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Peas in a pod: A highly aligned Au(np)@TiO2 photocatalyst was formed by self-organizing anodization of a Ti substrate followed by dewetting of a gold thin film. This leads to exactly one Au nanoparticle (np) per TiO2 nanocavity. Such arrays are highly efficient photocatalysts for hydrogen generation from ethanol.

In the present work we introduce a technique to form a photocatalyst based on Pt nanoparticles suspended over the mouth of anodic TiO2 nanotubes. These structures are obtained by decorating the top end of highly ordered TiO2 nanotubes with a web of TiO2 nanofibrils, followed by sputter deposition of a minimum amount of Pt. A subsequent thermal dewetting step forms 3-6 nm-sized Pt nanoparticles along the nanofibrils. These structures, when compared to conventional Pt decoration techniques of TiO2 nanotubes, show strongly enhanced photocatalytic H2 evolution efficiency.

TiO2 nanotubes have been investigated in photoelectrochemistry and photocatalysis for more than a decade. However, up to now, a systematic investigation of different hole scavengers is still lacking. Here we investigate the effect of the most relevant sacrificial hole scavengers on the photoelectrochemical properties and photocatalytic H2 evolution performance of pristine and Pt-decorated anodic TiO2 nanotubes. We examine methanol, isopropanol, ethylene glycol, EDTA-Na2, as well as Na2SO3, and find that the incident photocurrent conversion efficiency (IPCE) of the TiO2 nanotubes in 0.1 M Na2SO4 electrolytes increases by 1.8-3.1 times, depending on the used hole scavenger. The efficiency increases in the sequence Na2SO3 < isopropanol < MeOH < ethylene glycol < EDTA-Na2. In presence of any hole scavenger, for nanotubes in the length-range of 2-10 µm, the photocurrent spectra and the ICPE magnitude are independent of the tube length. The photocurrent onset potential (optical flatband potential) is significantly affected by the different type of scavengers, in line with their red-ox potential. Under open circuit conditions (photocatalytic conditions), organic hole scavengers lead to a 10.0-28.8 times higher H2 production by TiO2 nanotubes than the scavenger-free case, with a sequence MeOH > i-PrOH > EDTA-Na2 > EG, while a detrimental effect of Na2SO3 is observed. These results are compared to results obtained for TiO2 particles, and discussed in terms of various concepts in the literature.