Native defects and
nonmetal doping have
been shown to be an effective way to optimize the photocatalytic properties
of Bi2WO6. However, a detailed understanding
of defect physics in Bi2WO6 has been lacking.
Here, using the Heyd–Scuseria–Ernzerhof hybrid functional
defect calculations, we study the formation energies, electronic structures,
and optical properties of native defects and nonmetal element (C,
N, S, and P) doping into Bi2WO6. We find that
the Bi vacancy (Bivac), O vacancy (Ovac), S
doping on the O site (SO), and N doping on the O site (NO) defects in the Bi2WO6 can be stable
depending on the Fermi level and chemical potentials. By contrast,
the substitution of an O atom by a C or P atom (CO, PO) has high formation energy and is unlikely to form. The calculated
electronic structures of the Bivac, Ovac, SO, and NO defects indicate that the band-gap reduction
of Ovac
2+, Bivac
3–, and
SO defects is mainly due to forming shallow impurity levels
within the band gap. The calculated absorption coefficients of Ovac
2+, Bivac
3–, and
SO show strong absorption in the visible light region,
which is in good agreement with the experimental results. Hence, Ovac
2+, Bivac
3–, and
SO defects can improve the adsorption capacity of Bi2WO6, which helps enhance its photocatalytic performance.
Our results provide insights into how to enhance the photocatalytic
activity of Bi2WO6 for energy and environmental
applications through the rational design of defect-controlled synthesis
conditions.