Computational and experimental study of the Volcano behavior of the oxygen reduction activity of PdM@PdPt/C (M = Pt, Ni, Co, Fe, and Cr) core–shell electrocatalysts

Abstract

The activity of oxygen reduction electrocatalysts is governed by the Sabatier principle and follows a Volcano curve as a function of the oxygen-binding energy. Density functional theory calculations show that the oxygen-binding energy decreases in steps of about 10kJ/mol in a series of core–shell Pd3M@Pd3Pt (M=Ni, Co, Fe, Mn, and Cr) electrocatalysts, leading to a gradual, Volcano-like variation in the oxygen reduction activity. A series of carbon-supported PdM@PdPt (M=Ni, Co, Fe, and Cr) nanoparticles with similar particle sizes were prepared by an exchange reaction between PdM nanoparticles and an aqueous solution of PtCl42-. The variation in the surface electronic structure of the core–shell structures was evaluated by Pt 4f7/2 X-ray photo-electron spectroscopy and by CO-stripping voltammetry and agrees with the first principle calculations. At 0.85V, the PdM@PdPt/C core–shell electrocatalysts show a 6-fold variation in activity, following the Volcano trend predicted by the calculations. The Pt mass activity of the Volcano-optimal PdFe@PdPt/C catalyst is an order of magnitude higher than the activity of commercial 3.0-nm Pt/C catalysts. The core–shell catalysts also display a high methanol tolerance, which is important for use in direct methanol fuel cells. Calculated Pt–M segregation energies suggest that the Pd3M@Pd3Pt core–shell structures are stable, in particular in the presence of 1/4ML CO. Adsorption of oxygen-containing species may induce surface segregation of the 3d transition metal, except for the Volcano-optimal ORR catalyst, Pd3Fe@Pd3Pt.