Engineering bimetallic cluster architectures: Harnessing unique “remote synergy effect” between Mn and Y for enhanced electrocatalytic oxygen reduction reaction

Abstract

Integrating single atoms and clusters into a unified catalytic system represents a novel strategy for enhancing catalytic performance. Compared to single-atom catalysts, those incorporating both single atoms and clusters exhibit superior catalytic activity. However, the co-construction of these systems and the mechanisms of their catalytic efficacy remain challenging and poorly understood. In this study, we synthesized a Mn–N–C catalyst featuring MnY clusters and Mn single atoms via a straightforward two-step sintering method. Y doping facilitated the formation of Mn clusters and optimized the d-band center of Mn through a unique synergy effect, thereby reducing energy barriers and enhancing the reaction kinetics. Additionally, the electron-donating ability of Y single atoms promoted the formation of unsaturated Mn–N₃ coordination structures, resulting in excellent oxygen reduction reaction (ORR) performance. Consequently, the MnY/NC catalyst demonstrated a half-wave potential (E₁/₂) of 0.90 ​V and maintained stability in 0.1 ​M KOH, outperforming both Mn/NC and Pt/C. This work underscores the potential of rare earth metal doping in transition metals to create stable single-atom and cluster systems, effectively leveraging their synergy effect for superior catalytic performance and validating the concept of the “remote synergy effect” in heterogeneous catalysis.