Pt skin on Pd–Co–Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

Abstract

Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, a highly active, durable, carbon supported, and monolayer Pt coated Pd–Co–Zn nanoparticle is synthesized via a simple impregnation–reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition–activity volcano curve for the Pd–Co–Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd₈CoZn/C nanoparticles show a substantial enhancement in both the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd₈CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N₂-saturated 0.1 M HClO₄ solution, Pd₈CoZn@Pt/C shows improved mass activity (2.62 A mg⁻¹_Pt) and specific activity (4.76 A m⁻²_total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O₂-saturated 0.1 M HClO₄ solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. The results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.