Byungkwon Lim

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

Extending Platinum Catalysts Platinum performs extremely well as a catalyst for the oxygen-reduction reaction that runs under highly acidic conditions in proton-exchange membrane fuel cells, but is expensive. One strategy for reducing costs is to increase the surface area of the platinum. Lim et al. (p. 1302, published online 14 May) describe a simple chemical route, in which Pt ions in solution are reduced onto Pd seed crystals, which creates faceted Pt nanocrystals with a high area owing to their dendritic architecture. On a Pt mass basis, these catalysts are several times more active than conventional Pt catalysts. The catalytic activity of platinum is enhanced through a growth process that creates nanocrystals with high surface area. Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

Metal nanocrystals with highly branched morphologies.

Metal nanocrystals with highly branched morphologies are an exciting new class of nanomaterials owing to their unique structures, physicochemical properties, and great potential as catalysts, sensing materials, and building blocks for nanoscale devices. Various strategies have recently been developed for the solution-phase synthesis of metal nanocrystals with branched morphologies, such as multipods and nanodendrites. In this Minireview, the procedures and mechanisms underlying the formation of branched metal nanocrystals are presented in parallel with recent advances in synthetic approaches based on kinetically controlled overgrowth, aggregation-based growth, heterogeneous seeded growth, selective etching, and template-directed methods, as well as their properties for catalytic or electrocatalytic applications.

Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic Applications

Palladium is a marvelous catalyst for a rich variety of reactions in industrial processes and commercial devices. Most Pd-catalyzed reactions exhibit structure sensitivity, meaning that the activity or selectivity depends on the arrangement of atoms on the surface. Previously, such reactions could only be studied in ultrahigh vacuum using Pd single crystals cut with a specific crystallographic plane. However, these model catalysts are far different from real catalytic systems owing to the absence of atoms at corners and edges and the extremely small specific surface areas for the model systems. Indeed, enhancing the performance of a Pd-based catalyst, in part to reduce the amount needed of this precious and rare metal for a given reaction, requires the use of Pd with the highest possible specific surface area. Recent advances in nanocrystal synthesis are offering a great opportunity to investigate and quantify the structural sensitivity of catalysts based on Pd and other metals. For a structure-sensitive reaction, the catalytic properties of Pd nanocrystals are strongly dependent on both the size and shape. The shape plays a more significant role in controlling activity and selectivity, because the shape controls not only the facets but also the proportions of surface atoms at corners, edges, and planes, which affect the outcomes of possible reactions. We expect catalysts based on Pd nanocrystals with optimized shapes to meet the increasing demands of industrial applications at reduced loadings and costs. In this Account, we discuss recent advances in the synthesis of Pd nanocrystals with controlled shapes and their resulting performance as catalysts for a large number of reactions. First, we review various synthetic strategies based on oxidative etching, surface capping, and kinetic control that have been used to direct the shapes of nanocrystals. When crystal growth is under thermodynamic control, the capping agent plays a pivotal role in determining the shape of a product by altering the order of surface energies for different facets through selective adsorption; the resulting product has the lowest possible total surface energy. In contrast, the product of a kinetically controlled synthesis often deviates from the thermodynamically favored structure, with notable examples including nanocrystals enclosed by high-index facets or concave surfaces. We then discuss the key parameters that control the nucleation and growth of Pd nanocrystals to decipher potential growth mechanisms and build a connection between the experimental conditions and the pathways to different shapes. Finally, we present a number of examples to highlight the use of these Pd nanocrystals as catalysts or electrocatalysts for various applications with structure-sensitive properties. We believe that a deep understanding of the shape-dependent catalytic properties, together with an ability to experimentally maneuver the shape of metal nanocrystals, will eventually lead to rational design of advanced catalysts with substantially enhanced performance.

Synthesis of Pd−Au Bimetallic Nanocrystals via Controlled Overgrowth

This paper describes the synthesis of Pd-Au bimetallic nanocrystals with controlled morphologies via a one-step seeded-growth method. Two different reducing agents, namely, L-ascorbic acid and citric acid, were utilized for the reduction of HAuCl(4) in an aqueous solution to control the overgrowth of Au on cubic Pd seeds. When L-ascorbic acid was used as the reducing agent, conformal overgrowth of Au on the Pd nanocubes led to the formation of Pd-Au nanocrystals with a core-shell structure. On the contrary, localized overgrowth of Au was observed when citric acid was used as the reducing agent, producing Pd-Au bimetallic dimers. Through this morphological control, we were able to tune the localized surface plasmon resonance peaks of Pd-Au bimetallic nanostructures in the visible region.

