Ice-templated synthesis of tungsten oxide nanosheets and their application in arsenite oxidation.

Tungsten oxide (WO3) nanosheets were prepared as catalysts to activate hydrogen peroxide (H2O2) in arsenite (As(III)) oxidation. Ice particles were employed as templates to synthesize the WO3 nanosheets, enabling easy template removal via melting. Transmission electron microscopy and atomic force microscopy revealed that the obtained WO3 nanosheets were plate-like, with lateral sizes ranging from dozens of nanometers to hundreds of nanometers and thicknesses of <10 nm. Compared to that of the WO3 nanoparticle/H2O2 system, a higher efficiency of As(III) oxidation was observed in the WO3 nanosheet/H2O2 system. Electron spin resonance spectroscopy, radical quenching studies, and As(III) oxidation experiments under anoxic conditions suggested that the hydroperoxyl radical (HO2●) acted as the primary oxidant. The WO3 nanosheets possessed numerous surface hydroxyl groups and electrophilic metal centers, enhancing the production of HO2● via H2O2 activation. Various anions commonly present in As(III)-contaminated water exhibited little effect on As(III) oxidation in the WO3 nanosheet/H2O2 system. The high oxidation efficiency was maintained by adding H2O2 when it was depleted, suggesting that the catalytic activity of the WO3 nanosheets did not deteriorate after multiple catalytic cycles.

Temperature-boosted photocatalytic H2 production and charge transfer kinetics on TiO2 under UV and visible light.

This study investigates the effect of reaction temperature (298-353 K) on photocatalytic H2 production in bare and platinized TiO2 (Pt/TiO2) suspensions containing various organic hole scavengers (EDTA, methanol, and formic acid) under UV (λ > 320 nm) and visible light (λ > 420 nm for ligand-to-metal charge transfer). H2 production rates are enhanced ∼7.8- and ∼2.5-fold in TiO2 and Pt/TiO2 suspensions, respectively, with EDTA under UV by simply elevating the reaction temperature from 298 K to 323 K (ΔT = 25 °C). Such a temperature-boosted increase in H2 production is always observed, regardless of the TiO2 crystalline structure (anatase, rutile, and an anatase/rutile mixture), type of hole scavenger, and irradiation wavelength range. It is estimated that approximately 90% of incident photons are utilized in H2 production, for which the activation energy is 25.5 kJ mol-1. Detailed photoelectrochemical analyses show the positive relationship between reaction temperature and photocurrent generation, with charge carrier mobility and interfacial charge transfer improving at higher temperatures. Other possible factors, such as H2 solubility and mass transport, play a limited role.

Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery.

As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a "solar water battery". The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E(0) (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge.