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Kazuhiro Sayama

Publications and source records attributed to Kazuhiro Sayama.

8 recordsLinked to original sources
PubMed2006

Photoelectrochemical decomposition of water into H2 and O2 on porous BiVO4 thin-film electrodes under visible light and significant effect of Ag ion treatment.

The photoelectrochemical properties of porous BiVO4 thin-film electrodes on conducting glass for H2 production from water under visible light were investigated. BiVO4 films were prepared by the metal-organic decomposition method, and particles were 90-150 nm in diameter. Under visible-light irradiation, H2 and O2 evolved in a stoichiometric ratio (H2/O2 = 2) from an aqueous solution of Na2SO4 with an external bias. The photocurrent increased with addition of methanol. The band structure of BiVO4 was investigated by open-circuit potential, flat-band potential, X-ray photoelectron spectroscopy, and calculations based on density functional theory. The top of the valence-band potential of BiVO4 was shifted negatively compared to the potentials of the conventional oxide semiconductors without Bi. We surmise that hybridization between the O-2p and Bi-6s orbitals might contribute to the negative shift of the BiVO4 valence band. Treatment with an aqueous solution of AgNO3 improved the photocurrent of the BiVO4 electrode significantly. The maximum incident photon-to-current conversion efficiency at 420 nm was 44%. This value was the highest among mixed-oxide semiconductor electrodes under visible light irradiation. AgNO3 treatment also improved the stability of the photocurrent. The Ag+ ion in/on the BiVO4 catalyzed the intrinsic photogeneration of oxygen with the holes.

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PubMed2006

Microfaceting explains complicated structures on rutile TiO2 surfaces.

Surface structures on rutile TiO2 (001) have been studied by using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional calculations. Prior investigations have observed many kinds of complicated surface structures; however, detailed atomic structures and the mechanism of the reconstructions are still unknown. We evaluate the energetical stability of the surface structures. The calculational results suggest that a [111] microfaceting model is energetically stable compared with the unreconstructed (1 x 1) model. We propose microfaceting structural models that are in good agreement with atomically resolved STM images. This structural concept can be extended to other rutile TiO2 surfaces in general.

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PubMed2006

Photocatalytic activity of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) for water splitting into H2 and O2.

The photocatalytic activities of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) strongly depended on the crystal structure. Overall, photocatalytic water splitting into H2 and O2 proceeded over La3TaO7 and La3NbO7, which have an orthorhombic weberite structure, Y2Ti2O7 and Gd2Ti2O7, which have a cubic pyrochlore structure, and La2Ti2O7, which has a monoclinic perovskite structure. All of these materials are composed of a network of corner-shared octahedral units of metal cations (TaO6, NbO6, or TiO6); materials without such a network were inactive. The octahedral network certainly increased the mobility of electrons and holes, thereby enhancing photocatalytic activity.

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PubMed2005

Efficient eosin y dye-sensitized solar cell containing Br-/Br3- electrolyte.

We found that Br-/Br3- is more suitable than an I-/I3- couple in dye-sensitized solar cells in terms of higher open-circuit photovoltage (Voc) production and higher overall energy conversion efficiency (eta) if the dye sensitizer has a more positive potential than that of Br-/Br3-. Under simulated AM1.5 one sun, an eosin Y dye-sensitized solar cell containing 0.4 M LiBr + 0.04 M Br2 electrolyte in acetonitrile yielded a short-circuit photocurrent (Jsc) of 4.63 mA cm(-2), Voc of 0.813 V, and fill factor (FF) of 0.693, corresponding to 2.61% of eta. Under the same conditions except for the electrolyte 0.4 M LiI + 0.04 M I2 in acetonitrile instead, the device produced 1.67% of eta (Jsc = 5.15 mA cm(-2), Voc = 0.451 V, FF = 0.721). Replacement of I-/I3- with Br-/Br3- in eosin Y dye-sensitized solar cells yielded a significant increase in Voc offset by slight decreases in Jsc and FF, leading to an increase in eta by 56%. The significant gain in Voc was attributed to the enlarged energy level difference between the redox potential of the electrolyte and the Fermi level of TiO2 and the suppressed charge recombination as well. The rate for charge recombination between bromine and the injected electrons was determined to be first order in bromine.

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PubMed2005

Development of new photocatalytic water splitting into H2 and O2 using two different semiconductor photocatalysts and a shuttle redox mediator IO3-/I-.

A new type of photocatalytic reaction that splits water into H2 and O2 was designed using a two-step photoexcitation system composed of an iodate/iodide (IO3-/I-) shuttle redox mediator and two different photocatalysts, one for H2 evolution and the other for O2 evolution. Photocatalytic oxidation of water to O2 and reduction of IO3- to I- selectively proceeded with good efficiencies over TiO2-rutile and Pt-WO3 photocatalysts under UV and visible light irradiations, respectively. The O2 evolution selectively proceeded even in the presence of a considerable amount of I- in the solutions, although the oxidation of water is thermodynamically less favorable than oxidation of I-. Both the adsorption property of IO3- anions and the oxidation property of the photocatalysts are doubtless responsible for the selective oxidation of water. On the other hand, photocatalytic reduction of water to H2 and oxidation of I- to IO3- proceeded over Pt-TiO2-anatase and Pt-SrTiO3:Cr/Ta (codoped with Cr and Ta) photocatalysts under UV and visible light, respectively. The combination of two different photocatalysts results in a stoichiometric evolution of H2 and O2 via the redox cycle of IO3- and I-. The photocatalytic water splitting under visible light irradiation (lambda > 420 nm) was demonstrated by using the Pt-SrTiO3:Cr/Ta, Pt-WO3, and IO3-/I- shuttle redox mediator.

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PubMed2004

Effect of additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells.

The effects of deoxycholic acid (DCA) and 4-tert-butylpyridine (TBP) as additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells were investigated. DCA coadsorption improved both the photocurrent and photovoltage of the solar cells, even though it decreased the amount of dye adsorbed on the TiO2 electrode. The improved photocurrent may arise from suppression of the deactivation of the excited state via quenching processes between dye molecules or a more negative LUMO level of the dye in the presence of DCA, resulting in a high electron-injection yield from the dye into TiO2. The increased photovoltage is probably due to suppression of recombination between the injected electrons and I3- ions on the TiO2 surface (dark current). The addition of TBP to the electrolyte also markedly improved the photovoltage and fill factor of the solar cell, and consequently, the total conversion efficiency increased from 3.6% to 7.5%. FT-IR spectroscopy indicated that a large amount of TBP was adsorbed on the dye-coated TiO2 films in the presence of Li cations. This result suggests that TBP, like DCA, suppressed the dark current on the TiO2 surface, which resulted in the improved photovoltage.

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PubMed2003

Novel polyene dyes for highly efficient dye-sensitized solar cells.

We have developed an efficient and novel polyene-dye-sensitized nanocrystalline TiO2 solar cells producing a 6.8% solar energy-to-electricity conversion efficiency (eta) under AM 1.5 irradiation (100 mW cm(-2)): short-circuit current density (Jsc), 12.9 mA cm(-2), open-circuit photovoltage (Voc), 0.71 V, fill factor (ff), 0.74.

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