Effect of post heat-treatment of composition-controlled PdFe nanoparticles for oxygen reduction reaction

•Heat-treatment altered sample structures and generated a superlattice phase.•Pd d-band center shifted down leading to a decreased oxygen binding energy.•Outstanding ORR activity relative to Pt/C and other PdM catalysts was achieved.•ORR activities were verified by single cell performances.

Composition-controlled and carbon-supported PdFe nanoparticles (NPs) were prepared via a modified chemical synthesis after heat-treatment at high temperature under a reductive atmosphere. This novel synthesis, which combines the polyol reduction method and hydride method, was used to obtain monodispersed PdFe NPs. In addition, to induce structural modifications, the as-prepared PdFe NPs received heat-treatment under a reductive atmosphere. Structural characterization, including high-resolution powder diffraction (HRPD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) analysis, indicated that heat-treated PdFe NPs exhibited a higher degree of alloying and surface Pd atomic composition compared with as-prepared ones. Furthermore, new crystalline phases were detected after heat-treatment. Thanks to the structural alterations, heat-treated PdFe NPs showed ∼3 and ∼18 times higher mass- and area-normalized oxygen reduction reaction (ORR) activities, respectively than commercial Pt/C. Single cell testing with heat-treated PdFe catalysts exhibited a ∼2.5 times higher mass-normalized maximum power density than the reference cell. Surface structure analyses, including cyclic voltammetry (CV), COad oxidation, and XPS, revealed that, after heat-treatment, a downshift of the Pd d-band center occurred, which led to a decrease in the affinity of Pd for oxygen species, resulting in more favorable ORR kinetics.

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