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.

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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.

Reactive species, holes, and electrons in photoexcited nanocrystalline TiO 2 films were studied by transient absorption spectroscopy in the wavelength range from 400 to 2500 nm. The electron spectrum was obtained through a hole-scavenging reaction under steady-state light irradiation. The spectrum can be analyzed by a superposition of the free-electron and trapped-electron spectra. By subtracting the electron spectrum from the transient absorption spectrum, the spectrum of trapped holes was obtained. As a result, three reactive speciess trapped holes and free and trapped electronsswere identified in the transient absorption spectrum. The reactivity of these species was evaluated through transient absorption spectroscopy in the presence of hole-and electronscavenger molecules. The spectra indicate that trapped holes and electrons are localized at the surface of the particles and free electrons are distributed in the bulk.