Avoiding Sabatier's Limitation on Spatially Correlated Pt-Mn Atomic Pair Sites for Oxygen Electroreduction

The development of highly active and low-cost oxygen reduction reaction (ORR) catalysts is crucial for the practical application of hydrogen fuel cells. However, the linear scaling relation (LSR) imposes an inherent Sabatier's limitation for most catalysts including the benchmark Pt with an insurmountable overpotential ceiling, impeding the development of efficient electrocatalysts. To avoid such a limitation, using earth-abundant metal oxides with different crystal phases as model materials, we propose an effective and dynamic reaction pathway through constructing spatially correlated Pt-Mn pair sites, achieving an excellent balance between high activity and low Pt loading. Experimental and theoretical calculations demonstrate that manipulating the intermetallic distance and charge distribution of Pt-Mn pairs can effectively promote O-O bond cleavage at these sites through a bridge configuration, circumventing the formation of *OOH intermediates. Meanwhile, the dynamic adsorption configuration transition from the bridge configuration of O₂ to the end-on configuration of *OH improves *OH desorption at the Mn site within such pairs, thereby avoiding Sabatier's limitation. The well-designed Pt-Mn/β-MnO₂ exhibits outstanding ORR activity and stability with a half-wave potential of 0.93 V and barely any activity degradation for 70 h. When applied to the cathode of a H₂-O₂ anion-exchange membrane fuel cell, this catalyst demonstrates a high peak power density of 287 mW cm^-2 and 500 h of stability under a cell voltage of 0.6 V. This work reveals the adaptive bonding interactions of atomic pair sites with multiple reactant/intermediates, offering a new avenue for rational design of highly efficient atomic-level dispersed ORR catalysts beyond the Sabatier optimum.