Decorating Single‐Atomic Mn Sites with FeMn Clusters to Boost Oxygen Reduction Reaction

The regulation of electron distribution of single-atomic metal sites by atomic clusters is an effective strategy to boost their intrinsic activity of oxygen reduction reaction (ORR). Herein we report the construction of single-atomic Mn sites decorated with atomic clusters by an innovative combination of post-adsorption and secondary pyrolysis. The X-ray absorption spectroscopy confirms the formation of Mn sites via Mn-N4 coordination bonding to FeMn atomic clusters (FeMnac /Mn-N4 C), which has been demonstrated theoretically to be conducive to the adsorption of molecular O2 and the break of O-O bond during the ORR process. Benefiting from the structural features above, the FeMnac /Mn-N4 C catalyst exhibits excellent ORR activity with half-wave potential of 0.79 V in 0.5 M H2 SO4 and 0.90 V in 0.1 M KOH as well as preeminent Zn-air battery performance. Such synthetic strategy may open up a route to construct highly active catalysts with tunable atomic structures for diverse applications.