A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.

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We report a facile synthesis of multiply twinned Pd@Pt core-shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200 °C, naturally generating a core-shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm(2)Pt) and mass (1.60 A/mgPt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm(2)Pt and 0.32 A/mgPt, respectively). After 10,000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgPt, more than twice that of the pristine Pt/C catalyst.

Nanocages have received considerable attention in recent years for catalytic applications owing to their high utilization efficiency of atoms and well-defined facets. Here we report, for the first time, the synthesis of Ru cubic nanocages with ultrathin walls, in which the atoms are crystallized in a face-centered cubic (fcc) rather than hexagonal close-packed (hcp) structure. The key to the success of this synthesis is to ensure layer-by-layer deposition of Ru atoms on the surface of Pd cubic seeds by controlling the reaction temperature and the injection rate of a Ru(III) precursor. By selectively etching away the Pd from the Pd@Ru core-shell nanocubes, we obtain Ru nanocages with an average wall thickness of 1.1 nm or about six atomic layers. Most importantly, the Ru nanocages adopt an fcc crystal structure rather than the hcp structure observed in bulk Ru. The synthesis has been successfully applied to Pd cubic seeds with different edge lengths in the range of 6-18 nm, with smaller seeds being more favorable for the formation of Ru shells with a flat, smooth surface due to shorter distance for the surface diffusion of the Ru adatoms. Self-consistent density functional theory calculations indicate that these unique fcc-structured Ru nanocages might possess promising catalytic properties for ammonia synthesis compared to hcp Ru(0001), on the basis of strengthened binding of atomic N and substantially reduced activation energies for N2 dissociation, which is the rate-determining step for ammonia synthesis on hcp Ru catalysts.

Ruthenium nanocrystals with both a face-centered cubic (fcc) structure and well-controlled facets are attractive catalytic materials for various reactions. Here we report a simple method for the synthesis of Ru octahedral nanocrystals with an fcc structure and an edge length of 9 nm. The success of this synthesis relies on the use of 4.5 nm Rh cubes as seeds to facilitate the heterogeneous nucleation and overgrowth of Ru atoms. We choose Rh because it can resist oxidative etching under the harsh conditions for Ru overgrowth, it can be readily prepared as nanocubes with edge lengths less than 5 nm, and its atoms have a size close to that of Ru atoms. During the seed-mediated growth, the atomic packing of Ru overlayers follows an fcc lattice, in contrast to the conventional hexagonal close-packed (hcp) lattice associated with bulk Ru. The final product takes an octahedral shape, with the surface enclosed by {111} facets. Our in situ measurements suggest that both the octahedral shape and the fcc crystal structure can be well preserved up to 400 °C, which is more than 100 °C higher than what was reported for Ru octahedral nanocages. When utilized as catalysts, the Ru octahedral nanocrystals exhibited 4.4-fold enhancement in terms of specific activity toward oxygen evolution relative to hcp-Ru nanoparticles. We also demonstrate that Ru{111} facets are more active than Ru{100} facets in catalyzing the oxygen evolution reaction. Altogether, this work offers an effective method for the synthesis of Ru nanocrystals with an fcc structure and well-defined {111} facets, as well as enhanced thermal stability and catalytic activity. We believe these nanocrystals will find use in various catalytic applications.