Potential Dominates Structural Recombination of Single Atom Mn Sites for Promoting Oxygen Reduction Reaction

Abstract Single atom sites (SAS) often undergo structural recombination in oxygen reduction reaction (ORR), while the effect of valence state and reconstruction on active centers needs to be investigated thoroughly. Herein, the Mn‐SAS catalyst with uniform and precise Mn‐N 4 configuration is rationally designed. We utilize operando synchrotron radiation to track the dynamic evolution of active centers during ORR. Under the applied potential, the structural evolution of Mn‐N 4 into Mn‐N 3 C and further into Mn‐N 2 C 2 configurations is clarified. Simultaneously, the valence states of Mn are increased from +3.0 to +3.8 and then decreased to +3.2. When the potential is removed, the catalyst returned to its initial Mn +3.0 ‐N 4 configuration. Such successive evolutions optimize the electronic and geometric structures of active centers as evidenced by theory calculations. The evolved Mn +3.8 ‐N 3 C and Mn +3.2 ‐N 2 C 2 configurations respectively adjust the O 2 adsorption and reduce the energy barrier of rate‐determining step. Thus, it can achieve an onset potential of 0.99 V, superior stability over 10,000 cycles, and a high turnover frequency of 1.59 s −1 at 0.85 VRHE. Our present work provides new insights into the construction of well‐defined SAS catalysts by regulating the valence states and configurations of active centers.