A Cocatalytic Electron-Transfer Cascade Site-Selectively Placed on TiO2 Nanotubes Yields Enhanced Photocatalytic H2 Evolution

Separation and transfer of photogenerated charge carriers are key elements in designing photocatalysts. TiO2 in numerous geometries has been for many years the most studied photocatalyst. To overcome kinetic limitations and achieve swift charge transfer, TiO2 has been widely investigated with cocatalysts that are commonly randomly placed nanoparticles on a TiO2 surface. The poor control over cocatalyst placement in powder technology approaches can drastically hamper the photocatalytic efficiencies. Here in contrast it is shown that the site-selective placement of suitable charge-separation and charge-transfer cocatalysts on a defined TiO2 nanotube morphology can provide an enhancement of the photocatalytic reactivity. A TiO2–WO3–Au electron-transfer cascade photocatalyst is designed with nanoscale precision for H2 production on TiO2 nanotube arrays. Key aspects in the construction are the placement of the WO3/Au element at the nanotube top by site-selective deposition and self-ordered thermal dewetting of Au. In the ideal configuration, WO3 acts as a buffer layer for TiO2 conduction band electrons, allowing for their efficient transfer to the Au nanoparticles and then to a suitable environment for H2 generation, while TiO2 holes due to intrinsic upward band bending in the nanotube walls and short diffusion length undergo a facilitated transfer to the electrolyte where oxidation of hole-scavenger molecules takes place. These photocatalytic structures can achieve H2 generation rates significantly higher than any individual cocatalyst–TiO2 combination, including a classic noble metal–TiO2 configuration.