Tailored fabrication of iridium nanoparticle-sensitized titanium oxynitride nanotubes for solar-driven water splitting: experimental insights on the photocatalytic-activity-defects relationship

Understanding the photocatalytic-activity-defects relationship of titanium oxynitride nanotubes (TiON-NTs) is important for tailoring their photocatalytic performance. Herein, we fabricated highly ordered and vertically aligned nanotube arrays of TiON-NT-functionalized with iridium nanoparticles denoted as (Ir/TiON-NTs) for solar-driven water splitting. Positron annihilation lifetime spectroscopy (PALS) and variable-energy positron annihilation spectroscopy (VEPAS) were performed to quantify the vacancy-type defects of Ir/TiON-NTs relative to TiON-NTs and TiO2-NTs. The results display that the Ir/TiON-NTs exhibit abundant defects such as small nitrogen vacancies, larger size vacancy clusters, and small voids. The obtained photocurrent density of the Ir/TiON-NTs (11.3 mA cm(-2)) is about 3.97, 5, and 11.89 times higher than that of Ir/TiO2-NTs, TiON-NTs, and TiO2-NTs, respectively. The Mott-Schottky analysis revealed the highest significant negative shift in the band potential and the lowest donor density of Ir/TiON-NTs compared to its counterparts. This result is attributed to the unique structural and compositional merits of Ir/TiON-NTs despite the abundant defects, which delay the charge recombination and improve the photocatalytic activity. The presented study may open new frontiers on engineering the defects of metal oxynitrides with metal-based catalysts for photocatalytic applications.