Vertically Oriented Ti−Fe−O Nanotube Array Films:  Toward a Useful Material Architecture for Solar Spectrum Water Photoelectrolysis

In an effort to obtain a material architecture suitable for high-efficiency visible spectrum water photoelectrolysis, herein we report on the fabrication and visible spectrum (380-650 nm) photoelectrochemical properties of self-aligned, vertically oriented Ti-Fe-O nanotube array films. Ti-Fe metal films of variable composition, iron content ranging from 69% to 3.5%, co-sputtered onto FTO-coated glass are anodized in an ethylene glycol + NH4F electrolyte. The resulting amorphous samples are annealed in oxygen at 500 degrees C, resulting in nanotubes composed of a mixed Ti-Fe-O oxide. Some of the iron goes into the titanium lattice substituting titanium ions, and the rest either forms alpha-Fe2O3 crystallites or remains in the amorphous state. Depending upon the Fe content, the band gap of the resulting films ranges from about 380 to 570 nm. The Ti-Fe oxide nanotube array films are utilized in solar spectrum water photoelectrolysis, demonstrating 2 mA/cm2 under AM 1.5 illumination with a sustained, time-energy normalized hydrogen evolution rate by water splitting of 7.1 mL/W.hr in a 1 M KOH solution with a platinum counter electrode under an applied bias of 0.7 V. The surface morphology, structure, elemental analysis, optical, and photoelectrochemical properties of the Ti-Fe oxide nanotube array films are considered.