Oxygen reduction reaction on PdM/C (M = Pb, Sn, Bi) alloy nanocatalysts

In this work three PdM/C bimetallic catalysts were prepared with a second metal being either Bi, Pb or Sn. The synthesised Pd-alloy nanoparticles were supported on Vulcan carbon XC-72R. These catalysts were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM) and electrochemically using the rotating disk electrode (RDE) technique. The prepared Pd-based electrocatalysts were compared to pure Pd/C catalyst synthesised using the citrate method. The oxygen reduction reaction (ORR) kinetics on Pd-alloy catalysts in alkaline solution was systematically investigated. Pd content was determined by microwave plasma atomic emission spectroscopy, which was used to calculate the mass activities (MA) for ORR. Mass activities revealed that BiPd had two-fold higher and PbPd showed 1.6-times increase in MA as compared to Pd/C, however SnPd showed lower MA than Pd/C. BiPd/C catalyst showed around 45% increase in specific activity (SA) for ORR, PdSn catalyst showed around 25% increase and PbPd no increase in SA in comparison to the Pd/C catalyst. Methanol tolerance was also studied for the PdM/C alloy catalysts and a higher tolerance was observed for BiPd/C losing 17 mV in the half-wave potential value and even better methanol tolerance was in evidence with the other two catalysts that lost only ∼10 mV in 0.1 M KOH + 0.5 M MeOH.