Oxygen reduction reaction on Pt-skin Pt3V(111) fuel cell cathode: a density functional theory study

Abstract

Pt-non-precious transition metals (Pt-NPTMs) alloy electrocatalysts have gained considerable attention to develop cheaper and efficient electrocatalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). In this report, density functional theory (DFT) has been applied to study the catalytic activity of Pt-skin Pt₃V(111) electrocatalyst for ORR in PEMFCs. The results revealed that the ORR intermediates (O, OH and OOH) have lower binding energies on Pt-skin Pt₃V(111) compared to pure Pt(111) surface. The ORR on Pt-skin Pt₃V(111) surface proceed via OOH dissociation with an activation energy of 0.33 eV. The formation of OH is found to be the rate determining step with an activation energy of 0.64 eV, which is even lower than in pure Pt(111) surface (0.72 eV). This indicates a better performance of Pt-skin Pt₃V(111) for ORR compared to pure Pt(111) surface. Moreover, the DFT results revealed that the negative formation energy of the Pt₃V alloy and the positive dissolution potential shift of the surface Pt atoms revealed the better stability of Pt-skin Pt₃V(111) surface over pristine Pt(111) surface. Due to the improved activity and better stability, the new Pt₃V alloy electrocatalyst is very promising for the development of low-cost and efficient PEMFCs.