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Quasi-1D TiO nanostructures prepared by pulsed laser deposition (PLD) are tested as photoanodes for photoelectrochemical water splitting application and compared with TiO nanotube arrays prepared by anodic oxidation. PLD TiO films with controlled structure and morphology ranging from compact to vertically oriented or hierarchical porous nanostructures are deposited by ablating a TiO target with nanosecond UV laser pulses in the presence of an O background atmosphere at different pressures. Thermal treatments at different temperatures are used to transform the so-obtained amorphous systems into nanocrystalline structures (mainly anatase). The effect of film density and thickness is also considered by depositing different amounts of material per unit surface. The morphology and the phase composition of the samples are characterized by SEM and Raman spectroscopy, while the photoelectrochemical water splitting performances are investigated by monitoring the photocurrent generated under illumination in a three-electrode cell. Voltammetric scans and electrochemical impedance spectroscopy analysis were also used to correlate the morphology of PLD samples with their electrochemical properties and their working mechanism in the absence and presence of a light radiation. A clear correlation between structural/morphological properties and photoelectrochemical behavior is found and ideal values of the synthesis parameters are identified, which allow the identification of the optimal quasi-1D nanoporous morphology for water splitting applications. The use of sacrificial organic reagents as hole scavengers was also considered to improve the photoelectrochemical performance of the samples. [ABSTRACT FROM AUTHOR]

The availability of immobilized nanostructured photocatalysts is of great importance in the purification of both polluted air and liquids (e.g., industrial wastewaters). Metal-supported titanium dioxide films with nanotubular morphology and good photocatalytic efficiency in both environments can be produced by anodic oxidation, which avoids release of nanoscale materials in the environment. Here we evaluate the effect of different anodizing procedures on the photocatalytic activity of TiO2 nanostructures in gas and liquid phases, in order to identify the most efficient and robust technique for the production of TiO2 layers with different morphologies and high photocatalytic activity in both phases. Rhodamine B and toluene were used as model pollutants in the two media, respectively. It was found that the role of the anodizing electrolyte is particularly crucial, as it provides substantial differences in the oxide specific surface area: nanotubular structures show remarkably different activities, especially in gas phase degradation reactions, and within nanotubular structures, those produced by organic electrolytes lead to better photocatalytic activity in both conditions tested. [ABSTRACT FROM AUTHOR]

The plasmonic resonance of noble metal nanoparticles (NPs) can be exploited to enhance the photoresponse of wide band gap oxides in view of several solar energy applications. Here, we demonstrate single-step synthesis of plasmonic Au nanoparticles integrated in TiO 2 hierarchical nanoporous layers through a vapor phase pulsed laser co-deposition approach. Specifically, we report the fabrication and characterization of Au NPs-decorated TiO 2 forest-like systems with tunable porosity and density as well as the morphological/structural evolution as a function of Au content and we discuss the corresponding optical properties. The effect of post-deposition thermal treatment has been investigated as well in order to control TiO 2 crystallization and Au NPs nucleation and growth. Optical analyses show the onset of characteristic plasmonic resonance of Au NPs with the increase of film absorption in the visible range. Preliminary tests of photodegradation of methyl orange dye indicate that the integration of Au NPs leads to a significant increase of the catalytic activity of nanoporous TiO 2 . Our results suggest the potentiality of this approach for the synthesis and the integration of metallic NPs within wide band gap semiconductors, while paving the way toward novel plasmonic-based devices. [ABSTRACT FROM AUTHOR]