Platinum-rare earth nanoalloys have been predicted to
be promising
proton exchange membrane fuel cell (PEMFC) electrocatalysts for the
cathodic oxygen reduction reaction (ORR). However, their implementation
in PEMFCs is limited by the challenge of their preparation as carbon-supported
nanostructures. Consequently, the practical structure–activity–stability
trends for this class of nanoalloys remain largely unexplored. Herein,
carbon-supported Pt–Nd nanoalloys as ORR electrocatalysts are
described. The physical chemistry of selected electrocatalysts was
extensively investigated by means of combined ex situ and operando techniques, which reveal the unique
structural dynamics of Pt–Nd nanoalloys in a simulated PEMFC
cathode environment. The experimental observations, supported by theoretical
calculations, indicate that after initial significant structural modification
in the early stage of operation, the ORR activity is mediated in the
longer term by surface compressive strain rather than charge transfer
between Pt and Nd. Such key operando structure–activity–stability
relations underpin further optimization of carbon-supported Pt-rare
earth nanoalloys as fuel cell cathode catalysts.