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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]

Diverse topological defects arise in hexagonal manganites, such as ferroelectric vortices, as well as neutral and charged domain walls. The topological defects are intriguing because their low symmetry enables unusual couplings between structural, charge, and spin degrees of freedom, holding great potential for novel types of functional 2D and 1D systems. Despite the considerable advances in analyzing the different topological defects in hexagonal manganites, the understanding of their key intrinsic properties is still rather limited and disconnected. In particular, a rapidly increasing number of structural variants is reported without clarifying their relation, leading to a zoo of seemingly unrelated topological textures. Here, we combine picometer-precise scanning-transmission-electron microscopy with Landau theory modeling to clarify the inner structure of topological defects in Er1-xZrxMnO3. By performing a comprehensive parametrization of the inner atomic defect structure, we demonstrate that one primary length scale drives the morphology of both vortices and domain walls. Our findings lead to a unifying general picture of this type of structural topological defects. We further derive novel fundamental and universal properties, such as unusual bound-charge distributions and electrostatics at the ferroelectric vortex cores with emergent U(1) symmetry. [ABSTRACT FROM AUTHOR]