Asymmetric FeNi Atomic Local Electric Field‐Mediated Non‐Redox Activation of H₂O₂ for Selective Generation of Hydroxyl Radical

The activation of H 2 O 2 on heterogeneous catalysts to generate hydroxyl radicals typically involves external electron transfer, which can entrap the catalyst in a redox cycle and thus demonstrate limited catalytic efficiency. Herein, a nitrogen‐doped carbon‐supported FeNi dual‐atom catalyst is presented, wherein the asymmetric atomic pair‐induced local electric field can facilitate H 2 O 2 activation via non‐redox catalysis, achieving 94% selectivity for hydroxyl radicals generation. Experimental and theoretical calculations reveal that Ni in the second coordination shell enhances electron delocalization at the Fe site, endowing Fe with enhanced Lewis acidity and thereby improving H 2 O 2 adsorption. Moreover, the atomic local electric field induces electron redistribution within H 2 O 2 , which effectively promotes the polarization and cleavage of the O─O bond. This work offers a theoretical foundation for the rational design of efficient non‐redox catalysts for H 2 O 2 homolytic cleavage.