Heterointerface-engineered ZnO/CuO bimetallic sites enable pollutant-directed conversion with in situ catalyst regeneration

Polymerization-based wastewater treatment offers reduced oxidant demand and product recovery, yet practical application is hindered by catalyst fouling and unselective reactions due to single-site competition. Here, we report a readily synthesized and scalable ZnO/CuO catalyst featuring dual functional sites that decouple pollutant and oxidant activation. Zn sites preferentially adsorb/activate organics, whereas Cu sites predominantly activate the oxidant. This site differentiation programs two pathway regimes governed by pollutant electronic structure: electron-transfer-mediated polymerization for electron-rich substrates and radical-induced mineralization for electron-deficient substrates. Importantly, radicals generated during mineralization depolymerize the accumulated foulant layer in situ, effecting autonomous catalyst regeneration with a 2.5-fold performance recovery and reduced external regeneration demand. Process performance is validated in a 200 L self-circulating reactor, maintaining 98% removal efficiency for both pollutant classes over ten cycles. Toxicological profiling across multiple biological models, supported by metabolomics, confirmed effective detoxification of multi-pollutant wastewater, including restoration of normal metabolic function in zebrafish (e.g., lipid and glutathione metabolism). This study establishes a dual-site cooperative catalysis framework that leverages intrinsic wastewater chemistry for self-regeneration, showcasing a complete trajectory from atomic-scale design to reactor-scale implementation. A ZnO/CuO catalyst featuring dual-site cooperative framework for polymerization-based wastewater treatment. Zn sites preferentially adsorb/activate organics, whereas Cu sites predominantly activate the oxidant, showcasing atomic-scale design to reactor-scale implementation.