Dual‐Atomic‐Site Engineering of Pt‐Based Intermetallic Catalysts for Highly Efficient and Durable Oxygen Reduction

Abstract Developing high‐performance oxygen reduction reaction (ORR) catalysts with minimal Pt loading while maintaining excellent activity and durability remains a critical challenge for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a hybrid catalyst comprising Co‐Zn dual‐atomic sites and L1 0 ‐ordered PtCoZn intermetallics with a Pt‐rich shell (denoted as L1 0 ‐PtCoZn@Pt‐CoZn DA ) is presented for high ORR performance. The optimized catalyst delivers a remarkable mass activity of 2.33 A mg Pt −1 , exceeding that of commercial Pt/C (0.148 A mg Pt −1 ) by more than 16‐fold. PEMFC testing further verifies its excellent durability and high current density, verifying its practical potential. Combined experimental and theoretical studies attribute the superior performance to the synergistic interplay between the compressively strained Pt skin, encapsulating the atomically ordered L1 0 ‐PtCoZn core, and the adjacent Co‐Zn‐N 5 sites. This well‐integrated architecture not only tunes the electronic structure and optimizes intermediate adsorption energies but also facilitates a dual‐channel electron acceptance‐backdonation mechanism for efficient O─O bond activation. Furthermore, a dual‐site associative ORR pathway is promoted, where electronic coupling between the Co‐Zn‐N 5 sites and Pt skin enhances * O─OH bond cleavage and accelerates reaction kinetics. This work offers a viable strategy for the rational design of next‐generation Pt‐based electrocatalysts with enhanced activity and stability for PEMFC applications.