Carbon supported PdxPty nanoparticles for oxygen reduction. The effect of Pd:Pt ratio

Abstract

Studies concentrated on the development of carbon supported PdxPty/C electrocatalysts for the oxygen reduction reaction (ORR). The application of the reverse ‘water-in-oil’ microemulsion method allowed to obtain a number of electrocatalysts with metal nanoparticles of ca. 5–6nm in size. Catalysts with the constant metal loading of 10wt% and various Pd:Pt atomic ratios were investigated. The textural features of the PdPt/C catalysts (surface area, morphology) as well as the PdPt phase (metal particle size, bulk composition) were characterized by a number of techniques. A particular attention was paid to the characterization of the surface properties of the PdPt particles using cyclic voltammetry technique. For all Pt contents (5 to 70 at%) a segregation of metal components (Pt, Pd) occurred leading to the Pt enrichment in the top layers. The observed Pt enrichment manifested especially strongly for PdPt catalysts with bulk Pt content below 20 at%. The surface fraction of Pt as high as 0.8 to 0.9 was attained regardless of nominal Pt content, starting from 30 at%. Among the catalysts, those with Pt content of 50 and 70 at% exhibited the highest activity towards ORR in terms of positively shifted half-wave potential, even surpassing that of Pt/C. Moreover, the obtained specific activity and turnover frequency values also suggested similar activities of catalysts with Pt content of 50 and 70 at%. A negligible formation of hydrogen peroxide on these two catalysts, indicated almost exclusively a desired four-electron process leading to water formation. The observed effect of Pt content on ORR activity is discussed in terms of surface properties of the PdPt nanoparticles.