First-principles study on the d-band center of Pt alloyed with 3d transition metals

We study the catalytic activity properties of Pt doped and alloyed with 3d transition metal (Cr, Mn, and Fe). Using first-principles calculations, we investigate energetically favored configurations of doped Pt, including dopant locations in the Pt layers and distances between neighboring dopants. In a wide range of doping concentrations, our calculations on surface d-band centers reveal that the catalytic activity of the doped Pt is not considerably affected by transition metal impurities. In particular, Pt-Fe (1:1) alloys in an ordered face-centered tetragonal phase exhibit d-band centers aligned to the ideal value for the oxygen reduction reaction, which contrasts with disordered alloys whose d-band centers significantly deviate from the ideal one. This work suggests that doping and alloying Pt with transition metals is a promising route to design more affordable materials with lower Pt loading, while maintaining comparable to or even improved catalytic activity compared to pristine Pt.