for 24 h but in some parts remained at 1.1 nm. The XRD results indicated that the crystals in natural tobermorite are thicker than those of synthetic tobermorites in calcium silicate products. 29Si NMR results showed that the 1.1 nm tobermorite had a double chain silicate anion, which changed mainly into single chains, on heating at 300 deg C. The 1.4 nm tobermorite had a single-chain silicate anion.

Interstratification in expandable mica produced by cation-exchange treatment

A unique interstratified expandable mica was obtained by cation exchange treatments using an expandable mica synthesized from talc. The 23Na magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectrum of the expandable mica used as a starting material showed that it had 2 kinds of Na+: one was exchangeable and the other was not exchangeable. Half of the Na+ per unit cell of the expandable mica was replaced with Mg2+ by cation exchange treatments. The X-ray powder diffraction (XRD) analysis of the Mg2+-exchanged expandable mica, after heating at 73°C, indicated that Na+ in the interlayer sheets was exchanged with Mg2+ in every second layer and that it had an interstratified structure with a 12.5-Å layer thickness and a 9.6-Å layer thickness. The structure of the Mg2+-exchanged expandable mica was changed into a unique interstratified structure by the calcination at 600°C; one component had a stacking sequence of talc and a small amount of OH−, but the other had a different stacking sequence from talc and no structural OH—.

Formation conditions and stability of a toxic tridecameric Al polymer under a soil environment

It is important to study the formation conditions and the stability of the tridecameric Al polymer (Keggin-type Al(13) polycation, [AlO(4)Al(12)(OH)(24)(H(2)O)(12)](7+), known as Al(13)) due to its strong toxicity to living organisms of a soil environment. In order to examine the pH range where toxic Al(13) can exist in aqueous solution, (27)Al NMR spectra for sample solutions containing Al(3+) ions with various pH (pH 3.5-6.1) were measured. The results show that the peak due to Al(13) (peak due to 4-coordinated Al around 63 ppm) appeared at pH 3.6-5.7 and the peak intensity was relatively high at pH 4.1-4.8, suggesting that Al(13) can be formed at pH 3.6-5.7, while it can exist dominantly at pH 4.1-4.8. It was also found that Al(13) can stably adsorb onto a chelate resin, Chelex 100, by weak electrostatic interaction. The Chelex 100, with iminodiacetate groups, served as a model compound for surfaces of microbes covered with carboxyl groups and for surfaces of soil particles covered with humic substances having many carboxyl groups. Additionally, decomposition of Al(13) did not occur even after adsorption, and its pH stability range was wide compared to that in aqueous solution.

Piezoelectric Response to Pressure of Aluminum Nitride Thin Films Prepared on Nickel-Based Superalloy Diaphragms

Aluminum nitride (AlN) thin films were prepared on Inconel 600 superalloy diaphragms by rf magnetron sputtering for the first time to our knowledge. The crystal structure of the AlN films is hexagonal, and the c-axis of the AlN films orients perpendicular to the diaphragm surfaces. The full-width at half-maximum (FWHM) of the X-ray rocking curves of the AlN films is 5.7°, and the piezoelectric constants d33 and d31 are 2.0 and 0.7 pC/N, respectively. We have investigated the influence of the diaphragm structure on the piezoelectric response to pressure of the AlN films. The AlN films sensitively generate electric charges to pressure changes, and the generated charges show an excellent linearity with increasing pressure. The AlN films indicate a high sensitivity of 723 pC/N. The sensitivity of the AlN films agrees with the result calculated using a method in which the electroelastic energy is differentiated from the voltage in AlN films for unimorph circular diaphragms.

Silica deposition induced by isolated aluminum ions bound on chelate resin as a model compound of the surface of microbes

To elucidate the mechanism of silica biodeposition in hot spring water, which is induced by Al(3+) ions bound to the surface of microbes, a chelate resin (Chelex 100) was used as a model compound of the surface of microbes. No silicic acid was adsorbed on the Na type Chelex 100, whereas silicic acids were significantly adsorbed to the Al type Chelex 100. In the Al type Chelex 100, the Al(3+) ions were present as 1:1 tridentate complex with iminodiacetate (IDA) group. After adsorption of silicic acid to Al type Chelex 100, a IDA-Al-O-Si-(OH)(3) site formed. The site acted as a template for the successive adsorption of silicic acids to form silica sheets around Al type Chelex 100 particles. In conclusion, Al(3+) ions bound to the surface of microbes play a key role as a trigger for the biodeposition of silica in hot spring water.

Development of High-Temperature Acoustic Emission Sensor Using Aluminium Nitrade Thin Film

Aluminum nitride (AlN) is a promising Acoustic Emission (AE) sensor element for high-temperature environments such as gas turbines and other plants because AlN maintains its piezoelectricity up to 1200°C. Highly c-axis-oriented AlN thin-film sensor elements were prepared on silicon single crystals by rf magnetron sputtering. Both ordinary-temperature AE sensors and high-temperature AE sensors have been developed using these elements. In this paper, to study effects of d33 and thickness of AlN elements on sensor sensitivity, AlN elements with d33 from 2 to 7 pm/V and thickness from 3 to 9 /m were prepared. It is confirmed that the AE sensor sensitivity increased with d33 and thickness of AlN elements. The sensitivity of the high-temperature AE sensor was also improved by a design of the sensor structure. The sensor characteristics were evaluated at elevated temperatures from 200 to 600°C. It was confirmed that the AE sensor works well at 600°C and does not deteriorate.

Effect of Microchannel on Improving the Photoelectro- chemical Performance of Nanostructured TiO2 Electrodes Sensitized by Ru Complex

The photoelectrochemical behaviors of the dye-sensitized nanoporous T i 0 2 solar cell with and without microchannels were studied. A remarkably enhancement in the photocurrent of the cell with the microchannels on the T i 0 2 electrode was observed. The resistances of the cells were valuated by measuring the electrical impedance. It was found that the resistances of the cell with the microchannels became smaller than those of the cell without microchannnels. These results suggest that the diffusion of the iodide/triiodide species in the electrolyte was