Engineering Ni-mediated Fe electronic structure and micro-electric field for dual-engine nonradical PMS activation...

Activating peroxymonosulfate (PMS) via nonradical pathways for the selective removal of target pollutants in complex water matrices is highly desirable, but it remains challenging with conventional heterogeneous metal-based catalysts. Herein, we synthesized a melamine-derived foam carbon (CF) supported Fe-Ni bimetallic MOF composite (CF/F_0.75N_0.25) for advanced wastewater treatment. Ni incorporation narrowed the intrinsic O 2p-Fe 3d energy gap (Δ E_d-p) and enhanced the hybridization between Fe 3d states and ligands, thereby regulating the shift from radical pathways to the electron transfer pathway (ETP) in PMS activation. Meanwhile, graphitic N and N vacancies in CF created an intrinsic micro-electric field that directed electron transfer toward metal sites, further boosting the ETP process. Under these two synergistic driving forces, CF/F_0.75N_0.25 exhibited outstanding catalytic performance for PMS activation. It achieved rapid and preferential removal of TC across diverse water matrices (k_obs = 0.137 min^-1) with excellent matrix tolerance. Moreover, the system effectively inactivated TC-resistant bacteria and suppressed the horizontal transfer of antibiotic resistance genes. Reusability tests and continuous-flow experiments further confirmed the robustness and long-term application potential of this nonradical system. This study provides new insights into rational catalyst design for regulating nonradical PMS activation toward efficient contaminant and resistance risk control.