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 Ndoped 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 .

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To comprehend the photocatalytic mechanisms of anatase Ti 1−x Fe x O 2 with various concentrations of Fe, this study performed first principles calculations based on density functional theory with Hubbard U on-site correction to evaluate the crystal structure, impurity formation energy, and electronic structure. We adopted the effective Hubbard U values of 8.47 eV for Ti 3d and 6.4 eV for Fe 3d. The calculations show that higher concentrations of Fe are easily formed in anatase TiO 2 due to a reduction in the formation energy. The band gap of Fe-doped TiO 2 decreases Fe doping level increases as a result of the overlap among the Fe 3d, Ti 3d, and O 2p states, which enhances photocatalytic activity in the visible light region. Additionally, a broadening of the valence band and Fe impurity states within the band gap might also contribute to the photocatalytic activity.

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