Direct Interfacial Excitation from TiO₂ to Cu(II) Nanoclusters Enables Cathodic Photoresponse for Hydrogen Evolution...

The titanium dioxide (TiO₂ ) photocatalyst is only active under UV irradiation due to its wide-gap nature. A novel excitation pathway denoted as interfacial charge transfer (IFCT) has been reported to activate copper(II) oxide nanoclusters-loaded TiO₂ powder (Cu(II)/TiO₂ ) under visible-light irradiation for only organic decomposition (downhill reaction) so far. Here, the photoelectrochemical study shows that the Cu(II)/TiO₂ electrode exhibits a cathodic photoresponse under visible-light and UV irradiation. It originates from H₂ evolution on the Cu(II)/TiO₂ electrode, while O₂ evolution takes place on the anodic side. Based on the concept of IFCT, a direct excitation of electrons from the valence band of TiO₂ to Cu(II) clusters initiates the reaction. This is the first demonstration of a direct interfacial excitation-induced cathodic photoresponse for water splitting without any addition of a sacrificial agent. This study is expected to contribute to the development of abundant visible-light-active photocathode materials for fuel production (uphill reaction).