Well-dispersed Au co-catalyst deposited on a rutile TiO2 photocatalyst via electron traps.

We deposited Au nanoparticles as a co-catalyst onto a TiO2 photocatalyst by reducing [AuCl4]- using electrons trapped in the oxygen vacancies of TiO2. The dispersibility and hydrogen production ability of the Au co-catalyst are higher than those prepared using the conventional photodeposition method.

Highly Efficient Photocatalytic Degradation of Hydrogen Sulfide in the Gas Phase Using Anatase/TiO2(B) Nanotubes.

Hydrogen sulfide (H2S) is a highly toxic and corrosive gas that causes a foul odor even at very low concentrations [several parts per billion (ppb)]. However, industrially discharged H2S has a concentration range of several tens of ppb to several parts per million (ppm), which conventional methods are unable to process. Therefore, advanced and sustainable methods for treating very low concentrations of H2S are urgently needed. TiO2-based photocatalysts are eco-friendly and have the ability to treat environmental pollutants, such as low-concentration gases, using light energy. However, there are no reports on H2S decomposition or oxidation at concentrations below several ppb. Therefore, in this study, we employed anatase/TiO2(B) nanotubes, which have a high specific surface area and an efficient charge-transfer interface, to treat H2S. We successfully reduced 10 ppm of H2S to 1 ppb or less at a kinetic rate of 75 µmol h-1 g-1. The suitability of our method was further demonstrated by the generation of sulfate ions and sulfur (as detected by X-ray photoelectron spectroscopy and ion chromatography), which are industrially useful as oxidation products, whereas sulfur dioxide, a harmful substance, was not produced. This is the first study to report H2S decomposition down to the ppb level, providing meaningful solutions for malodor problems and potential health hazards associated with H2S.

Photoreforming of Organic Waste into Hydrogen Using a Thermally Radiative CdOx/CdS/SiC Photocatalyst.

To achieve superior efficiency for photocatalytic reactions, it is necessary to utilize visible light, which accounts for most of the solar energy. Herein, by applying a photocatalytic reaction, we aimed to develop a method for generating hydrogen by reforming organic waste, which is discharged as part of domestic, agricultural, forestry, and industrial practice. In the prepared CdS/SiC composite photocatalyst, etching of the oxide film of SiC and oxidation of the atomic-level surface of CdS proceeded in an alkaline reaction solution to form a CdOx/CdS/SiC composite. This composite is stable under light irradiation in a high-temperature alkaline reaction solution and can steadily promote hydrogen production. CdOx/CdS/SiC exhibits absorption in the entire ultraviolet and visible light region. In particular, the visible light region on the long-wavelength side, which is derived from the crystal defect of SiC, was used for heat radiation, and it was effective in increasing the temperature of the reaction solution. The high-temperature alkaline reaction solution promoted the hydrolysis of organic wastes with high molecular weight. Elution of small organic molecules by this process facilitated the progress of photocatalytic reactions and improved the rate of hydrogen production. Furthermore, in the absorption region derived from the interband transition below 580 nm, electron transfer between SiC and CdS suppressed recombination and improved the photocatalytic activity. Particularly, we achieved a high quantum yield of almost 20% in the ultraviolet region of 380 nm, where electron transfer from SiC was remarkable. Even in the visible light region, 2.0% was achieved at 420 nm, indicating an activity superior to that of conventional photoreforming systems. Using the developed photocatalytic system, we succeeded in producing hydrogen by photoreforming organic waste, such as cellulosic biomass, animal biomass, and plastic, under sunlight. Therefore, it is possible to solve waste disposal, environmental, and energy problems using sustainable photocatalytic processes.

Elucidating the Factors Affecting Hydrogen Production Activity Using a CdS/TiO2 Type-II Composite Photocatalyst.

CdS/TiO2 is a composite photocatalyst that has been studied over many years and in which electron transfer from CdS to TiO2 is believed to lead to high photocatalytic activity. However, most reports on improved activity involve hydrogen production in the presence of a sulfide reducing agent. In this study, we comprehensively examined the effects of electron transfer, hydrogen overvoltage, substrate adsorption, and the cocatalyst from relationships between hydrogen production ability and the total number of trapped electrons in the presence of various reducing agents. As a result, we clarified that the electron transfer between CdS and TiO2 does not necessarily lead to high activity. We showed that the composite photocatalyst needs to be designed for the intended purpose and that evaluating the hydrogen production ability using sacrificial reagents provides insufficient information for use in an actual environment.

