Temperature‐Dependent Dynamics of Superoxide and Peroxide Anions in Hydrocarbon Catalytic Oxidation Over Single‐Atom Pt Catalysts

Understanding the properties of reactive oxygen species (ROS) is crucial for efficient oxidation catalyst design, yet their dynamics during oxidative reactions are still unclear. Herein, using a CeZrO 2 ‐supported single‐atom Pt catalyst (Pt SA /CeZrO 2 ), we studied temperature‐dependent behaviors of superoxide (O 2 •− ) and peroxide (O 2 2− ) anions and how multiple ROS are involved in the catalytic oxidation of mixed hydrocarbons. We show that O 2 •− species, having an unpaired electron and a Pt‐O‐O structure, accounts for surface reactivity at lower temperatures, which is critical to toluene ring‐opening below 200°C. At higher temperatures (200°C–450°C), O 2 •− desorbs, while the O 2 2− anion, anchored by an oxygen vacancy (Vo) in the form of Pt‐O‐O@Vo, exhibits high stability and activity, promoting initial propane activation. Through the “relay” cooperation of O 2 •− and O 2 2− species, the Pt SA /CeZrO 2 (Pt loading of 0.4 g Pt /L) achieves complete removal of mixed toluene and propane at 450°C, 150°C lower than on a commercial high‐Pt loading Pt NP /CeZrO 2 catalyst (0.9 gPt/L). Our study advances the understanding of the dynamics and synergism of multiple ROS in mixed hydrocarbon oxidation process and paves the way for the development of next‐generation catalysts suited for a broad operational temperature window.