Oxygen Doping Cooperated with Co‐N‐Fe Dual‐Catalytic Sites: Synergistic Mechanism for Catalytic Water Purification within Nanoconfined Membrane

Atom-site catalysts, especially for graphitic carbon nitride-based catalysts, represents one of the most promising candidates in catalysis membrane for water decontamination. However, unravelling the intricate relationships between synthesis-structure-properties remains a great challenge. This study addresses the impacts of coordination environment and structure units of metal central sites based on Mantel test, correlation analysis, and evolution of metal central sites. An optimized unconventional oxygen doping cooperated with Co-N-Fe dual-sites (OCN Co/Fe) exhibits synergistic mechanism for efficient peroxymonosulfate activation, which benefits from a significant increase in charge density at the active sites and the regulation in the natural population of orbitals, leading to selective generation of SO₄ ^•-. Building upon these findings, the OCN-Co/Fe/PVDF composite membrane demonstrates a 33 min^-1 ciprofloxacin (CIP) rejection efficiency and maintains over 96% CIP removal efficiency (over 24 h) with an average permeance of 130.95 L m^-2 h^-1. This work offers a fundamental guide for elucidating the definitive origin of catalytic performance in advance oxidation process to facilitate the rational design of separation catalysis membrane with improved performance and enhanced stability.