Reaction-driven restructuring of defective PtSe₂ into ultrastable catalyst for the oxygen reduction reaction

PtM (M = S, Se, Te) dichalcogenides are promising two-dimensional materials for electronics, optoelectronics and gas sensors due to their high air stability, tunable bandgap and high carrier mobility. However, their potential as electrocatalysts for the oxygen reduction reaction (ORR) is often underestimated due to their semiconducting properties and limited surface area from van der Waals stacking. Here we show an approach for synthesizing a highly efficient and stable ORR catalyst by restructuring defective platinum diselenide (DEF-PtSe₂) through electrochemical cycling in an O₂-saturated electrolyte. After 42,000 cycles, DEF-PtSe₂ exhibited 1.3 times higher specific activity and 2.6 times higher mass activity compared with a commercial Pt/C electrocatalyst. Even after 126,000 cycles, it maintained superior ORR performance with minimal decay. Quantum mechanical calculations using hybrid density functional theory reveal that the improved performance is due to the synergistic contributions from Pt nanoparticles and the apical active sites on the DEF-PtSe₂ surface. This work highlights the potential of DEF-PtSe₂ as a durable electrocatalyst for ORR, offering insights into PtM dichalcogenide electrochemistry and the design of advanced catalysts.