Atomically Dispersed p‐Block Aluminum‐Based Catalysts for Oxygen Reduction Reaction

Abstract The main group metals are commonly perceived as catalytically inert in the context of oxygen reduction reactions (ORR) due to the delocalized valence orbitals. Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M‐N x ) is a promising approach to accelerate catalytic dynamics. Herein, we, for the first time, report the atomically dispersed Al catalysts coordinated with N and C atoms for 4‐electron ORR. The axial coordinated pyrrolyl N group (N o ) is constructed in the Al‐N 4 ‐N o moiety to regulate the p‐band structure of Al center, effectively steering the local environment and structure of the square planar Al‐N 4 sites, which typically exhibit too strong interaction with ORR intermediates. The dynamic covalency competition of axial Al‐N o and Al‐O bonding could endow the Al center with moderate hybridization between Al 3p orbital and O 2p orbital, alleviating the binding energy of ORR intermediates. The as‐prepared Al‐N 4 ‐N o electrocatalyst exhibits excellent ORR activity, selectivity, and durability, along with the rapid kinetics as demonstrated by in situ Raman spectroscopy. This work offers a fundamental comprehension of the fine regulation on p‐band and guides the rational design of main‐group metal‐based single atom catalysts.