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

ABSTRACT 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.