Nanoscale Pt-Ni bimetallic octahedra with controlled sizes have been actively explored in recent years owning to their outstanding activity for the oxygen reduction reaction (ORR). Here we report the synthesis of uniform 9 nm Pt-Ni octahedra with the use of oleylamine and oleic acid as surfactants and W(CO)6 as a source of CO that can promote the formation of {111} facets in the presence of Ni. Through the introduction of benzyl ether as a solvent, the coverage of both surfactants on the surface of resultant Pt-Ni octahedra was significantly reduced while the octahedral shape was still attained. By further removing the surfactants through acetic acid treatment, we observed a specific activity 51-fold higher than that of the state-of-the-art Pt/C catalyst for the ORR at 0.93 V, together with a record high mass activity of 3.3 A mgPt(-1) at 0.9 V (the highest mass activity reported in the literature was 1.45 A mgPt(-1)). Our analysis suggests that this great enhancement of ORR activity could be attributed to the presence of a clean, well-preserved (111) surface for the Pt-Ni octahedra.

Controlling the shape or morphology of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addition of atomic species. In this case, manipulating the rates at which the atomic species are added onto different crystallographic planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphology taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. Herein, we demonstrated that the growth pathway of a seed is indeed determined by the ratio between the rates for atom deposition and surface diffusion. Our result suggests that surface diffusion needs to be taken into account when controlling the shape or morphology of metal nanocrystals. seeded growth | shape control | noble metals S urface diffusion is a general process that involves the motion of adsorbed atoms (adatoms), molecules, or atomic clusters on the surface of a solid material (1, 2). Over the past decades, it has emerged as an important concept in many areas of surface science, including catalysis, epitaxial growth, and electromigration of voids (3-7). Here, we demonstrated that surface diffusion also plays a pivotal role in determining the growth pathway of a seed and thus the shape or morphology taken by the final product in a solutionphase synthesis of metal nanocrystals. Fig. 1 schematically illustrates four possible pathways for the growth of a cubic seed. As a model system, we focused on Pd nanocubes with slight truncation at corners and edges, together with six side faces passivated by chemisorbed Br -ions. In the following discussion, we refer to them as "Pd cubic seeds" for simplicity. We chose them as seeds for two major reasons: (i) they had a well-defined shape, together with a set of low-index facets on the surface (8, 9); and (ii) their side faces are blocked by Br -ions to ensure selective deposition of atoms onto the corner sites during seed-mediated growth (10-12). These two distinctive features allowed us to easily track the deposition of atoms and their surface diffusion during a growth process by analyzing the shape or morphology of the final product.The newly formed Pd atoms resulting from the reduction of a Pd precursor are expected to deposit at the corners of a cubic seed because the side faces are blocked by the chemisorbed Br -ions (Fig. 1A, 1). Upon deposition, there will be two different options for these adatoms: staying at the corner sites or migrating to other sites, including edges and side faces, through surface diffusion (Fig. 1A, 2 and 3). It should be pointed out that only surface diffusion was allowed here to move atoms from corners to edg...

Kinetic control is a powerful means for maneuvering the twin structure and shape of metal nanocrystals and thus optimizing their performance in a variety of applications. However, there is only a vague understanding of the explicit roles played by reaction kinetics due to the lack of quantitative information about the kinetic parameters. With Pd as an example, here we demonstrate that kinetic parameters, including rate constant and activation energy, can be derived from spectroscopic measurements and then used to calculate the initial reduction rate and further have this parameter quantitatively correlated with the twin structure of a seed and nanocrystal. On a quantitative basis, we were able to determine the ranges of initial reduction rates required for the formation of nanocrystals with a specific twin structure, including single-crystal, multiply twinned, and stacking fault-lined. This work represents a major step forward toward the deterministic syntheses of colloidal noble-metal nanocrystals with specific twin structures and shapes.

Controlling the shape and thus facets of metal nanocrystals is an effective way to enhance their performance in catalytic reactions. While Pd nanocrystals with a myriad of shapes have been successfully prepared with good uniformity and in high yield, Pd right bipyramids (RBPs) that have a singly twinned structure have been elusive. We report a facile route based on polyol reduction for the synthesis of Pd RBPs with purity >90% and sizes controlled in the range 5-15 nm. The success of our synthesis relies on the use of iodide ions to manipulate the strength of an oxidative etchant and selectively cap the Pd{100} facets. The as-prepared RBPs could serve as seeds to generate a set of Pd nanocrystals with novel shapes and structures. The RBPs also exhibited enhanced catalytic activity toward formic acid oxidation, with a current density 2.5 and 7.1 times higher than those of the single-crystal Pd nanocubes (which were also mainly covered by {100} facets) and commercial Pd black, respectively.

