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

Abstract

Abstract Separation and transfer of photogenerated charge carriers are key elements in designing photocatalysts. TiO 2 in numerous geometries has been for many years the most studied photocatalyst. To overcome kinetic limitations and achieve swift charge transfer, TiO 2 has been widely investigated with cocatalysts that are commonly randomly placed nanoparticles on a TiO 2 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 TiO 2 nanotube morphology can provide an enhancement of the photocatalytic reactivity. A TiO 2 –WO 3 –Au electron‐transfer cascade photocatalyst is designed with nanoscale precision for H 2 production on TiO 2 nanotube arrays. Key aspects in the construction are the placement of the WO 3 /Au element at the nanotube top by site‐selective deposition and self‐ordered thermal dewetting of Au. In the ideal configuration, WO 3 acts as a buffer layer for TiO 2 conduction band electrons, allowing for their efficient transfer to the Au nanoparticles and then to a suitable environment for H 2 generation, while TiO 2 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 H 2 generation rates significantly higher than any individual cocatalyst–TiO 2 combination, including a classic noble metal–TiO 2 configuration.