Proximity‐Engineered Dual‐Atomic Cobalt Sites Enable Adaptive Spin Catalysis for Simultaneous Oxygen and Peroxide Reduction

ABSTRACT Breaking the intrinsic adsorption conflicts among oxygen intermediates remains a central challenge in oxygen reduction reaction (ORR) electrocatalysis. Although spin‐state engineering offers an effective strategy for tuning catalytic activity, conventional approaches generally focus on a single‐spin configuration, which cannot simultaneously satisfy the distinct energetic requirements of different ORR intermediates. Here, we introduce an adaptive spin catalysis concept through proximity engineering of dual‐atomic Co sites confined within a one‐dimensional covalent organic framework. Precisely regulating the Co–Co separation while preserving the local coordination environment induces inter‐site electronic coupling, giving rise to coexisting high‐spin and low‐spin Co configurations. Combined spectroscopic characterizations and theoretical calculations support a mechanistic framework in which these coexisting spin configurations provide complementary catalytic functions for distinct intermediates along the multistep ORR pathway, thereby alleviating adsorption conflicts. Consequently, the proximity‐engineered catalyst delivers outstanding ORR activity with a half‐wave potential of 0.96 V versus reversible hydrogen electrode, outperforming both its spatially separated counterpart and commercial Pt/C. The catalyst also efficiently mediates both O 2 and H 2 O 2 reduction while suppressing peroxide decomposition, enabling enhanced performance in rechargeable zinc–air batteries and peroxide‐assisted aluminum–air batteries. This work establishes a molecular framework for exploiting spin‐state complementarity in atomic catalysts for advanced energy‐conversion reactions.