The electrochemical oxygen reduction reaction (ORR) is at the heart of modern sustainable energy technologies. However, the linear scaling relationship of this multistep reaction now becomes the bottleneck for accelerating kinetics. Herein, we propose a strategy of using intermetallic-distance-regulated atomic-scale bimetal assembly (ABA) that can catalyse direct O‒O radical breakage without the formation of redundant *OOH intermediates, which could regulate the inherent linear scaling relationship and cause the ORR on ABA to follow a fast-kinetic dual-sites mechanism. Using in situ synchrotron spectroscopy, we directly observe that a self-adjustable N-bridged Pt = N₂ = Fe assembly promotes the generation of a key intermediate state (Pt‒O‒O‒Fe) during the ORR process, resulting in high reaction kinetics and selectivity. The well-designed Pt = N₂ = Fe ABA catalyst achieves a nearly two orders of magnitude enhanced kinetic current density at the half-wave potential of 0.95 V relative to commercial Pt/C and an almost 99% efficiency of 4-electron pathway selectivity, making it one of the potential ORR catalysts for application to the energy device of zinc‒air cells. This study provides a helpful design principle for developing and optimizing other efficient ORR electrocatalysts.

电化学氧还原反应 (ORR) 是现代可持续能源技术的核心。然而，这种多步反应的线性比例关系现在成为加速动力学的瓶颈。在此，我们提出了一种使用金属间距离调节的原子尺度双金属组件（ABA）的策略，该策略可以催化直接 O-O 自由基断裂，而不会形成多余的*OOH 中间体，这可以调节固有的线性比例关系并导致ABA 上的 ORR 遵循快速动力学双位点机制。使用原位同步加速器光谱，我们直接观察到一个自调节的 N 桥接 Pt = N ₂ = Fe 组装在 ORR 过程中促进关键中间态 (Pt-O-O-Fe) 的产生，从而产生高反应动力学和选择性。精心设计的 Pt = N ₂  = Fe ABA 催化剂在 0.95 V 的半波电位下相对于商业 Pt/C 实现了近两个数量级的增强动力学电流密度和几乎 99% 的 4 电子途径选择性效率，使其成为应用于锌空气电池能量装置的潜在 ORR 催化剂之一。本研究为开发和优化其他高效 ORR 电催化剂提供了有益的设计原则。