Metal-Cluster-Decorated TiO2 Nanotube Arrays: A Composite Heterostructure toward Versatile Photocatalytic and Photoelectrochemical Applications

Recent years have witnessed increasing interest in the solution‐phase synthesis of atomically precise thiolate‐protected gold clusters (Aux); nonetheless, research on the photocatalytic properties of Aux–semiconductor nanocomposites is still in its infancy. In this work, recently developed glutathione‐capped gold clusters and highly ordered nanoporous layer‐covered TiO2 nanotube arrays (NP‐TNTAs) are employed as nanobuilding blocks for the construction of a well‐defined Aux/NP‐TNTA heterostructure via a facile electrostatic self‐assembly strategy. Versatile photocatalytic performances of the Aux/NP‐TNTA heterostructure which acts as a model catalyst, including photocatalytic oxidation of organic pollutant, photocatalytic reduction of aromatic nitro compounds and photoelectrochemical (PEC) water splitting under simulated solar light irradiation, are systematically exploited. It is found that synergistic interaction stemming from monodisperse coverage of Aux clusters on NP‐TNTAs in combination with hierarchical nanostructure of NP‐TNTAs reinforce light absorption of Aux/NP‐TNTA heterostructure especially within visible region, hence contributing to the significantly enhanced photocatalytic and PEC water splitting performances. Moreover, photocatalytic and PEC mechanisms over Aux/NP‐TNTA heterostructure are elucidated and corresponding reaction models were presented. It is anticipated that this work could boost new insight for photocatalytic properties of metal‐cluster‐sensitized semiconductor nanocomposites. A well‐defined heterostructure consisting of monodisperse Au clusters and hierarchically ordered nanoporous TiO2 nanotube arrays (Aux/NP‐TNTAs) is fabricated via a facile two‐step anodization approach combined with efficient electrostatic self‐assembly. The hierarchically ordered Aux/NP‐TNTA heterostructure demonstrates versatile photocatalytic redox and photoelectrochemical performances under simulated solar light irradiation under ambient conditions.