Revitalization of Bulk Transition Metal Oxides by Ligand‐Assisted Metal Abstraction for Superior Fenton‐Like Catalysis

Unlocking the full potential of bulk transition metal oxides (TMOs) is often hindered by their limited atomic exposure and restricted tunability of active sites, which collectively lead to suboptimal catalytic activity. Herein, we present a facile ligand‐assisted metal abstraction strategy to construct an amorphous shell embedded with single Cu atoms on a crystalline CuO core. The synergistic coordination of ─COOH and ─NH 2 groups at the Cu single site promotes selective orbital coupling between Cu d xz / d yz and O p orbitals, facilitating O‐O bond cleavage of peroxymonosulfate (PMS) via electron backdonation and increasing Cu(III) selectivity from 53.9% to 90.4%. This coordination effect also demonstrates a 46.4‐fold enhancement in PMS activation efficiency over bare CuO, surpasses most state‐of‐the‐art Fenton‐like catalysts, and restricts Cu leaching to only 0.467 mg/L, 2.30 times lower than that of bare CuO. More importantly, the elevated Cu(III) redox potential upon coordination with the electron‐donating ─NH 2 group enables deep polymerization of pollutants, which generates fewer toxic oligomeric intermediates and achieves a significant reduction in the biotoxicity of treated effluent compared with the CuO/PMS system. This strategy offers a novel design approach to revitalize the site‐specific activity of TMOs for superior Fenton‐like reactions.