Selective Cleavage of Cu─N Bonds Reshaped Asymmetric Dicopper Centers and Surface Polarity for Enhanced Biomimetic Oxidation

Efficient O 2 activation at dicopper sites was often stifled by the symmetric coordination configuration of the active center and a long‐overlooked interface shielding‐triggered mass‐transfer barrier dictated by the surface polarity of the catalyst. Herein, we reported a phosphorus‐mediated chemical editing strategy to simultaneously overcome these constraints. By utilizing Hard and Soft Acids and Bases‐guided selective cleavage of partial Cu─N bonds, we transformed a Cu‐based precursor with the N 4 Cu‐CuN 4 S configuration into an asymmetric low‐coordinated N 2 Cu‐CuN 2 S center. Such an asymmetric reconfiguration not only induced a pivotal reversal in surface polarity to reshape the catalytic interface from a dense cation‐rich inner Helmholtz plane to a loose O 2 ‐permeable outer Helmholtz plane, thereby facilitating O 2 diffusion and enrichment, but also upshifted the d‐band center to strengthen intrinsic O 2 adsorption and polarization. This dual regulation significantly accelerated the generation of reactive oxygen species, endowing the N 2 Cu‐CuN 2 S site with superior 4e oxidase‐like activity over its N 4 Cu‐CuN 4 S counterpart and most previous Cu‐based catalysts with symmetric configurations. Leveraging the high activity and thiophilic nature of this N 2 Cu‐CuN 2 S site, we developed a glutathione sensor with a 0.383 ppm detection limit. This work offered a selective editing avenue to engineer high‐performance biomimetic catalysts with precise control over both the molecular and interfacial environment for catalysis and biosensing.