Iron‐Induced Interfacial Electronic Asymmetry Steers Pathway Divergence in Cobalt‐Centered Fenton‐Like Catalysis

ABSTRACT Deep mineralization and matrix tolerance are difficult to reconcile in advanced oxidation processes because radical and nonradical pathways are often coupled in a composition‐defined paradigm. Although multimetal materials can catalyze both pathways, the parallel reactions typically occur at different active sites, and their relative contributions are often governed by catalyst composition and active‐site distribution, making deliberate regulation of pathway competition difficult. Here, we propose a multimetal catalyst with an electronically asymmetric Fe─O─Co interface to enable pathway divergence within a Co‐centered catalytic environment. Fe introduction into CoNi layered hydroxides leads to electron density redistribution at neighboring Co sites and shifts PMS activation from a high‐valent Co IV ═O‐biased route toward a sulfate‐radical‐enriched regime while retaining complementary nonradical oxidation. The optimized catalyst achieved 1.43‐fold greater TOC removal and a 1.47‐fold higher PMS utilization efficiency (PUE) for norfloxacin (NOR) degradation than the Fe‐free control, with robust decontamination performance against common background matrix interference and sustained activity over 96 h of high‐flux continuous‐flow operation. This work establishes interfacial Fe regulation as a pathway‐engineering strategy for steering oxidant‐activation selectivity through heterometal‐induced electronic asymmetry, providing a route to reconcile mineralization depth with matrix tolerance in Fenton‐like water treatment.