Design of Pt‐Based Bimetallic Active Sites for Efficient Oxygen Reduction Reaction on C 6 N 6 Skeleton

Abstract In this work, Pt‐based bimetal catalysts PtM@C 6 N 6 (M = 3d, 4d, 5d) for the oxygen reduction reaction (ORR) is systematically investigated by comprehensive consideration of different coordination modes and anchored sites of Pt and M atoms on experimentally synthesized C 6 N 6 substrate, different adsorption configuration of O 2 molecule from both above and below the catalyst surface, different reaction pathway, and structure‐activity relationship via computer‐aided screening and density functional theory (DFT) computations. Comprehensive search and in‐deep analysis reveal that seven representative electrocatalysts (i.e., PtAg@, PtCd@, PtCu@, PtIr@, PtRh@, PtHf@, and PtZr@C 6 N 6 ) demonstrate high ORR catalytic activities under both acidic and basic conditions with favorable overpotentials. Full reaction pathway search demonstrates that the ORR follows a 4‐electron mechanism with the final product H 2 O/OH − . PtCd@, PtCu@, PtIr@, PtRh@, and PtZr@C 6 N 6 exhibit superior activities with low η ORR due to their moderate adsorption strength of *OH, while PtAg@ and PtHf@C 6 N 6 exhibit excellent catalytic performance is attributed to moderate O 2 adsorption Furthermore, a series of descriptors (e.g., ΔG 0 a , ΔG 4 a , ΔG 4 a –d(Pt‐M), and [d(Pt‐O2)×d(M‐O2)]×[d(M‐O2)/d(M‐O1)], etc) are uncovered to unveil the origin of catalyst activity. These findings pave a significant path for the development of efficient ORR catalysts and are expected to stimulate experimental efforts in this direction.