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The supersonic cluster beam deposition (SCBD) of titanium oxide nanoparticles is a versatile and effective bottom-up approach for the fabrication of nanostructured titanium dioxide (ns-TiO 2 ) thin films; here we report on its application to the production of photoelectrodes for photoelectrochemical water splitting. The use of a cluster-assembled carbon (ns-C) thin film deposited by SCBD as a substrate layer for the titania nanoparticles deposition is also investigated and demonstrated to originate C:TiO 2 nanocomposite photoelectrodes with increased surface roughness and more than four-fold enhanced IPCE (ca. 4.5% under monochromatic illumination at 330 nm employing KOH 1 M as aqueous electrolyte solution and without any external bias) compared to pure TiO 2 photoelectrodes deposited by the same technique and featuring the same TiO 2 thickness (ca. 250 nm). Electrochemical impedance spectroscopy (EIS) has been used to correlate the increase of the IPCE to an optimized electrode structure, electrolyte accessibility and electric conductivity. These results are promising towards the practical use of nanoparticle-assembled materials and the improving of their properties.

Photoactive membranes coated with TiO 2 and Pt/TiO 2 nanostructured thin films were produced by one-step deposition of gas phase nanoparticles on glass fiber filters. Pt/TiO 2 nanoparticles (0–1.5 wt.% Pt content) were produced by flame spray pyrolysis, starting from liquid solutions of the Ti and Pt precursors, and then expanded in a supersonic beam to be deposited on the filters. The nanostructured coatings were composed of crystalline nanoparticles (mainly anatase phase), without any need of post-deposition annealing. The so obtained photocatalytic membranes were tested in hydrogen production by photo-steam reforming of ethanol in an expressly set-up diffusive photoreactor. The reaction rate was found to increase with increasing the Pt content in the photoactive material, up to 1.5 wt.% Pt. The use of these membranes allowed a significant increase of the hydrogen production rate compared to that obtained with the same photoactive Pt/TiO 2 films deposited on a quartz substrate.

Nanostructured carbon sp(2) (ns-C) thin films with up to 30% of sp-coordinated atoms (carbynes) were produced in a high vacuum by the low kinetic energy deposition of carbon clusters produced in the gas phase and accelerated by a supersonic expansion. Immediately after deposition the ns-C films were immersed in situ in an ionic liquid electrolyte. The interfacial properties of ns-C films in the ionic liquid electrolyte were characterized by electrochemical impedance spectroscopy and cyclic voltammetry (CV). The so-prepared carbyne-rich electrodes showed superior electric double layer (EDL) capacitance and electric conductivity compared to ns-C electrodes containing only sp(2) carbon, showing the substantial influence of carbynes on the electrochemical properties of nanostructured carbon electrodes.

The photocatalytic activity of thin, nanostructured films of titanium dioxide, synthesized by supersonic cluster beam deposition (SCBD) from the gas phase, has been investigated employing the photodegradation of salicylic acid as test reaction. Because of the low deposition energy, the so-deposited highly porous TiO2 films are composed of nanoparticles maintaining their original properties in the film, which can be fully controlled by tuning the deposition and post-deposition treatment conditions. A systematic investigation on the evolution of light absorption properties and photoactivity of the films in relation to their morphology, determined by AFM analysis, and phase composition, determined by Raman spectroscopy, has been performed. The absorption and photocatalytic activity of the nanostructured films in the visible region could be enhanced either through post-deposition annealing treatment in ammonia containing atmosphere or employing mild oxidation conditions, followed by annealing in N2 at 600 °C.