Conversion of toluene and water to methylcyclohexane and oxygen using niobium-doped strontium titanate photoelectrodes.

Methylcyclohexane (MCH) is regarded as a promising hydrogen carrier that enables hydrogen to be harnessed as an alternate fuel source, which paves the way to a clean-energy future. A photoelectrochemical (PEC) system with a Nb:SrTiO3 photoelectrode for oxygen evolution from an aqueous electrolyte and a Pt/C electrode for toluene (TL) hydrogenation to MCH was investigated under UV irradiation. A Nb:SrTiO3 single-crystal electrode and an ionomer/Pt/C membrane-electrode assembly (MEA) were used as the photoanode and cathode, respectively. A steady-state current density of 0.12 mA cm(-2) was observed for the two-electrode system without any bias voltage for >2 h, and a Faradaic efficiency of 97% was obtained for MCH production from TL. This is the first demonstration of the production of MCH from TL and water using only light energy. This means that light energy was converted directly into MCH from TL and water without any electricity. The PEC properties of the devices are discussed.

High photocatalytic activity of transparent films composed of ZnO nanosheets.

Nanometric thin films were prepared by dip-coating and inkjet printing ZnO nanosheets on glass plates. The side-by-side alignment of the ZnO nanosheets on the substrate resulted in thin, transparent, oriented ZnO surfaces with the high-energy {001} facets exposed. The method of nanosheet deposition affected the film morphology; the dip-coated films were very smooth and nonporous, while the inkjet-printed films were rough and porous with the estimated void volume approximately 60-70% of the total film volume. The first-order rate constants for the photocatalytic degradation of 4-chlorophenol on the nanosheet-based films were approximately 2 times larger than those on nanocolumnar ZnO films or ZnO films prepared by the sol-gel technique. We attribute the high photocatalytic activity of the ZnO nanosheets to the fact that their {001} facets were predominantly exposed to the oxidized substrate. This surface arrangement and the simplicity of fabricating the ZnO nanosheet-based films make them promising for the construction of optical devices and dye-sensitized solar cells.

Adsorption and photocatalytic and photosensitised bleaching of acid orange 7 on multilayer mesoporous films of TiO2.

A series of mesoporous films of titania of different thicknesses are prepared and their surface areas and porosities determined by physical adsorption using Kr as the adsorbate. The amounts of acid orange 7 (AO7) adsorbed by these films are found to be proportional to their measured surface areas and so the possibility of using this as a method of determining the surface area of thin titania films is discussed. The initial rates of UV-driven photocatalytic- and visible-driven photosensitised-bleaching of AO7 in solution, upon UVA and visible light irradiation, respectively, are also directly dependent upon the measured surface areas of the titania films. The quantum efficiencies for the UV photocatalytic- and visible photosensitised-bleaching of AO7 by the thickest of the AO7 films were estimated to be 0.08 and 0.01%, respectively.

Mesoporous films of TiO(2) as efficient photocatalysts for the purification of water.

Variably thick mesoporous TiO(2) films were prepared by alternately dip- and spray-coating using sol containing titanium(IV) alkoxide, concentrated HCl and suitable block-copolymer as a structure directing agent. The film thickness was controlled by varying the number of deposited layers. Their porosity was homogeneous: surface area and pore volume increased linearly with increasing number of deposited layers. Photoactivity of the films was tested employing photocatalytic degradation of 10(-4) M 4-chlorophenol in a 60 mL photoreactor under UV irradiation at 365 nm. The incident light intensity was 1 mW cm(-2). The degradation rate constants increased with increasing number of layers, proportional to their absorbances. However, the progressive improvement of the photocatalytic performance slightly decreased with the increasing number of layers. The spray-coating layers exhibited lower photocatalytic performance due to their smaller thicknesses.

Ultrasmall titania nanocrystals and their direct assembly into mesoporous structures showing fast lithium insertion.

Ultrasmall and highly soluble anatase nanoparticles were synthesized from TiCl(4) using tert-butyl alcohol as a new reaction medium. This synthetic protocol widens the scope of nonaqueous sol-gel methods to TiO(2) nanoparticles of around 3 nm with excellent dispersibility in ethanol and tert-butanol. Microwave heating was found to enhance the crystallinity of the nanoparticles and to drastically shorten the reaction time to less than 1 h at temperatures as low as 50 degrees C. The extremely small size of the nanoparticles and their dispersibility make it possible to use commercial Pluronic surfactants for evaporation-induced self-assembly of the nanoparticulate building blocks into periodic mesoporous structures. A solution of particles after synthesis can be directly used for preparation of mesoporous films without the need for particle separation. The mesoporous titania coatings fabricated using this one-pot procedure are crystalline and exhibit high surface areas of up to 300 m(2)/g. The advantages of the retention of the mesoporous order with extremely thin nanocrystalline walls were shown by electrochemical lithium insertion. The films made using microwave-treated nanoparticles showed supercapacitive behavior with high maximum capacitance due to quantitative lithiation with a 10-fold increase of charging rates compared to a standard reference electrode made from 20 nm anatase particles.