The photocatalytic splitting of water into hydrogen and oxygen using solar energy is a potentially clean and renewable source for hydrogen fuel. The first photocatalysts suitable for water splitting, or for activating hydrogen production from carbohydrate compounds made by plants from water and carbon dioxide, were developed several decades ago. But these catalysts operate with ultraviolet light, which accounts for only 4% of the incoming solar energy and thus renders the overall process impractical. For this reason, considerable efforts have been invested in developing photocatalysts capable of using the less energetic but more abundant visible light, which accounts for about 43% of the incoming solar energy. However, systems that are sufficiently stable and efficient for practical use have not yet been realized. Here we show that doping of indium-tantalum-oxide with nickel yields a series of photocatalysts, In(1-x)Ni(x)TaO(4) (x = 0-0.2), which induces direct splitting of water into stoichiometric amounts of oxygen and hydrogen under visible light irradiation with a quantum yield of about 0.66%. Our findings suggest that the use of solar energy for photocatalytic water splitting might provide a viable source for 'clean' hydrogen fuel, once the catalytic efficiency of the semiconductor system has been improved by increasing its surface area and suitable modifications of the surface sites.

We have developed novel coumarin dyes for use in dye-sensitized nanocrystalline TiO2 solar cells (DSSCs). The absorption spectra of these novel coumarin dyes are red-shifted remarkably in the visible region relative to the spectrum of C343, a conventional coumarin dye. Introduction of a methine unit (−CHCH−) connecting both the cyano (−CN) and carboxyl (−COOH) groups into the coumarin framework expanded the π conjugation in the dye and thus resulted in a wide absorption in the visible region. These novel dyes performed as efficient photosensitizers for DSSCs. The monochromatic incident photon-to-current conversion efficiency (IPCE) from 420 to 600 nm for a DSSC based on NKX-2311 was over 70% with the maximum of 80% at 470 nm, which is almost equal to the efficiency obtained with the N3 dye system. The IPCE performance of DSSCs based on coumarin dyes depended remarkably on the LUMO levels of the dyes, which are estimated from the oxidation potential and 0−0 energy of the dye. The slow charge recombination, on the order of micro to milliseconds, between NKX-2311 cations and injected electrons in the conduction band of TiO2 (observed by transient absorption spectroscopy) resulted in efficient charge separation in this system. A HOMO−LUMO calculation indicated that the electron moves from the coumarin framework to the −CHCH− unit by photoexcitation of the dye (a π−π* transition). Our results strongly suggest that molecular design of the sensitizer is essential for the construction of highly efficient DSSCs. The structure of NKX-2311, whose carboxyl group is directly connected to the −CHCH− unit, is advantageous for effective electron injection from the dye into the conduction band of TiO2. In addition, the cyano group, owing to its strong electron-withdrawing ability, might play an important role in electron injection in addition to a red shift in the absorption region.

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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The stoichiometric splitting of water into H2 and O2 (H2/O2 = 2) under visible light irradiation (lambda > 420 nm) took place for the first time using a mixture of Pt-WO3 and Pt-SrTiO3 (Cr-Ta-doped) photocatalysts and an IO3-/I- shuttle redox mediator.

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.

In studying the photoelectrochemical properties of TiO 2 , Nb 2 O 5 , ZnO, SnO 2 , In 2 O 3 , WO 3 , Ta 2 O 5 , and ZrO 2 porous semiconductor films sensitized by the ruthenium(II) cis-bis-(thiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylic acid) complex, it was found that the Nb 2 O 5 semiconductor cell had the next highest incident of monochromatic photon-to-current efficiency (IPCE ) 18%) compared to the TiO 2 cell and showed the highest open-circuit photovoltage (V oc ) among them. The V oc of the dye-sensitized cell was proved to be related to the flatband potential of the semiconductor electrode. The Ru dye adhered to the Nb 2 O 5 surface mainly through an ester-like linkage. It is speculated that electrons are transferred mainly through the conjugated orbitals of the ester linkage and semiconductor conduction band and that the TiO 2 and Nb 2 O 5 conduction bands consisting of d-orbitals are more advantageous than those of s-orbitals in attaining the desired IPCE. The IPCE of the Nb 2 O 5 cell was markedly improved by treating the Nb 2 O 5 electrode with Nb alkoxide, and the maximum IPCE was 32% at 548 nm. The overall solar-to-electric energy conversion efficiency was about 2% (AM-1.5, 100 mW/cm 2 ).

It was found for the first time that the photocatalytic decomposition of pure water proceeded over ZrO2 powder without any loaded metals under UV irradiation. The rate of H2 and 0 2 evolution increased upon addition of Na2CO3 and NaHCO3. Moreover, the evolution of CO (the photocatalytic reduction product of COz) was observed from NaHCO3 solutions. The special characteristics of Zr02 semiconductor are believed to be associated with its highly negative flat-band potential and wide bandgap. In the case of Cu(1 wt 96)-ZrO2 catalyst suspended in NaHCO3 aqueous solution, the rates of gas evolutions were 19.5 pmol/h of H2, 10.8 pmollh of 0 2 , and 2.5 pmollh of CO. These mass balances were indicative of a stoichiometric and catalytic reaction.