Anionic Group Self-Doping as a Promising Strategy: Band-Gap Engineering and Multi-Functional Applications of High-Performance CO₃^2–-Doped Bi₂O₂CO₃

We herein demonstrate self-doping of the CO32– anionic group into a wide bandgap semiconductor Bi2O2CO3 realized by a one-pot hydrothermal technique. The photoresponsive range of the self-doped Bi2O2CO3 can be extended from UV to visible light and the band gap can be continuously tuned. Density functional theory (DFT) calculation results demonstrate that the foreign CO32– ions are doped in the caves constructed by the four adjacent CO32– ions and the CO32– self-doping can effectively narrow the band gap of Bi2O2CO3 by lowering the conduction band position and meanwhile generating impurity level. The photocatalytic performance is evaluated by monitoring NO removal from the gas phase, photodegradation of a colorless contaminant (bisphenol A, BPA) in an aqueous solution, and photocurrent generation. In comparison with the pristine Bi2O2CO3 which is not sensitive to visible light, the self-doped Bi2O2CO3 exhibits drastically enhanced visible-light photoreactivity, which is also superior to that of many other well-known photocatalysts such as P25, C3N4, and BiOBr. The highly enhanced photocatalytic performance is attributed to combination of both efficient visible light absorption and separation of photogenerated electron–hole pairs. The self-doped Bi2O2CO3 also shows decent photochemical stability, which is of especial importance for its practical applications. This work demonstrates that self-doping with an anionic group enables the band gap engineering and the design of high-performance photocatalysts sensitive to visible light.