Ligand Thermal Reactivity Optimizing the Synergism of Mass Transfer and Catalysis Kinetics of Dual‐Phase Iron Components for High‐Efficiency Zinc‐Air Batteries

ABSTRACT The intrinsic pyrolysis behavior of organic ligands determines the performance of Fe‒N‒C oxygen reduction reaction (ORR) electrocatalysts, yet its coupled effects on pore evolution and active species composition remain largely overlooked. Herein, imidazole‐, triazole‐, and tetrazole‐based ligands with distinct thermal reactivity are employed to construct Fe‒N‒C catalysts. Ligand‐dependent decomposition pathways precisely regulate hierarchical micro‐meso‐macroporous and the local coordination of Fe‒N x sites and Fe 3 O 4 nanoparticles for the Fe 3 O 4 /Fe‒N‒C catalyst. Optimized hierarchical pores can construct unobstructed channels for reactants, proton and electron transfer. In situ electrochemical spectroscopy and density functional theory calculations verify that the local electron modulation between Fe 3 O 4 nanoparticles and atomic Fe‒N x sites, together with rapid mass diffusion enabled by hierarchical porous structure, thus achieves weakening *OH adsorption, and conversion kinetics of oxygenated intermediates, further exhibiting an outstanding ORR half‐wave potential of that surpasses Pt/C. As the cathodic catalyst, the zinc‐air battery demonstrates an outstanding peak power density of 205 mW·cm − 2 and robust long‐term cycling stability with a charge‐discharge voltage gap of 0.80 V. This work demonstrates that ligand thermal reactivity serves as a key descriptor governing pore evolution and the local coordination of active sites, providing a reference strategy for high‐performance Fe‒N‒C electrocatalysts.