Electric-Dipole Effect of Defects on Energy Band Alignment of Rutile and Anatase TiO2

TL;DR

This study uses DFT+U calculations to show that defects in TiO2 surfaces induce electric dipoles that can reverse the band alignment from straddling to staggered, impacting photocatalytic efficiency.

Contribution

It reveals how defects influence the energy band alignment of TiO2 phases, providing a possible explanation for contradictory experimental observations.

Findings

Perfect surfaces have straddling band alignment.

Defects induce electric dipoles that reverse the alignment.

Defects can be used to tune photocatalytic activity.

Abstract

Titanium dioxide materials have been studied intensively and extensively due to photocatalytic applications. A long-standing open question is the energy band alignment of rutile and anatase TiO2 phases, which can affect the photocatalytic process in the composite system. There are basically two contradictory viewpoints about the alignment of these two TiO2 phases supported by respective experiments: 1) straddling type and 2) staggered type. In this work, our DFT plus U calculations find that the perfect rutile (110) and anatase (101) surfaces have the straddling type band alignment, whereas the surfaces with defects can turn the band alignment into the staggered type. The electric dipoles induced by defects are responsible for the reversal of band alignment. Thus the defects introduced during preparations and post-treatment processes of materials are probably the answer to above open question regarding the band alignment, which can be considered in real practice to tune the photocatalytic activity of materials.