Trap-state passivation of titania nanotubes by electrochemical doping for enhanced photoelectrochemical performance

Abstract

TiO₂ nanotubes are widely investigated materials for photoelectrochemical water splitting, but the presence of trap states limits their performance by facilitating the recombination of electron/hole pairs. In this investigation we unequivocally demonstrate that the photocurrent improvement observed in TiO₂ nanotubes after performing electrochemical doping with hydrogen or lithium ions is due to trap state passivation. Specifically, electrochemical impedance spectroscopy evidences that trap state defects disappear upon electrochemical doping, concurrent with an increase in the electron lifetime and faster photocurrent transients. This results in a two-fold enhancement in the photocurrent under simulated sunlight at 1.0 V vs. SCE. Li intercalation was confirmed and the structure as well as the composition of the modified nanotubes was elucidated by GDOES, XPS, and TEM.