The influence of the texture, structure, and chemistry of different carbon supports on the morphological properties, oxygen reduction reaction (ORR) activity, and stability of porous hollow PtNi nanoparticles (NPs) was investigated. The carbon nanomaterials included carbon blacks, carbon nanotubes, graphene nanosheets, and carbon xerogel and featured different specific surface areas, degrees of graphitization, and extent of surface functionalization. The external and inner diameters of the supported porous hollow PtNi/C NPs were found to decrease with an increase in the carbon mesopore surface area. Despite these differences, similar morphological properties and electrocatalytic activities for the ORR were reported. The stability of the synthesized electrocatalysts was assessed by simulating electrochemical potential variations occurring at a proton exchange membrane fuel cell (PEMFC) cathode during startup/shutdown events. Identical location transmission electron microscopy (IL-TEM) and electrochemical methods revealed the occurrence of a carbon-specific degradation mechanism: carbon corrosion into CO2 and particle detachment were noticed on carbon xerogels and graphene nanosheets while, on carbon blacks, surface oxidation prevailed (C → COsurf) and did not result in modified electrical resistance of the catalytic layers, rendering these carbon supports better suited to prepare highly active and stable ORR electrocatalysts.
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