Mesoporous black TiO2 array employing sputtered Au cocatalyst exhibiting efficient charge separation and high H2 evolution activity

The separation and transfer of photogenerated carriers are the key issue in the design of high performance TiO2 photocatalysts. In order to overcome the kinetic limitations and achieve rapid charge transfer, TiO2-related multi-component catalysts have been extensively studied. Among all the TiO2 supports, the impressive black TiO2 (BT) with broad visible light absorption spectrum and oxygen vacancies are preferable, but still suffers from low quantum efficiency. Meanwhile, poor control of cocatalyst placement by conventional loading method can also severely impede photocatalytic efficiency. Herein a fast and simple metal magnetron sputter approach was used to place highly-uniformed Au nanoparticles cocatalyst on the top of the mesoporous TiO2–BT nanotube array fabricated by in situ electrochemical anodization approach on a Ti film. This confined plasmonic photocatalyst with highly uniformly distributed Au cocatalysts exhibited greatly enhanced charge-separation and charge-transfer behavior, and a remarkable 10 times enhancement of the photocatalytic H2 evolution reactivity over conventional TiO2 nanotube. The TiO2-BT-Au electron transfer cascade structure is proposed in which black TiO2 acts as a buffer layer for TiO2 conduction band electrons, allowing efficient photogenerated electrons to be transferred to Au nanoparticles and then into the TiO2 pores that suitable for H2 generation. Since the nanotube walls themselves are curved upwards, the short diffusion length allows electrons to be easily transferred to the cocatalyst, where recombination of photogenerated electron pairs is limited. The metal magnetron sputter technique for noble metal cocatalyst immobilization and the unique TiO2–BT–Au electron-transfer system are promising and can be extended to the design of other supported catalysts.