Electronic structure and photocatalytic activities of (Bi2−δYδ)Sn2O7 solid solution

Abstract

A series of (Bi2−δYδ)Sn2O7 solid solutions were prepared by a one-step hydrothermal method to investigate the correlation between the electronic structures and photocatalytic activity. All the (Bi2−δYδ)Sn2O7 samples were characterized by X-ray diffraction, transmission electron microscopy, infrared and UV–vis absorption spectroscopy, and the Brunauer–Emmett–Teller technique. The effects of Bi 6s orbitals in (Bi2−δYδ)Sn2O7 solid solutions on the electronic structures and photogradation of colorless 2-naphthol solution were investigated experimentally and theoretically. It is found that the introduction of Y3+ induces the shrinkage of the lattice of (Bi2−δYδ)Sn2O7 solid solutions. Consequently, the contribution of Bi 6s orbitals to electronic structures of (Bi2−δYδ)Sn2O7 solid solutions can be continuously tuned by Y3+ substitution for Bi3+. Density function theory calculations reveal that the Bi 6s and O 2p states dominate the top of valence band of Bi2Sn2O7, while the bottom of conduction band mainly consists of the states of Sn 5s, O 2p and Bi 6p. Once the Bi3+ ions are substituted by Y3+, the intensity of Bi 6s states is weakening at the top of valence band while the bottom of conduction band retains the same feature observed for pure Bi2Sn2O7. Moreover, the band dispersions of valence band and conduction band become narrower after Y3+ introduction into the lattice of (Bi2−δYδ)Sn2O7 solid solutions. As a result, the photocatalytic performance for decomposition of 2-naphthol has been suppressed by the Y3+ substitution, since the electronic structure limits the mobility of the photoinduced charge carriers. Our results suggest that high photocatalytic activity of Bi-containing compounds should originate from the good band dispersions of valence band and conduction band involving the Bi 6s orbitals.