Insights into the photocatalytic peroxymonosulfate activation over defective boron-doped carbon nitride for efficient pollutants degradation

The metal-free graphitic carbon nitride is a promising photocatalyst for peroxymonosulfate (PMS) activation towards water decontamination, but bearing low efficiency due to its electronic structure and surface chemistry. Herein, the non-metallic element boron was adopted for catalyst development. The boron dopants and defects were simultaneously introduced by potassium borohydride, resulting in an excellent activity towards PMS activation. The dominant reactive oxygen species was singlet oxygen, which was determined to originate from PMS activation over photo-induced holes initiated by an electron transfer process. Calculations based on density functional theory revealed that at excited states, due to the dopants and defects, the electron-hole distribution was altered from an even population to a significant separation, which was beneficial for photocatalytic performance. Besides, the engineered electronic structure weakened the catalyst resistance to charge transfer, enabling easier electron transfer between the catalyst and the PMS. Moreover, the strengthened and enlarged positive electrostatic potential areas on heptazine rings oriented the electron transfer process from the negatively charged PMS to the catalyst, facilitating the generation of singlet oxygen. These findings provide underlying mechanism insights into the contribution of dopants and defects to catalytic performance on persulfate-based photocatalytic water treatment.