Observing the Structural Evolution of Quasi-Monolayer Pt Shell on Pd Core in the Electrocatalytic Oxygen-Reduction Reaction.

Abstract

The use of a quasi-monolayer Pt shell (Ptqms) on a Pd core (Pdc) can reach cost and activity targets for the electrocatalytic oxygen-reduction reaction (ORR). The structure of PdcPtqms in the ORR will vary; however, direct observation of this issue is scarce. Here, during cyclic staircase voltammetry (ranging from 0.5 to 1.15 VRHE) in 0.1 M O2-saturated HClO4, the structure of PdcPtqms was monitored by in situ X-ray absorption spectroscopy. The qualitative and quantitative structural information clearly exhibits a complete picture that Ptqms will directly restructure to form Pt clusters and holes, while Pdc almost remains stable. These findings identify the initial structural evolution of PdcPtqms in the ORR, highlighting the importance of protecting Pdc in the development of high-performance PdcPtqms electrocatalysts.