Heterophase homojunction construction by amorphous TiOx and N–TiO2 photoanode for oxygen evolution reaction kinetics and charge carriers’ transportation enhancement

Abstract

Photoelectrochemical (PEC) water splitting by TiO2 photoanode for clean hydrogen production is limited by the poor charge separation and inert oxygen evolution reaction (OER) kinetics issues for now. In this work, a band-matched heterophase homojunction (TiOx/N–TiO2) by amorphous TiOx and N-doped TiO2 nanotube arrays is constructed by two-step anodic oxidation and impregnation. The photocurrent density of TiOx/N–TiO2 reaches 0.69 mA/cm2 at 1.23 V vs. RHE, which is 1.86 folds than bare TiO2. The enhanced charge carriers' injection/separation efficiency, smaller Tafel slope (37.79 mF dec−1) and larger electrochemical active surface area (ECSA) (1.98 mF cm−2) of TiOx/N–TiO2 indicate that N doping and heterophase homojunction with amorphous TiOx effectively facilitate the surface OER kinetics and charge carriers' transportation. TiOx/N–TiO2 is annealed with a transformation of the surface amorphous TiOx layer into anatase TiO2 (a-TiOx/N–TiO2) to study the role of amorphous TiO2 in PEC water splitting. The photocurrent density and applied bias photon-to-current efficiency (ABPE) for a-TiOx/N–TiO2 decrease, even lower than the pristine TiO2. This is due to the reduction of surface oxygen vacancies, which causes the slowdown of OER kinetics and the weakening of charge carrier transportation ability. That is favorable for a better understanding of the OER kinetics and charge carriers’ transportation enhancement mechanism by the surficial modification on the semiconductor during the PEC water splitting.