p‐Block Tin Single‐Atom Catalysts with Tuned p‐Orbital State for Oxygen Reduction Reaction

ABSTRACT Single‐atomic p‐block main‐group metal catalysts have garnered increasing attention for oxygen reduction reaction (ORR) in previous studies. However, their catalytic performance is not sufficiently satisfactory, as the electronic structure of p‐block metals is difficult to regulate to enable them to have appropriate adsorption free energy for the intermediate species of ORR. Herein, a Sn‐N‐GDY catalyst was synthesized under the guidance of density functional theory (DFT) calculations. As an innovative active site, Sn is bonded to two pyrrolic N, with two sp‐N in close proximity to them. Both pyrrolic N and sp‐N diminish the Sn 5p states, which reduces the adsorption energy of Sn toward ORR intermediates. Experimentally, the Sn single‐atom catalyst (SAC) is prepared with an anhydrous method to mitigate the agglomeration tendency of tin. The as‐synthesized Sn‐N‐GDY achieves a half‐wave potential ( E 1/2 ) of 0.86 V in alkaline electrolyte for ORR and exhibits exceptional cycling stability in zinc‐air batteries, operating 1,147 h at 2 mA cm −2 . With better performance than most main‐group ORR catalysts, this material shows excellent application potential. This work establishes a new paradigm for main‐group SACs on GDY and offers a design strategy for highly efficient non‐precious metal SACs.