Aqueous‐Phase Synthesis of Pt/CeO2 Hybrid Nanostructures and Their Catalytic Properties

DOI: 10.1002/adma.201002763 Metal nanocrystals supported on metal oxides often exhibit improved catalytic activity and selectivity as compared to unsupported ones, [ 1–4 ] which is known to arise from several factors, including the shape and size of metal nanocrystals, the metal oxidation state, and the support effect. [ 5–11 ] Early methods for preparing metal nanocrystal on metal oxide hybrid nanostructures mainly involved calcination of metal oxide powders impregnated with metal precursors at high temperatures ( > 400 ° C). [ 12–17 ]

Facile Synthesis of Highly Faceted Multioctahedral Pt Nanocrystals through Controlled Overgrowth

Highly faceted Pt nanocrystals with a large number of interconnected arms in a quasi-octahedral shape were synthesized simply by reducing H2PtCl6 precursor with poly(vinyl pyrrolidone) in aqueous solutions containing a trace amount of FeCl3. The iron species (Fe(3+) or Fe(2+)) play a key role in inducing the formation of the multioctahedral structure by decreasing the concentration of Pt atoms and keeping a low concentration for the Pt seeds during the reaction. This condition favors the overgrowth of Pt seeds along their corners and thus the formation of multiarmed nanocrystals. Electron microscopy studies revealed that the multioctahedral Pt nanocrystals exhibit a large number of edge, corner, and surface step atoms. The size of the multioctahedral Pt nanocrystals can be controlled by varying the concentration of FeCl3 added to the reaction and/or the reaction temperature. These multioctahedral Pt nanocrystals were tested as electrocatalysts for the oxygen reduction reaction in a proton exchange membrane fuel cell and exhibited improved specific activity and durability compared to commercial Pt/C catalyst.

Facile Synthesis of Bimetallic Nanoplates Consisting of Pd Cores and Pt Shells through Seeded Epitaxial Growth

Pd-Pt core-shell nanoplates with hexagonal and triangular shapes were synthesized through the heterogeneous, epitaxial growth of Pt on Pd nanoplates. The Pd nanoplates were synthesized by reducing Na2PdCl4 precursor with PVP as a reducing agent, which then served as seeds for the nucleation of Pt atoms formed by reducing H2PtCl6 with citric acid. Characterization of the as-prepared Pd-Pt nanoplates by scanning transmission electron microscopy and high-resolution transmission electron microscopy reveals that a thin, uniform Pt shell was formed around the Pd nanoplate, demonstrating the layer-by-layer epitaxial growth of Pt on Pd surface in this approach. The close lattice match between Pd and Pt (lattice mismatch of only 0.77%) and the slow reduction rate associated with the mild reducing power of citric acid play key roles in achieving the epitaxial growth of Pt shells on Pd nanoplates.

Mechanistic Study of the Synthesis of Au Nanotadpoles, Nanokites, and Microplates by Reducing Aqueous HAuCl4 with Poly(vinyl pyrrolidone)

This article describes a simple approach to anisotropic Au nanostructures with various shapes by reducing HAuCl 4 with poly(vinyl pyrrolidone) (PVP) in aqueous solutions without the use of any additional capping agent or reductant. In this approach, the commercially available PVP servers as a mild reducing agent thanks to its hydroxyl (-OH) end groups, enabling kinetic control over both nucleation and growth. As the volume of HAuCl 4 solution added to the reaction was increased, the morphology of Au nanostructures evolved from nanotadpoles to nanokites and then triangular and hexagonal microplates. The slow reduction rate associated with the mild reducing power of PVP plays a critical role in forming nanoplates during nucleation as well as their growth into highly anisotropic nanostructures. Electron microscopy studies reveal that the nanotadpoles and nanokites are formed through the linear fusion of small Au particles (<10 nm) to the initially formed nanoplates, whereas the microplates result from the continuous addition of Au atoms to the side faces of nanoplates. Through this morphological control, the localized surface plasmon resonance peaks of these Au nanostructures can be tuned in the visible and near-IR regions.

A sinter-resistant catalytic system based on platinum nanoparticles supported on TiO2 nanofibers and covered by porous silica.

Platinum is a key catalyst that is invaluable in many important industrial processes such as CO oxidation in catalytic converters, oxidation and reduction reactions in fuel cells, nitric acid production, and petroleum cracking. Many of these applications utilize Pt nanoparticles supported on oxides or porous carbon. However, in practical applications that involve high temperatures (typically higher than 300 8C), the Pt nanoparticles tend to lose their specific surface area and thus catalytic activity during operation because of sintering. Recent studies have shown that a porous oxide shell can act as a physical barrier to prevent sintering of unsupported metal nanoparticles and, at the same time, provide channels for chemical species to reach the surface of the nanoparticles, thus allowing the catalytic reaction to occur. This concept has been demonstrated in several systems, including Pt@SiO2, [3] Pt@CoO, Pt/CeO2@SiO2, [5] Pd@SiO2, [6] Au@SiO2, [7] Au@SnO2 [8] and Au@ZrO2 [9] core– shell nanostructures. Despite these results, a sinter-resistant system has not been realized in supported Pt nanoparticle catalysts. Improved catalytic or photocatalytic properties are often achieved when metal nanoparticles are supported on oxides such as TiO2 and CeO2 that interact strongly with late transition metals. Herein, we demonstrate a thermally stable catalytic system consisting of Pt nanoparticles that are supported on a TiO2 nanofiber and coated with a porous SiO2 sheath. In this system, the porous SiO2 coating offers an energy barrier to prevent the migration of individual Pt atoms or nanoparticles because of its weak interaction with late transition metals, including Pt. The porous-SiO2/Pt/TiO2 catalytic system was prepared in three steps (Figure 1):