Single‐Atom Mn Catalysts via Integration with Mn Sub Nano‐Clusters Synergistically Enhance Oxygen Reduction Reaction

Integrating single atoms and clusters into one system represents a novel strategy for achieving the desired catalytic performance. In comparison to single‐atom catalysts, catalysts combining single atoms and clusters harness the advantages of both, thus displaying greater potential. Nevertheless, constructing single‐atom‐cluster systems remains challenging, and the fundamental mechanism for enhancing catalytic activity remains elusive. In this study, a directly confined preparation of a 3D hollow sea urchin‐like carbon structure (MnSA/MnAC‐SSCNR) is developed. Mn single atoms synergistically interact with Mn clusters, optimizing and reducing energy barriers in the reaction pathway, thus enhancing reaction kinetics. Consequently, in contrast to Mn single‐atom catalysts (MnSA‐SSCNR), MnSA/MnAC‐SSCNR exhibits significantly improved oxygen reduction activity, with a half‐wave potential (E1/2) of 0.90 V in 0.1 m KOH, surpassing that of MnSA‐SSCNR and Pt/C. This work demonstrates a strategy of remote synergy between heterogeneous single atoms and clusters, which not only contributes to electrocatalytic reactions but also holds potential for reactions involving more complex products. This work demonstrates a strategy of remote synergy between heterogeneous single atoms and clusters, which contributes to an electrocatalytic oxygen reduction reaction. The synthesized a single‐atom‐cluster catalyst (MnSA/MnAC‐SSCNR) catalyst exhibits a half‐wave potential (E1/2) of 0.90 V in 0.1 m KOH, along with excellent stability and methanol tolerance, surpassing that of commercial Pt/C catalysts.