Shape-selective monometallic nanocatalysts offer activity benefits based on structural sensitivity and high surface area. In bimetallic nanoalloys with well-defined shape, site-dependent metal surface segregation additionally affects the catalytic activity and stability. However, segregation on shaped alloy nanocatalysts and their atomic-scale evolution is largely unexplored. Exemplified by three octahedral PtxNi1-x alloy nanoparticle electrocatalysts with unique activity for the oxygen reduction reaction at fuel cell cathodes, we reveal an unexpected compositional segregation structure across the {111} facets using aberration-corrected scanning transmission electron microscopy and electron energy-loss spectroscopy. In contrast to theoretical predictions, the pristine PtxNi1-x nano-octahedra feature a Pt-rich frame along their edges and corners, whereas their Ni atoms are preferentially segregated in their {111} facet region. We follow their morphological and compositional evolution in electrochemical environments and correlate this with their exceptional catalytic activity. The octahedra preferentially leach in their facet centres and evolve into 'concave octahedra'. More generally, the segregation and leaching mechanisms revealed here highlight the complexity with which shape-selective nanoalloys form and evolve under reactive conditions.

We demonstrate how shape selectivity and optimized surface composition result in exceptional oxygen reduction activity of octahedral PtNi nanoparticles (NPs). The alloy octahedra were obtained by utilizing a facile, completely surfactant-free solvothermal synthesis. We show that the choice of precursor ligands controls the shape, while the reaction time tunes the surface Pt:Ni composition. The 9.5 nm sized PtNi octahedra reached a 10-fold surface area-specific (~3.14 mA/cm(Pt)(2)) as well as an unprecedented 10-fold Pt mass based (~1.45 A/mg(Pt)) activity gain over the state-of-art Pt electrocatalyst, approaching the theoretically predicted limits.

Sulfur-stabilized intermetallic nanoparticles Nanoparticles of intermetallic alloys of platinum could have enhanced electronic properties that improve their catalytic activity, but the high temperatures needed to ensure complete atomic diffusion often lead to the growth of larger nanoparticles—sintering—with low surface area and hence low overall activity. Yang et al . show that sulfur-doped carbon supports create strong platinum-sulfur bonds that stabilize small platinum alloy nanoparticles (<5 nanometers in diameter) to temperatures up to 1000ºC. They screened libraries of platinum alloys and identified ones with high mass activity for the oxygen reduction reaction in hydrogen fuel cells. —PDS

Morphological shape in chemistry and biology owes its existence to anisotropic growth and is closely coupled to distinct functionality. Although much is known about the principal growth mechanisms of monometallic shaped nanocrystals, the anisotropic growth of shaped alloy nanocrystals is still poorly understood. Using aberration-corrected scanning transmission electron microscopy, we reveal an element-specific anisotropic growth mechanism of platinum (Pt) bimetallic nano-octahedra where compositional anisotropy couples to geometric anisotropy. A Pt-rich phase evolves into precursor nanohexapods, followed by a slower step-induced deposition of an M-rich (M = Ni, Co, etc.) phase at the concave hexapod surface forming the octahedral facets. Our finding explains earlier reports on unusual compositional segregations and chemical degradation pathways of bimetallic polyhedral catalysts and may aid rational synthesis of shaped alloy catalysts with desired compositional patterns and properties.

A free‐standing Pt‐nanowire membrane fabricated via a multistep templating process is used as an electrocatalyst for the oxygen reduction reaction (ORR). It exhibits remarkably high stability and good catalytic activity due to its unique nanowire‐network structure.