Vapor Deposition of Semiconducting Phosphorus Allotropes into TiO2 Nanotube Arrays for Photoelectrocatalytic Water Splitting

Recent evidence of exponential environmental degradation will demand a drastic shift in research and development toward exploiting alternative energy resources such as solar energy. Here, we report the successful low-cost and easily accessible synthesis of hybrid semiconductor@TiO2 nanotube photocatalysts. In order to realize its maximum potential in harvesting photons in the visible-light range, TiO2 nanotubes have been loaded with earth-abundant, low-band-gap fibrous red and black phosphorus (P). Scanning electron microscopy- and scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron microscopy, and UV-vis measurements have been performed, substantiating the deposition of fibrous red and black P on top and inside the cavities of 100-mu m-long electrochemically fabricated nano-tubes. The nanotubular morphology of titania and a vapor-transport technique are utilized to form heterojunctions of P and TiO2. Compared to pristine anatase 3.2 eV TiO2 nanotubes, the creation of heterojunctions in the hybrid material resulted in 1.5-2.1 eV photoelectrocatalysts. An enhanced photoelectrochemical water-splitting performance under visible light compared with the individual components resulted for the P@TiO2 hybrids. This feature is due to synergistically improved charge separation in the heterojunction and more effective visible-light absorption. The electronic band structure and charge-carrier dynamics are investigated in detail using ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy to elucidate the charge-separation mechanism. A Fermi-level alignment in P@TiO2 heterojunctions leads to a more reductive flat-band potential and a deeper valence band compared to pristine P and thus facilitates a better water-splitting performance. Our results demonstrate effective conversion efficiencies for the nanostructured hybrids, which may enable future applications in optoelectronic applications such as photodetectors, photovoltaics, photoelectrochemical catalysts, and sensors.