Protection Against Absorption Passivation on Platinum by a Nitrogen-Doped Carbon Shell for Enhanced Oxygen Reduction Reaction.

In polymer electrolyte type fuel cells, the platinum-based catalysts are applied for the oxygen reduction reaction. However, the specific adsorption from the sulfo group in perfluorosulfonic acid ionomers has been considered to passivate the active sites of the platinum. Herein, we present platinum catalysts covered by an ultrathin two-dimensional nitrogen-doped carbon shell (CNx) layer to protect the platinum from the specific adsorption of perfluorosulfonic acid ionomers. Such coated catalysts were obtained by the facile polydopamine coating method, which is available to tune the thickness of the carbon shell by tuning the polymerization time. The coated catalysts that possess a CNx with a thickness of 1.5 nm demonstrated superior ORR activity and comparable oxygen diffusivity when compared to the commercial Pt/C. These results were supported by the changes in the electronic statements observed in the X-ray photoelectron spectroscopy (XPS) and CO stripping analyses. Furthermore, the oxygen coverage, CO displacement charge, and operando X-ray absorption spectroscopy (XAS) tests were employed to identify the protection effect of CNx in coated catalysts compared with the Pt/C catalysts. In summary, the CNx could not only suppress the oxide species generation but also prevent the specific adsorption of the sulfo group in the ionomer.