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.

We demonstrate the unprecedented proton exchange membrane fuel cell (PEMFC) performance durability of a family of dealloyed Pt-Ni nanoparticle catalysts for the oxygen reduction reaction (ORR), exceeding scientific and technological state-of-art activity and stability targets. We provide atomic-scale insight into key factors controlling the stability of the cathode catalyst by studying the influence of particle size, the dealloying protocol and post-acid-treatment annealing on nanoporosity and passivation of the alloy nanoparticles. Scanning transmission electron microscopy coupled to energy dispersive spectroscopy data revealed the compositional variations of Ni in the particle surface and core, which were combined with an analysis of the particle morphology evolution during PEMFC voltage cycling; together, this enabled the elucidation of alloy structure and compositions conducive to long-term PEMFC device stability. We found that smaller size, less-oxidative acid treatment and annealing significantly reduced Ni leaching and nanoporosity formation while encouraged surface passivation, all resulting in improved stability and higher catalytic ORR activity. This study demonstrates a successful example of how a translation of basic catalysis research into a real-life device technology may be done.DFG, SPP 1613, Regenerativ erzeugte Brennstoffe durch lichtgetriebene Wasserspaltung: Aufklärung der Elementarprozesse und Umsetzungsperspektiven auf technologische Konzep

Using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy line profiles with Ångstrom resolution, we uncover novel core-shell fine structures in a series of catalytically active dealloyed Pt(x)Ni(1-x) core-shell nanoparticles, showing the formation of unusual near-surface Ni-enriched inner shells. The radial location and the composition of the Ni-enriched inner shells were sensitively dependent on the initial alloy compositions. We further discuss how these self-organized Ni-enriched inner shells play a key role in maintaining surface lattice strain and thus control the surface catalytic activity for oxygen reduction.

Nanoporosity is a frequently reported phenomenon in bimetallic particle ensembles used as electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. It is generally considered a favorable characteristic, because it increases the catalytically active surface area. However, the effect of nanoporosity on the intrinsic activity and stability of a nanoparticle electrocatalyst has remained unclear. Here, we present a facile atmosphere-controlled acid leaching technique to control the formation of nanoporosity in Pt-Ni bimetallic nanoparticles. By statistical analysis of particle size, composition, nanoporosity, and atomic-scale core-shell fine structures before and after electrochemical stability test, we uncover that nanoporosity formation in particles larger than ca. 10 nm is intrinsically tied to a drastic dissolution of Ni and, as a result of this, a rapid drop in intrinsic catalytic activity during ORR testing, translating into severe catalyst performance degradation. In contrast, O2-free acid leaching enabled the suppression of nanoporosity resulting in more solid core-shell particle architectures with thin Pt-enriched shells; surprisingly, such particles maintained high intrinsic activity and improved catalytic durability under otherwise identical ORR tests. On the basis of these findings, we suggest that catalytic stability could further improve by controlling the particle size below ca. 10 nm to avoid nanoporosity. Our findings provide an explanation for the degradation of bimetallic particle ensembles and show an easy to implement pathway toward more durable fuel cell cathode catalysts.