Elucidation of the electron energy structure of TiO2(B) and anatase photocatalysts through analysis of electron trap density.

A clear understanding of the electron energy structure of TiO2(B)/anatase is needed to study the related catalytic reactions and design new composite photocatalysts. In this study, the electron energy structures of TiO2(B) and anatase were estimated by analyzing the energy-resolved distribution of electron traps measured by reversed double-beam photoacoustic spectroscopy. In the mixture of TiO2(B) and anatase, interfacial charge-transfer excitation from anatase to electron traps of TiO2(B) was suggested. By analyzing this for TiO2(B), the electron level with a relatively high density of states was found to be located ∼0.07 eV deeper than that for anatase. Furthermore, a similar electron energy structure was suggested for a composite photocatalyst having a mixed phase of TiO2(B) and anatase.

Efficient hydrogen production using photosystem I enhanced by artificial light harvesting dye.

In this study, we improved the hydrogen production efficiency by combining photosystem I with an artificial light harvesting dye, Lumogen Red. In the reaction system, Lumogen Red allows light absorption and energy transfer to photosystem I by Förster resonance energy transfer; therefore, the Pt nanoparticles act as active sites for hydrogen generation.

In situ synthesis of CdS/CdWO4 nanorods core-shell composite via acid dissolution.

The prevention of photocorrosion in photocatalysts allows for the use of a wide variety of visible-light-responsive photocatalysts, leading to highly efficient photocatalytic reactions. This study aimed to avoid the photocorrosion issues associated with pure CdS, a known photocorrosive photocatalyst, by forming a stable CdWO4 shell on the surface of a CdS core. The CdS/CdWO4 core-shell composite was formed using a unique method based on CdS elution under acidic conditions. An optimal CdWO4 nanorod shell was formed at a pH of 0.8, a reaction time of 30 min, and a calcination temperature of 400 °C, where the core remained intact and was sufficiently coated. The prepared CdS/CdWO4 core-shell composite was shown to be stable when exposed to light irradiation in pure water. Furthermore, it was successfully used in water splitting with an oxidation reaction side photocatalyst. This core-shell synthesis method based on core dissolution was easily and highly controlled, and is suitable for use in other similar core-shell composite applications.

Effective Photocatalytic Hydrogen Evolution by Cascadal Carrier Transfer in the Reverse Direction.

Visible-light-responsive photocatalysts used in the highly efficient hydrogen production exhibit several disadvantages such as photocorrosion and fast recombination. Because of the potential important applications of such catalysts, it is crucial that a simple, effective solution is developed. In this respect, in this study, we combined SiC (ß modification) and TiO2 with CdS to overcome the challenges of photocorrosion and fast recombination of CdS. Notably, we found that when irradiated with visible light, CdS was excited, and the excited electrons moved to the conduction band of TiO2, thereby increasing the efficiency of charge separation. In addition, by moving the holes generated on CdS to the valence band of SiC, in the opposite direction of TiO2, photocorrosion and fast recombination were prevented. As a result, in the sulfide solution, the CdS/SiC composite catalyst exhibited 4.3 times higher hydrogen generation ability than pure CdS. Moreover, this effect was enhanced with the addition of TiO2, giving 10.8 times higher hydrogen generation ability for the CdS/SiC/TiO2 catalyst. Notably, the most efficient catalyst, which was obtained by depositing Pt as a cocatalyst, exhibited 1.09 mmol g-1 h-1 hydrogen generation ability and an apparent quantum yield of 24.8%. Because water reduction proceeded on the TiO2 surface and oxidative sulfide decomposition proceeded on the SiC surface, the exposure of CdS to the solution was unnecessary, and X-ray photoelectron spectroscopy confirmed that photocorrosion was successfully suppressed. Thus, we believe that the effective composite photocatalyst construction method presented herein can also be applied to other visible-light-responsive powder photocatalysts having the same disadvantages as CdS, thereby improving the efficiency of such catalysts.