The oxygen reduction reaction (ORR) on the cathode of a polymer electrolyte fuel cell requires the use of a catalyst based on Pt, one of the most expensive metals on the earth. A number of strategies, including optimization of shape or facet, formation of alloys with other metals, and incorporation of a different metal into the core, have been investigated to enhance the activity of a Pt-based catalyst and thus reduce the loading of Pt. This article reports the synthesis and characterization of Pd@Pt-Ni core-shell octahedra with high activity toward ORR. The octahedra with an edge length of 8 nm were obtained by directly depositing thin, conformal shells of a Pt-Ni alloy on Pd octahedra of 6 nm in edge length. The key to the success of this synthesis is the use of an amphiphilic solvent to ensure good compatibility between the solvents typically used for the syntheses of Pd and Pt-Ni nanocrystals. The core-shell structure was confirmed by a number of techniques, including scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, in situ X-ray diffraction under H2 and He, and electrochemical measurements. Relative to the state-of-the-art Pt/C catalyst, the Pd@Pt-Ni/C catalyst showed mass and specific ORR activities enhanced by 12.5- and 14-fold, respectively. The formation of a core-shell structure helped increase the electroactive surface area in terms of Pt and thus the mass activity. During an accelerated durability test, the mass activity of the Pd@Pt-Ni/C catalyst only dropped by 1.7% after 10,000 cycles.

This article reports a robust method based upon polyol reduction for the deterministic synthesis of Pd decahedra or icosahedra with tunable sizes and a purity approaching 100%. The success of such a selective synthesis relies on an ability to fine-tune the reaction kinetics through the addition of Na2SO4 and HCl for decahedra and icosahedra, respectively. In the absence of any additive, the product of a similar synthesis in diethylene glycol contained 10% decahedra and 90% icosahedra. By optimizing the amount of Na2SO4 (or HCl) added into the reaction solution, the percent of decahedra (or icosahedra) in the product could be increased up to 100%. The roles of Na2SO4 and HCl were also investigated in great detail, and two plausible mechanisms were proposed and validated through a set of experiments. In general, a faster reduction rate is needed for the synthesis of Pd decahedra when compared with what is needed for Pd icosahedra. This work not only offers a simple approach to the deterministic syntheses of Pd decahedra and icosahedra but also provides an in-depth understanding of the mechanisms involved in shape-controlled syntheses of noble-metal nanocrystals from the perspective of reaction kinetics. On the basis of the mechanistic understanding, we have also achieved successful synthesis of Pd decahedra as pure samples by adding a proper amount of NaOH into the system to speed up the reduction kinetics.

This article describes a seed-mediated approach to the synthesis of Ag nanorods with thin diameters and tunable aspect ratios. The success of this method is built upon our recent progress in the synthesis of Pd decahedra as uniform samples, together with controllable sizes. When used as a seed, the Pd decahedron could direct the deposition of Ag atoms along the 5-fold axis to generate a nanorod, with its diameter being determined by the lateral dimension of the seed. We were able to generate Ag nanorods with uniform diameters down to 20 nm. Under the conditions we used for growth, symmetry breaking occurred as the Ag atoms were only deposited along one side of the Pd decahedral seed to generate a Ag nanorod with the Pd seed being positioned at one of its two ends. We also systematically investigated the localized surface plasmon resonance (LSPR) properties of the Ag nanorods. With the transverse mode kept below 400 nm, the longitudinal mode could be readily tuned from the visible to the near-infrared region by varying the aspect ratio. As an important demonstration, we obtained Ag nanorods with no LSPR peak in the visible spectrum (400-800 nm), which are attractive for applications related to the fabrication of touchscreen displays, solar films, and energy-saving smart windows.

We describe a synthesis of Au wavy nanowires in an aqueous solution in the presence of cetyltrimethylammonium bromide (CTAB). The resultant Au nanowires automatically separated from the solution and floated at the air/water interface. We investigated the formation mechanism by characterizing the samples obtained at different stages of the synthesis. Both particle attachment and cold welding were found to be involved in the formation of such nanowires. Based on X-ray photoelectron spectroscopy and thermogravimetric analysis, the CTAB molecules adsorbed on the surface of a Au nanostructure went through a change in structure from a bilayer to a monolayer, converting the Au surface from hydrophilic to hydrophobic. As a result, the Au wavy nanowires were driven to the air/water interface during the synthesis. This growth mechanism is potentially extendable to many other systems involving small surfactant molecules.