Electronic structure of titania nanosheets with vacancies based on first-principles calculations

Abstract

Titania nanosheets (TNSs) are expected to lead to higher photocatalytic performance than bulk TiO2 because its high reactivity arises from the two-dimensional structure. While their electronic properties are considered to be easily affected by structural vacancies, the effects of vacancies in TNSs on the photocatalytic performance are not clear. In order to study them, we have performed first-principles molecular dynamics simulations for structure models of TNSs with several vacancies. First, we have calculated the electronic density of states and bandgap energies Eg. It has been found that Eg of our structure modes of TNSs with vacancies are larger than bulk anatase. This tendency is consistent with the experimentally observed relationship of Eg between TNSs and anatase. It has been clarified from non-adiabatic calculations that the existence of vacancies in TNSs causes spatial charge separation and leads to longer recombination time.