Site-selective Pt dewetting on WO3-coated TiO2 nanotube arrays: An electron transfer cascade-based H-2 evolution photocatalyst

Among several parameters that affect the yield of a photocatalytic process mediated by a metal oxide semiconductor, key is the efficient separation and transfer of photo-generated charge carriers. To overcome kinetic limitations and enable charge transfer, an effective strategy is to decorate the photocatalyst surface with cocatalytic nanoparticles of either a second semiconductor metal oxide or a noble metal. Nevertheless, classical deposition techniques based on powder technology approaches lead to randomly placed cocatalytic nano particles at the photocatalytic surface. The poor control over cocatalyst placement can drastically hamper the photocatalytic efficiencies, and can also prevent a full understanding of the charge carrier dynamics and photocatalytic mechanism. Here we investigate a highly defined charge separation platform for photocatalytic H-2 evolution based on a Pt-WO3-TiO2 stacked structure constructed on anodically grown TiO2 nanotube arrays. Key is the formation of a site-selective and sequential W and Pt metal sputter-decoration only at the mouth of highly-ordered TiO2 nanotubes. After placing the W-Pt bilayer at the nanotubes mouth, a suitable thermal treatment forms a WO3 layer atop the nanotubes while the Pt film undergoes solid state dewetting into 2-6 nm-sized Pt nanoparticles. These structures show strongly improved photocatalytic H-2 evolution efficiency compared to any other single-cocatalyst system (Pt-TiO2 and WO3-TiO2) and pristine TiO2 nanotubes. The photo catalytic activity improvement is ascribed to an enhanced charge carrier separation mechanism enabled by the well-defined TiO2-WO3-Pt architecture that provides swift electron transfer through WO3 and towards Pt for H-2 evolution.