Insightful Understanding of Synergistic Oxygen Reduction on PtCo3(111) Toward Zinc‐Air Batteries

Theory‐guided materials design is an effective strategy for designing catalysts with high intrinsic activity whilst minimizing the usage of expensive metals like platinum. As proof‐of‐concept, herein it demonstrates that using density functional theory (DFT) calculations and experimental validation that intermetallic PtCo3 alloy nanoparticles offer enhanced electrocatatalytic performance for the oxygen reduction reaction (ORR) compared to Pt nanoparticles. DFT calculations established that PtCo3(111) surfaces possess better intrinsic ORR activity compared to Pt(111) surfaces, owing to the synergistic action of adjacent Pt and Co active sites which optimizes the binding strength of ORR intermediates to boost overall ORR kinetics. With this understanding, a PtCo3/NC catalyst, comprising PtCo3 nanoparticles exposing predominantly (111) facets dispersed on an N‐doped carbon support, is successfully fabricated. PtCo3/NC demonstrates a high specific activity (3.4 mA cm−2 mgPt−1), mass activity (0.67 A mgPt−1), and cycling stability for the ORR in 0.1 M KOH, significantly outperforming a commercial 20 wt.% Pt/C catalyst. Moreover, a zinc‐air battery (ZAB) assembled with PtCo3/NC as the air‐electrode catalyst delivered an open‐circuit voltage of 1.47 V, a specific capacity of 775.1 mAh gZn−1 and excellent operation durability after 200 discharge/charge cycles, vastly superior performance to a ZAB built using commercial Pt/C+IrO2 as the air‐electrode catalyst. Density functional theory calculations show that intermetallic PtCo3(111) alloy surfaces offer a more optimal adsorption configuration and binding strength for oxygen reduction reaction (ORR) intermediates compared to Pt(111) surfaces. Electrochemical analyses validated this prediction, with a PtCo3/NC catalysts offering superior ORR performance relative to a commercial 20 wt.% Pt/C catalyst.