Spin Channels Enable •H‐Triggered Ozone Activation for Self‐Accelerating Degradation of Reduced‐Sulfur Pollutant

The practical application of catalytic ozonation for sulfurous volatile organic compounds (S-VOCs) is limited by two key challenges: sluggish electron transfer in ozone activation and irreversible catalyst deactivation from sulfur poisoning. Here, we report a strategy to overcome the "activation-poisoning" cycle through the engineering of CuxMn₃₋ xO₄ spinels, which repurpose CH₃SH from a poison into a co-catalyst, triggering self-accelerating degradation. The optimized Cu0.75Mn2.25O₄ demonstrated exceptional stability with complete CH₃SH mineralization over 28 h, sharply contrast to the rapid deactivation of Mn₃O₄. Mechanistic studies reveal that this enhancement originates from hydrogen radical (•H)-triggered chain reaction: Cu sites selectively mediate S─H homolysis to generate •H, which directly reduces O₃ at Mn sites, driving rapid hydroxyl radical (•OH) formation. This •H-mediated O₃ activation is enabled by spin-polarized electron transfer along Cu─O─Mn spin channels, where Cu doping enhances the O 2p─Mn 3d hybridization, builds delocalized electron pathways, and sustains Cu²⁺/Cu⁺ and Mn⁴⁺/Mn³⁺ redox cycling. Instantaneous •H consumption prevents sulfur intermediates accumulation and poisoning. This work transforms catalyst poisoning into a pollutant‑driven, self‑accelerating process via engineered spin‑polarized channels, offering a design strategy for anti-poisoning environmental catalysts and advancing sustainable S-VOC abatement.