Boosting Mass Transfer and Electron Kinetics in PMS Activation: D-Band Modulation via Nitrogen-Coordinated Cobalt Catalysts

Mass transfer limitations in Co-based heterogeneous peroxymonosulfate (PMS) activation systems were effectively mitigated via electronic structure modulation. Nitrogen doping introduces electron-withdrawing effects into Co/NC catalysts, which shifts the Co d-band center upward and optimizes orbital hybridization between the Co 3d and O 2p orbitals. This electronic configuration lowers the antibonding state occupancy in the Co-PMS complex, thereby facilitating PMS adsorption and activation. The engineered Co/NC catalyst completely degrades sulfamethoxazole within 3 min (rate constant: 2.3 min –1 ), demonstrating enhanced interfacial electron transfer kinetics. Its robust performance is maintained in complex aqueous matrices containing Cl –, NO 3 –, H 2 PO 4 –, and SO 4 2– anions. Moreover, effective pollutant removal persists for over 240 min in a continuous-flow membrane reactor, confirming the practical applicability. This orbital-level design strategy advances cobalt-based PMS activation systems by synergistically optimizing the mass transfer and electronic interactions.