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Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of "ordered" catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. Here, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order-disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing process to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity. [ABSTRACT FROM AUTHOR]

Shape-controlled octahedral Pt-Ni alloy nanoparticles exhibit remarkably high activities for the electroreduction of molecular oxygen (oxygen reduction reaction, ORR), which makes them fuel-cell cathode catalysts with exceptional potential. To unfold their full and optimized catalytic activity and stability, however, the nano-octahedra require post-synthesis thermal treatments, which alter the surface atomic structure and composition of the crystal facets. Here, we address and strive to elucidate the underlying surface chemical processes using a combination of ex situ analytical techniques with in situ transmission electron microscopy (TEM), in situ X-ray diffraction (XRD), and in situ electrochemical Fourier transformed infrared (FTIR) experiments. We present a robust fundamental correlation between annealing temperature and catalytic activity, where a ~25 times higher ORR activity than for commercial Pt/C (2.7 A mgPt-1 at 0.9 VRHE) was reproducibly observed upon annealing at 300 °C. The electrochemical stability, however, peaked out at the most severe heat treatments at 500 °C. Aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy (EDX) in combination with in situ electrochemical CO stripping/FTIR data revealed subtle, but important, differences in the formation and chemical nature of Pt-rich and Ni-rich surface domains in the octahedral (111) facets. Estimating trends in surface chemisorption energies from in situ electrochemical CO/FTIR investigations suggested that balanced annealing generates an optimal degree of Pt surface enrichment, while the others exhibited mostly Ni-rich facets. The insights from our study are quite generally valid and aid in developing suitable post-synthesis thermal treatments for other alloy nanocatalysts as well. [ABSTRACT FROM AUTHOR]