There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

THE large-scale use of photovoltaic devices for electricity generation is prohibitively expensive at present: generation from existing commercial devices costs about ten times more than conventional methods1. Here we describe a photovoltaic cell, created from low-to medium-purity materials through low-cost processes, which exhibits a commercially realistic energy-conversion efficiency. The device is based on a 10-µm-thick, optically transparent film of titanium dioxide particles a few nanometres in size, coated with a monolayer of a charge-transfer dye to sensitize the film for light harvesting. Because of the high surface area of the semiconductor film and the ideal spectral characteristics of the dye, the device harvests a high proportion of the incident solar energy flux (46%) and shows exceptionally high efficiencies for the conversion of incident photons to electrical current (more than 80%). The overall light-to-electric energy conversion yield is 7.1-7.9% in simulated solar light and 12% in diffuse daylight. The large current densities (greater than 12 mA cm-2) and exceptional stability (sustaining at least five million turnovers without decomposition), as well as the low cost, make practical applications feasible.

A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films

Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references)

Heterogeneous photocatalyst materials for water splitting

Dye-sensitized solar cells (DSCs) offer the possibilities to design solar cells with a large flexibility in shape, color, and transparency. DSC research groups have been established around the worl ...

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Dye-Sensitized Solar Cells

Although titanium dioxide photocatalysts having anatase phase are a promising substrate for photodegradation of pollutants in water and air, their photocatalytic activities show only under ultraviolet (UV) light. For us to utilized a wide range of incident light such as solar light, development of the photocatalysts whose activities show under visible light is one of the most important strategies. We have synthesized chemically modified titanium dioxide photocatalysts in which S (S4+) substitutes for some of the lattice titanium atoms. They show strong absorption for visible light and high activities for degradation of methylene blue, 2-propanol in aqueous solution and partial oxidation of adamantane under irradiation at wavelengths longer than 440 nm. The oxidation state of the S atoms incorporated into the TiO2 particles is determined to be mainly S4+ from X-ray photoelectron spectra (XPS) spectra.

Preparation of S-doped TiO2 photocatalysts and their photocatalytic activities under visible light

Morphology of a TiO2 Photocatalyst (Degussa, P-25) Consisting of Anatase and Rutile Crystalline Phases

In order to effectively utilize visible light in photocatalytic reactions, we have developed S-doped TiO2 particles. They show strong absorption for visible light and high activities for degradation of methylene blue in aqueous solution under irradiation at wavelengths longer than 440 nm. The oxidation state of the S atoms incorporated into the TiO2 particles is determined to be S6+ from the XPS spectra.

Photocatalytic Activity of S-doped TiO2 Photocatalyst under Visible Light

A titanium dioxide powder consisting of 1 μm size rutile and anatase particles was obtained, on which developed crystal faces were observed by a scanning electron microscope. From electron diffraction analyses, it was found that the rutile particles exposed {011} and {110} crystal faces, and the anatase particles exposed {001} and {011} faces. This powder showed high activity for some photocatalytic reactions, including oxidation of water. After photocatalytic oxidation of water on the powder using hexachloroplatinate(IV) ions as the electron acceptors, Pt deposits were observed mostly on the rutile particles, especially on the {110} face. When 2-propanol was added to the solution, Pt was deposited on both the anatase and rutile particles. Using the thus prepared Pt-deposited TiO2 powder, Pb2+ ions were photocatalytically oxidized into PbO2. After this reaction, PbO2
deposits were seen on the {011} face of the rutile particles. On the anatase particles, PbO2 deposits were observed in a larger amount on the {001} face than on the {011} face. These results indicate that the crystal faces help in the separation of electrons and holes, and that this effect is stronger for the rutile particles than for the anatase particles.

Crystal faces of rutile and anatase TiO2 particles and their roles in photocatalytic reactions

Photocatalytic oxidation of naphthalene was investigated in a mixed solution of acetonitrile and water using various kinds of titanium dioxide (TiO 2 ) powders as the photocatalysts and molecular oxygen as the electron acceptor. The main product from naphthalene is 2-formylcinnamaldehyde. For this reaction, anatase small TiO 2 particles, which are commonly used as photocatalyst, are inactive, probably because band bending is necessary for the oxidation of naphthalene. If the particles are not extremely small, pure rutile and pure anatase powders show fairly high activity, and those containing both anatase and rutile phases show the highest activity. When a pure anatase powder is partly (about 90%) converted to the rutile form by heat treatment, the activity is largely enhanced. The activity of pure rutile particles is also enhanced by physically mixing them with a small amount of small-sized anatase particles, which are inactive for this reaction. These results can be explained by the synergism between rutile and anatase particles. We consider that electrons are transferred from rutile particles to anatase particles, i.e. naphthalene is mainly oxidized on rutile particles and oxygen is mainly reduced on anatase particles. This electron transfer process is supported by electrochemical properties of TiO 2 electrodes for reduction of oxygen.

Michio Matsumura

Papers

Preparation of S-doped TiO2 photocatalysts and their photocatalytic activities under visible light

Morphology of a TiO2 Photocatalyst (Degussa, P-25) Consisting of Anatase and Rutile Crystalline Phases

Photocatalytic Activity of S-doped TiO2 Photocatalyst under Visible Light

Crystal faces of rutile and anatase TiO2 particles and their roles in photocatalytic reactions

Synergism between rutile and anatase TiO2 particles in photocatalytic oxidation of naphthalene