Electronic Reconfiguration and Acidic Tailoring: Design of a CoMn Spinel Catalyst for Selective Catalytic Reduction-Coupled Chlorobenzene Deep Oxidation

The interplay between surface oxygen activation and acidity optimization poses fundamental challenges in developing multifunctional catalysts. In this work, we present a dual-functional design strategy through Al³⁺ doping and phosphate modification to engineer electronic reconfigured, acid-tailored CoMn microspherical spinel for chlorobenzene (CB) deep oxidation. Systematic characterizations combined with theoretical calculations indicated that Al-induced charge redistribution creates electron-deficient Co and Mn metal centers that promote electron density rearrangement of the O 2p orbital, generating reactive oxygen species (ROS). Phosphate coordination further boosted the Bro̷nsted acid sites (BASs) while enhancing ROS activity. In CB oxidation, the modified CoMn spinel not only exhibited high HCl selectivity but also deeply oxidized CB and its intermediates due to abundant surface ROSs and rapid O₂ activation. Finally, a tandem catalytic system was proposed for the efficient simultaneous elimination of NO_<i>x</i> and CB, achieving over 90% NO_<i>x</i> and CB conversions within a wide temperature range (210-400 °C). This work establishes a general paradigm for designing multifunctional catalysts through orbital hybridization and acid-base synergy, particularly applicable to industrial multipollutant control scenarios.