Dynamically Dual‐Center Coupled Synergistic Catalysis for Highly Efficient Oxygen Reduction
Jingjing Jiang, Jiulong Wu, Chenyu Yang, Shuowen Bo, Jing Zhang, Baojie Li, Yuhao Zhang, Qizheng An, Xin Chen, Qinghua Liu, Wanlin Zhou
Abstract
Abstract The oxygen reduction reaction (ORR) suffers from inherent kinetic limitations arising from the competitive adsorption behavior of *OOH intermediates and their divergent conversion pathways toward either the 4e⁻‐dominant route or the 2e⁻‐peroxide byproduct. Conventional single‐component catalysts fundamentally lack temporal‐spatial control to simultaneously accelerate O─O bond cleavage while suppressing *H 2 O 2 desorption. To overcome this kinetic dilemma, herein, we propose a dynamically dual‐center coupled synergistic (DCCS) catalytic mechanism enabled by precisely engineered PdRh─Pt nanosheet binary‐component interfaces. Multidimensional in situ synchrotron radiation spectroscopy and theoretical studies reveal that the activated 4e⁻ pathway primarily occurs at PdRh sites. Additionally, Pt centers selectively reduce *OOH to *O and *H 2 O 2 , whereas neighboring PdRh sites facilitate ultrafast *H 2 O 2 migration and dissociation, effectively complementing the 4e⁻‐dominant pathway. Hence, the DCCS catalysis redirects traditionally divergent product pathways toward a singular target product. This interfacial kinetic synergy achieves ultrahigh 4e⁻ kinetics, demonstrated by a six‐fold increase of turnover frequency compared to that of commercial Pt/C. Moreover, the derived rechargeable Zn‒air batteries demonstrate exceptional stability over 200 h, establishing a new design principle for breaking kinetics trade‐offs in heterogeneous catalysis through molecularly scheduling reaction pathways.