Strong Electronic Metal–Support Interactions Enable the Increased Spin State of Co–N₄ Active Sites and Performance for Acidic Oxygen Reduction Reaction

Nonprecious metal catalysts, particularly M –N–C catalysts, are widely recognized as promising contenders for the oxygen reduction reaction (ORR). However, a notable performance gap persists between M –N–C catalysts and Pt-based catalysts under acidic conditions. In this study, hybrid catalysts comprising single Co atoms and ultralow concentrations of Pt 3 Co intermetallic nanoparticles (NPs) are introduced to enhance ORR performance. Under acidic conditions, these hybrid catalysts demonstrate ORR efficiency with a half-wave potential of 0.895 V, negligible decay even after 80 000 cycles, and a high maximum power density of 1.34 W cm –2 in fuel cells. This performance surpasses those of Co–N–C and Pt/Co–N–C catalysts. Both experimental findings and theoretical computations suggest that the heightened ORR activity stems from an increase in the spin density of Co sites induced by noble metal NPs, facilitating the activation of O–O bonds via side-on overlapping and enabling a transition in the reaction pathway from associative to dissociative processes. This research offers a promising avenue for the systematic design of M –N–C cathodes with an enhanced performance for acidic fuel cells.