Titanium dioxide (TiO2) and zinc oxide (ZnO) nanostructures have been widely used as photo-catalysts due to their low-cost, high surface area, robustness, abundance and non-toxicity. In this work, four TiO2 and ZnO-based nanostructures, i.e. TiO2 nanoparticles (TiO2 NPs), TiO2 nanotubes (TiO2 NTs), ZnO nanowires (ZnO NWs) and ZnO@TiO2 core-shell structures, specifically prepared with a fixed thickness of about 1.5 μm, are compared for the solar-driven water splitting reaction, under AM1.5G simulated sunlight. Complete characterization of these photo-electrodes in their structural and photo-electrochemical properties was carried out. Both TiO2 NPs and NTs showed photo-current saturation reaching 0.02 and 0.12 mA cm(-2), respectively, for potential values of about 0.3 and 0.6 V vs. RHE. In contrast, the ZnO NWs and the ZnO@TiO2 core-shell samples evidence a linear increase of the photocurrent with the applied potential, reaching 0.45 and 0.63 mA cm(-2) at 1.7 V vs. RHE, respectively. However, under concentrated light conditions, the TiO2 NTs demonstrate a higher increase of the performance with respect to the ZnO@TiO2 core-shells. Such material-dependent behaviours are discussed in relation with the different charge transport mechanisms and interfacial reaction kinetics, which were investigated through electrochemical impedance spectroscopy. The role of key parameters such as electronic properties, specific surface area and photo-catalytic activity in the performance of these materials is discussed. Moreover, proper optimization strategies are analysed in view of increasing the efficiency of the best performing TiO2 and ZnO-based nanostructures, toward their practical application in a solar water splitting device.

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A fast and low-cost sol-gel synthesis used to deposit a shell of TiO2 anatase onto an array of vertically aligned ZnO nanowires (NWs) is reported in this paper. The influence of the annealing atmosphere (air or N2) and of the NWs preannealing process, before TiO2 deposition, on both the physicochemical characteristics and photoelectrochemical (PEC) performance of the resulting heterostructure, was studied. The efficient application of the ZnO@TiO2 core-shells for the PEC water-splitting reaction, under simulated solar light illumination (AM 1.5G) solar light illumination in basic media, is here reported for the first time. This application has had a dual function: to enhance the photoactivity of pristine ZnO NWs and to increase the photodegradation stability, because of the protective role of the TiO2 shell. It was found that an air treatment induces a better charge separation and a lower carrier recombination, which in turn are responsible for an improvement in the PEC performance with respect to N2-treated core-shell materials. Finally, a photocurrent of 0.40 mA/cm(2) at 1.23 V versus RHE (2.2 times with respect to the pristine ZnO NWs) was obtained. This achievement can be regarded as a valuable result, considering similar nanostructured electrodes reported in the literature for this application.