Tailoring the defects of sub-100 nm multipodal titanium nitride/oxynitride nanotubes for efficient water splitting performance

Deciphering the photocatalytic-defect relationship of photoanodes can pave the way towards the rational design for high-performance solar energy conversion. Herein, we rationally designed uniform and aligned ultrathin sub-100 nm multipodal titanium nitride/oxynitride nanotubes (TiON(x)NTs) (x = 2, 4, and 6 h) via the anodic oxidation of Ti-foil in a formamide-based electrolyte followed by annealing under ammonia gas for different durations. XPS, XPS imaging, Auger electron spectra, and positron annihilation spectroscopy disclosed that the high nitridation rate induced the generation of a mixture of Ti-nitride and oxynitride with various vacancy-type defects, including monovacancies, vacancy clusters, and a few voids inside TiO(x)NTs. These defects decreased the bandgap energy to 2.4 eV, increased visible-light response, and enhanced the incident photon-to-current collection efficiency (IPCE) and the photocurrent density of TiON(x)NTs by nearly 8 times compared with TiO(2)NTs, besides a quick carrier diffusion at the nanotube/electrolyte interface. The water-splitting performance of sub-100 nm TiON(6)NT multipodal nanotubes was superior to the long compacted TiON(x)NTs with different lengths and TiO(2) nanoparticles. Thus, the optimization of the nitridation rate tailors the defect concentration, thereby achieving the highest solar conversion efficiency.