Simultaneously Integrate Iron Single Atom and Nanocluster Triggered Tandem Effect for Boosting Oxygen Electroreduction

Abstract Atomically nitrogen‐coordinated iron atoms on carbon (FeNC) catalysts are emerging as attractive materials to substitute precious‐metal‐based catalysts for the oxygen reduction reaction (ORR). However, FeNC usually suffers from unsatisfactory performance due to the symmetrical charge distribution around the iron site. Elaborately regulating the microenvironment of the central Fe atom can substantially improve the catalytic activity of FeNC, which remains challenging. Herein, N/S co‐doped porous carbons are rationally prepared and are verified with rich Fe‐active sites, including atomically dispersed FeN 4 and Fe nanoclusters (FeSA‐FeNC@NSC), according to systematically synchrotron X‐ray absorption spectroscopy analysis. Theoretical calculation verifies that the contiguous S atoms and Fe nanoclusters can break the symmetric electronic structure of FeN 4 and synergistically optimize 3 d orbitals of Fe centers, thus accelerating OO bond cleavage in OOH* for improving ORR activity. The FeSA‐Fe NC @NSC delivers an impressive ORR activity with half‐wave‐potential of 0.90 V, which exceeds that of state‐of‐the‐art Pt/C (0.87 V). Furthermore, FeSA‐Fe NC @NSC‐based Zn‐air batteries deliver excellent power densities of 259.88 and 55.86 mW cm –2 in liquid and all‐solid‐state flexible configurations, respectively. This work presents an effective strategy to modulate the microenvironment of single atomic centers and boost the catalytic activity of single‐atom catalysts by tandem effect.