From Passive Targets to Chemical Fuels: Mechanistic Insights and Engineering Implementation of Pollutant–Catalyst Synergy in Oxidant‐Free Fenton‐Like Catalysis

ABSTRACT Conventional Fenton‐like water treatment systems predominantly rely on the activation of external oxidants to generate powerful oxidative species, a paradigm frequently bottlenecked by poor reaction selectivity, intensive chemical consumption, and secondary environmental footprint. To circumvent these limitations, the self‐driven strategy rooted in pollutant‐catalyst synergy has emerged as a frontier eco‐technology. At its core, this approach redefines organic pollutants as active electron‐donating components, rather than passive substrates, leveraging their inherent chemical potentials to trigger, regulate, and sustain interfacial electron transfer without external oxidant input. This review systematically conceptualizes the fundamental mechanisms, rational material design principles, and engineering translation pathways of self‐driven pollutant‐catalyst architectures. We dissect the multi‐scale interfacial coupling processes, highlighting critical mechanisms such as direct electron transfer, dissolved oxygen activation, background‐ion‐mediated charge transport, and external‐field‐assisted surface reactions. Moreover, the practical viability of these systems is critically appraised through the lenses of catalytic selectivity, long‐term stability, and biosafety, complemented by comprehensive life‐cycle assessment (LCA) and techno‐economic analysis (TEA) to envision their scalability and environmental sustainability.