Regulating the scaling relationship for high catalytic kinetics and selectivity of the oxygen reduction reaction

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 = N 2 = 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 = N 2 = 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. Improving kinetics for electrochemical oxygen reduction reaction is relevant to important sustainable energy technologies. The authors propose an atomic-scale bimetal assembly consisting Pt and Fe dual sites to regulate the inherent scaling relationship between intermediates for fast kinetics.