Molecular Bridging Enables Isolated Iron Atoms on Stereoassembled Carbon Framework To Boost Oxygen Reduction for Zinc‐Air Batteries

Abstract Realizing the synergy between active site regulation and rational structural engineering is essential in the electrocatalysis community but still challenging. Here, a matrix‐confined co‐pyrolysis strategy based on molecular bridging is demonstrated to realize highly dispersed Fe atoms on stereoassembled carbon framework. Both polyacrylonitrile matrix and organic linker from metal–organic frameworks (MOFs) provide sufficient N‐anchoring sites for the generation of Fe−N 4 moieties. A high Fe loading of 2.9 wt.% is readily achieved based on the scalable approach without post‐treatment. Owing to the presence of highly exposed Fe−N−C sites and well‐tuned pore structures, isolated Fe atoms on porous carbon nanofiber framework (Fe−SA/NCF) exhibits decent oxygen reduction activity and stability in alkaline conditions via a near four‐electron path, demonstrating superior performance as air cathode for zinc‐air batteries (ZABs) to commercial Pt/C catalyst.