Cyclable Cu^Ⅰ-O_v-Mn sites accelerate O₂ activation to enhance photo-driven catalytic oxidation performance

Molecular oxygen activation (MOA) plays a crucial function in various oxidation reactions. Nonetheless, facile, continuous and efficient MOA remains challenging. Herein, we have successfully constructed recyclable Cu^Ⅰ-O_v-Mn sites (O_v: oxygen vacancy) for MOA by incorporating Cu single atoms in MnO₂ matrix. The localized photogenerated electron at Cu^Ⅱ site drives the generation of electron-rich Cu^Ⅰ species and an adjacent photoinduced O_v, which possesses stronger O₂ affinity and affords a durable O₂ activation site. The Cu^Ⅱ/Cu^Ⅰ cycle accelerates the separation of charge carriers to supply adequate photogenerated electrons and assures the renewability of photoinduced O_v, thus realizing rapid and sustained O₂ activation and generating abundant monatomic oxygen ions (O^-). Consequently, Cu-MnO₂ catalyst performed extraordinarily high activity in O₂-involved reactions. For instance, in toluene oxidation, toluene conversion reached as high as 96 %, comparable to that on the state-of-the-art supported Pt catalysts. This work will bring more possibilities for modulating the O₂-involved oxidative reactions.