Cellulose nanofiber-templated three-dimension TiO2 hierarchical nanowire network for photoelectrochemical photoanode.

Three dimensional (3D) nanostructures with extremely large porosity possess a great promise for the development of high-performance energy harvesting and storage devices. In this paper, we developed a high-density 3D TiO2 fiber-nanorod (NR) heterostructure for efficient photoelectrochemical (PEC) water splitting. The hierarchical structure was synthesized on a ZnO-coated cellulose nanofiber (CNF) template using atomic layer deposition (ALD)-based thin film and NR growth procedures. The tubular structure evolution was in good agreement with the recently discovered vapor-phase Kirkendall effect in high-temperature ALD processes. The NR morphology was formed via the surface-reaction-limited pulsed chemical vapor deposition (SPCVD) mechanism. Under Xenon lamp illumination without and with an AM 1.5 G filter or a UV cut off filter, the PEC efficiencies of a 3D TiO2 fiber-NR heterostructure were found to be 22-249% higher than those of the TiO2-ZnO bilayer tubular nanofibers and TiO2 nanotube networks that were synthesized as reference samples. Such a 3D TiO2 fiber-NR heterostructure offers a new route for a cellulose-based nanomanufacturing technique, which can be used for large-area, low-cost, and green fabrication of nanomaterials as well as their utilizations for efficient solar energy harvesting and conversion.