Mechanisms of Visible Light Photocatalysis in N-Doped Anatase TiO_2 with Oxygen Vacancies from GGA+U Calculations

摘要

We have systematically studied the photocatalytic mechanisms of nitrogen doping in anatase TiO_2 using first-principles calculations based on density functional theory, employing Hubbard U (8.47 eV) on-site correction. The impurity formation energy, charge density, and electronic structure properties of TiO_2 supercells containing substitutional nitrogen, interstitial nitrogen, or oxygen vacancies were evaluated to clarify the mechanisms under visible light. According to the formation energy, a substitutional N atom is better formed than an interstitial N atom, and the formation of an oxygen vacancy in N-doped TiO_2 is easier than that in pure TiO_2. The calculated results have shown that a significant band gap narrowing may only occur in heavy nitrogen doping. With light nitrogen doping, the photocatalysis under visible light relies on N-isolated impurity states. Oxygen vacancies existence in N-doped TiO_2 can improve the photocatalysis in visible light because of a band gap narrowing and n-type donor states. These findings provide a reasonable explanation of the mechanisms of visible light photocatalysis in N-doped TiO_2.