Benefiting from its strong oxidizing properties, the singlet oxygen has garnered serious attentions in physical, chemical, as well as biological studies. However, the photosensitizers for the generation of singlet oxygen bear in low quantum yields, lack of long wavelength absorption band, poor biocompatibility, undegradable in living tissues, and so on. Here we first demonstrate the exfoliated black phosphorus nanosheets to be effective photosensitizers for the generation of singlet oxygen with a high quantum yield of about 0.91, rendering their attractive applications in catalysis and photodynamic therapy. Through in vitro and in vivo studies, the water dispersible black phosphorus nanosheets show notable cancer therapy ability. In addition, the photodegradable character of black phosphorus from element to biocompatible phosphorus oxides further highlights its therapeutic potential against cancer. This study will not only expand the breadth of study in black phosphorus but also offer an efficient catalyst and photodynamic therapy agent.

Excitonic effects mediated by Coulomb interactions between photogenerated electrons and holes play crucial roles in photoinduced processes of semiconductors. In terms of photocatalysis, however, efforts have seldom been devoted to the relevant aspects. For the catalysts with giant excitonic effects, the coexisting, competitive exciton generation serves as a key obstacle to the yield of free charge carriers, and hence, transformation of excitons into free carriers would be beneficial for optimizing the charge-carrier-involved photocatalytic processes. Herein, by taking bismuth oxybromide (BiOBr) as a prototypical model system, we demonstrate that excitons can be effectively dissociated into charge carriers with the incorporation of oxygen vacancy, leading to excellent performances in charge-carrier-involved photocatalytic reactions such as superoxide generation and selective organic syntheses under visible-light illumination. This work not only establishes an in-depth understanding of defective structures in photocatalysts but also paves the way for excitonic regulation via defect engineering.