Aluminum oxides as alternative building blocks for efficientlayer-by-layerblocking layers in dye-sensitized solar cells.

All inorganic layer-by-layer (LbL) thin films composed by TiO2nanoparticles and [Al(OH)4]-anions (TiO2/AlOx) as well as Al2O3and Nb2O5nanoparticles (Al2O3/Nb2O5) have been deposited to fluorine-doped tin-oxide coated glass (FTO) surfaces and applied as blocking layers in dye-sensitized solar cells (DSCs). Structural and morphological characterization of the LbL films by different techniques reveal that inTiO2/AlOxassembly, aluminate anions undergo condensation reactions on the TiO2surface leading to the formation of highly homogeneous films with unique optical properties. After 25 depositions transmittance losses below 10% in relation to the bare FTO substrate are observed. Electrochemical impedance spectroscopy shows thatTiO2/AlOxlayers impose an effective barrier for the charge recombination at FTO/electrolyte interface with an electron exchange time constant 50-fold higher than that for bare FTO. As a result, an improvement of 85% in the overall conversion efficiency of DSCs was observed with the employment of TiO2/AlOxblocking layers.Al2O3/Nb2O5LbL films can also work as blocking layers in DSCs but not as efficient, which is associated with the poor homogeneity of the film and its capacitive behavior. The production of cost-effective blocking layers with a low light scattering in the visible region is an important feature toward the application of DSC in other Building-integrated photovoltaic applications.

Unraveling the photocatalytic properties of TiO2/WO3 mixed oxides.

TiO2/WO3 heterojunctions are one of the most investigated systems for photocatalytic applications. However, distinct behavior can be found in the literature depending on the pollutant to be degraded and the photocatalyst preparation conditions. Some authors reported improved photocatalytic activities in relation to TiO2, while others a deleterious effect. Different factors have been identified to influence the activity of such systems. In this work, a systematic investigation of TiO2/WO3 samples with different W/Ti ratios (0-100%) was carried out using different pollutants as targets (gaseous NO, acetaldehyde and aqueous methylene blue solutions). A detailed structural investigation along with transient absorption studies and photoelectrochemical measurements allowed the rationalization of some of the previously reported factors that control the TiO2/WO3 photoactivity, i.e. the inability to reduce molecular oxygen, the stabilization of the anatase phase and the adsorption surface properties. The investigations also identified a factor not previously reported: in TiO2/WO3 systems, a fraction of long-lived holes do not take part in the interfacial charge transfer to efficient hole quenchers, such as methanol. This behavior seems to be related to the doping of the TiO2 matrix with W(vi) and plays a key role in the photocatalytic activity.

Layer-by-layer TiO(2)/WO(3) thin films as efficient photocatalytic self-cleaning surfaces.

New TiO2/WO3 films were produced by the layer-by-layer (LbL) technique and successfully applied as self-cleaning photocatalytic surfaces. The films were deposited on fluorine doped tin oxide (FTO) glass substrates from the respective metal oxide nanoparticles obtained by the sol-gel method. Thirty alternative immersions in pH = 2 TiO2 and pH = 10 WO3 sols resulted in ca. 400 nm thick films that exhibited a W(VI)/Ti(IV) molar ratio of 0.5, as determined by X-ray photoelectron spectroscopy. Scanning electron microscopy, along with atomic force images, showed that the resulting layers are constituted by aggregates of very small nanoparticles (<20 nm) and exhibited nanoporous and homogeneous morphology. The electronic and optical properties of the films were investigated by UV-vis spectrophotometry and ultraviolet photoelectron spectroscopy. The films behave as nanoscale heterojunctions, and the presence of WO3 nanoparticles caused a decrease in the optical band gap of the bilayers compared to that of pure LbL TiO2 films. The TiO2/WO3 thin films exhibited high hydrophilicity, which is enhanced after exposition to UV light, and they can efficiently oxidize gaseous acetaldehyde under UV(A) irradiation. Photonic efficiencies of ξ = 1.5% were determined for films constituted by 30 TiO2/WO3 bilayers in the presence of 1 ppm of acetaldehyde, which are ∼2 times higher than those observed for pure LbL TiO2 films. Therefore, these films can act as efficient and cost-effective layers for self-cleaning, antifogging applications.