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 Cu x Mn 3− x O 4 spinels, which repurpose CH 3 SH from a poison into a co‐catalyst, triggering self‐accelerating degradation. The optimized Cu 0.75 Mn 2.25 O 4 demonstrated exceptional stability with complete CH 3 SH mineralization over 28 h, sharply contrast to the rapid deactivation of Mn 3 O 4 . 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 O 3 at Mn sites, driving rapid hydroxyl radical (•OH) formation. This •H‐mediated O 3 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 Cu 2+ /Cu + and Mn 4+ /Mn 3+ 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.