Abstract
In this work, we study the mechanism and kinetics of the oxygen reduction reaction (ORR) over Pd/C, Pd2Co/C and PdCo2/C electrocatalysts synthesized by thermal reduction of organometallic precursors, such as [Pd3(μ-3-Ph-pz)6], [Et4N]2[Pd2Co(μ-4-I-3,5-Me2-pz)4Cl4], and [Et4N]2[PdCo2(μ-4-I-3,5-Me2-pz)4Cl4]. The methanol tolerance and formation of peroxide under oxygen reduction reaction conditions were determined using a rotating disk electrode (RDE) and a rotating ring disk electrode (RRDE). The Pd2Co/C catalysts prepared from [Et4N]2[PdCo2(4-I-3,5-Me2-pz)4Cl4] showed the best ORR activity and higher methanol tolerance, compared with commercial platinum catalysts. The ORR electron transfer number for Pd2Co/C was 3.7, similar to the Pd/C commercial catalysts. Compared to the commercial catalysts, Pd2Co/C and PdCo2/C showed the highest hydrogen peroxide formation (%H2O2), 16 and 24%, respectively. Electrogeneration of hydrogen peroxide has potential application in advanced oxidation processes.
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