N-doped Graphitic C3N4 Nanosheets Decorated with CoP Nanoparticles: A highly efficient activator in singlet oxygen dominated visible-light-driven peroxymonosulfate activation for degradation of pharmaceuticals and personal care products

Abstract CoP nanoparticle-loaded N-doped graphitic C3N4 nanosheets (CoP/N-g-C3N4) were fabricated via a facile three-step method to degrade pharmaceuticals and personal care products (PPCPs) via a visible-light-driven (VLD) peroxymonosulfate (PMS) activation system. 2 ppm carbamazepine (CBZ) can be removed completely within 10 minutes by the VLD-PMS system with a kinetic constant of k = 0.29128 min-1, as 25.8 times compared to that under dark conditions (k = 0.01128 min-1). The experimental and theoretical results showed that the doped graphitic N atoms could modulate the electronic properties of the g-C3N4 nanosheets. Subsequently, the Density Functional Theory (DFT) explained that CoP showed preference to bonding with the nitrogen atoms involved in the newly formed N=N bond, and the Co-N bond dramatically enhanced the transfer of photo-generated electrons from the N-g-C3N4 nanosheets. Electron paramagnetic resonance (EPR) tests show that singlet oxygen (1O2) plays a leading role in this case. Moreover, PMS molecules are also tended to be absorbed onto the electron-deficient carbon atoms near the newly formed N=N bonds for PMS reduction, synergistically enhancing the degradation efficiency for CBZ and benzophenone-3 (BZP). The newly established VLD-PMS activation system was shown to treat the actual sewage in Hong Kong sewage treatment plants (STPs) very well. This work supplements the fundamental theory of radical and non-radical pathways in the sulfate radical (SO4•-)-based advanced oxidation process (SR-AOP) for environmental cleanup purposes.