Axial Sulfur Ligation Unlocks the Rigidity of p‐Block Aluminum Single‐Atoms for Accelerated Oxygen Reduction

ABSTRACT Main‐group single‐atom catalysts (SACs) offer improved Fenton resistance but suffer from catalytic inertness due to rigid, delocalized s/p‐bands. Herein, we report a targeted “p‐band engineering” strategy to unlock the oxygen reduction reaction (ORR) activity of aluminum via an axially sulfur‐coordinated architecture (AlN 4 ‐S). Theoretical and spectroscopic analyses indicate that this asymmetric S‐ligation drives vertical charge polarization and shifts the spin‐summed occupied Al p z ‐state centroid. These coupled changes rebalance oxygenated‐intermediate adsorption by mitigating the overly strong Al–*OH thermodynamic sink, shifting the potential‐determining step to *OOH formation with a maximum uphill free‐energy change of 0.61 eV at U = 1.23 V. In situ ATR‐SEIRAS and in situ DRT impedance support more facile intermediate progression and reduced charge‐transfer resistance. Consequently, the engineered AlSNC catalyst delivers an ORR half‐wave potential of 0.920 V. In practical zinc‐air batteries, it achieves a 185.6 mW cm −2 peak power density and operation for over 1500 h under the reported cycling protocol. This work provides a framework for ligand‐induced p‐band modulation that combines Fenton resistance with high electrocatalytic activity.