Ce和O空位共掺杂TiO_2的电子结构与光学性质

Electronic structures and optical properties of Ce-doped anatase TiO_2 with oxygen vacancy

采用基于密度泛函理论加U的计算方法,研究了Ce和O空位单(共)掺杂锐钛矿相TiO_2的电子结构和光吸收性质.计算结果表明,Ce和O空位共掺杂TiO_2的带隙中出现了杂质能级,且带隙窄化为2.67 eV,明显比纯TiO_2和Ce,O空位单掺杂TiO_2的要小,因而可提高TiO_2对可见光的响应能力,使TiO_2的光吸收范围增加.光吸收谱显示,掺杂后TiO_2的光吸收边发生了显著红移;在400.0—677.1 nm的可见光区,共掺杂体系的光吸收强度显著高于纯TiO_2和Ce单掺杂TiO_2,而略低于O空位单掺杂TiO_2.此外,Ce掺杂TiO_2中引入O空位后,TiO_2的导带边从-0.27 eV变化为-0.32 eV,这表明TiO_2的导带边的还原能力得到了加强.计算结果为Ce和O空位共掺杂TiO_2在可见光光解水方面的进一步研究提供了有力的理论依据.

The crystal structures,defect formation energy,electronic structures and optical properties of oxygen vacancy and/or Ce-(co)doped anatase TiO2 are investigated by using density functional theory plus U calculations.The calculated results indicate that lattice distortion induces the enhanced octahedral dipole moment in Ce doped TiO2 crystal when introducing oxygen vacancy into the lattice of the TiO2 crystal,which is effective for separating the photo-excited electron-hole pairs;meanwhile,compared with the valence band of pure TiO2 and TiO2 mono-doped separately with Ce and oxygen vacancy,the valence band of TiO2 co-doped with Ce and oxygen vacancy broadens drastically,which is mainly contributed from the electronic states of Ce 5 d,Ti 4 s and O 2 p in the valence band shifting toward the lower energy direction.As a result,Ce doped TiO2 with oxygen vacancy is beneficial to the mobility of photo-generated carriers in TiO2.Similarly,the anti-bonding states also move toward the lower band energy direction,which are formed by the mixture of Ce 4 f,Ce 5 d,Ti 3 d,and O 2 p orbits in the conduction band.Due to these shifts,the energy gap of Ce and oxygen vacancy codoped TiO2 is narrowed to 2.67 eV with the emerge of the occupied impurity energy levels near Fermi level.Because of the above-mentioned excellence features,the absorption spectra for doped systems exhibit remarkable red-shift,especially,the intensity of optical absorption of TiO2 co-doped with Ce and oxygen vacancy in the visible region and the infra-red region are obviously stronger than those of the Ce mono-doped TiO2.When introducing oxygen vacancy into the Ce-doped system,the calculated conduction band energy edge position changes from-0.27 eV to-0.32 eV,which implies that the reducing power of the conduction band edge of TiO2 is remarkably enhanced.More fascinatingly,the calculated band energy edges for the Ce and oxygen vacancy codoped TiO2 can satisfy the basic requirement for water splitting under visible light irradiation.In conclusion,Ce and oxygen vacancy co-doped system can effectively strengthen the photo-catalytic activity of TiO2 and improve the utilization of the solar light;and our calculated results provide a powerful theoretical basis for the applications of the Ce and oxygen vacancy co-doped anatase TiO2 in visible-light-driven water splitting in the future research.