Synergistic Bimetallic Metallic Organic Framework-Derived Pt-Co Oxygen Reduction Electrocatalysts

The rational design of Pt-based electrocatalysts is of paramount importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Pt-Co alloys and nitrogen-doped carbons have been shown to be effective in enhancing the kinetics of the oxygen reduction reaction (ORR). Herein, we reported on two kinds of Pt-Co electrocatalysts, PtCo ordered intermetallic and PtCo₂ disordered alloys, supported on bimetallic MOF-derived N-doped carbon. The synergistic interaction between Pt-Co nanoparticles and Co-N-C enhanced the overall ORR activity and maintained the integrity of both structures and their electrochemical properties during long-term stability testing. The optimal activity for both PtCo and PtCo₂ occurred after 20 000 potential cycles. The enhanced performance of PtCo was ascribed to the formation of a two-atomic-layer Pt-rich shell and the lattice strain caused by the core-shell PtCo@Pt structure. The increased activity of PtCo₂ was ascribed to the formation of large, spongy, and small solid nanoparticles during electrochemical dealloying and thus the exposure of more Pt sites on the surface. The strategy described herein advances our understanding of the structure-activity relationship in electrocatalysis and sheds light on the future development of more active and durable ORR electrocatalysts.