Effect of potassium adsorption on the photochemical properties of titania nanotube arrays

It is demonstrated that vertically-aligned titania nanotube planar arrays fabricated by electrochemical anodization using standard potassium-containing electrolytes invariably contain a significant amount of surface-adsorbed potassium ions, hitherto undetected, that affect the titania photoelectrochemical or PEC performance. Synchrotron-based near edge X-ray absorption fine structure (NEXAFS) spectroscopy reveals the strong ionic nature of surface potassium-titania bonds that alters the PEC performance over that of pure titania nanotubes through reduction of the external electrical bias needed to produce hydrogen at maximum efficiency. This result implies that the external electrical energy input required per liter of solar hydrogen produced with potassium-adsorbed titania nanotubes may be reduced. Tailoring the potassium content may thus be an alternative means to fine-tune the photoelectrochemical response of TiO₂ nanotube-based PEC electrodes.