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Precious metals represent some of the least abundant elements in the earth’s crust. There is an urgent need to maximize the utilization efficiency of these metals and thereby attain affordable and sustainable products. One approach for achieving this goal is based on the development of hollow nanocrystals with a well-controlled surface structure, together with a wall thickness kept below 2 nm, or roughly 10 layers of atoms. The hollow structure eliminates the waste of interior atoms and creates an inner surface, while the controllable surface structures contribute to the optimization of catalytic activity and selectivity. In this article, we begin with a brief introduction to two methods that have been developed for the synthesis of hollow nanocrystals: the first relying on the galvanic replacement with a sacrificial template, and the second involving layer-by-layer deposition of metal atoms followed by etching. We then showcase some remarkable properties and applications of this novel class of nanostructures, including their use as effective catalysts for energy conversion, photoresponsive carriers for controlled release and drug delivery, and theranostic agents. A discussion of the existing barriers to their commercialization is also presented.
Engineering the surface structure, together with the incorporation of a second metal, is an effective strategy for boosting the catalytic activities of Pt-based catalysts toward various reactions. Here, we report a facile approach to the synthesis of Pt–Ag octahedral and tetrahedral nanocrystals covered by concave surfaces. The presence of the Ag(I) precursor not only facilitated the reduction of the Pt(IV) precursor but also led to the formation of concaved facets on the Pt–Ag nanocrystals. Besides, poly(vinylpyrrolidone) (PVP) was demonstrated to serve as a co-reductant, in addition to its role as a colloidal stabilizer. Using PVP with different molecular weights, we were able to tune the size of the Pt–Ag nanocrystals in the range of 9–25 and 14–32 nm for the octahedral and tetrahedral shapes, respectively. The Pt–Ag nanocrystals exhibited 4.6- and 2.0-fold enhancements in terms of specific and mass activities, respectively, toward methanol oxidation, when benchmarked against the commercial Pt/C catalyst. After 1000 cycles of the accelerated tests, the specific and mass activities of the Pt–Ag nanocrystals were still 3.6 and 1.6 times as high as those of the original commercial Pt/C.
The implication of shape control in nanocrystal synthesis goes far beyond aesthetic appeal. For metal nanocrystals, the shape not only determines their physicochemical properties but also their technological relevance for catalytic, plasmonic, photonic, and electronic applications. In particular, heterogeneous catalysis is a field that can benefit tremendously from the availability of metal nanocrystals with well-controlled shapes, which may serve to significantly increase reaction efficiency while decreasing material cost. This article provides a brief overview of our recent progress in generating shape-controlled nanocrystals with enhanced catalytic activity toward oxygen reduction and formic acid oxidation, two reactions that are crucial for the successful commercialization of fuel cell technology. The impact on other industrially important reactions will be discussed as well. We hope that this article provides a roadmap for further development of metal nanocrystal-based catalysts with enhanced performance through shape-controlled synthesis.
The ability to control the shape of metal nanocrystals is central to advances in many areas of modern science and technology, including catalysis, plasmonics, electronics, and biomedicine. This article provides a brief overview of our recent efforts toward the development of solution-phase methods for shape-controlled synthesis of metal nanocrystals. While the synthetic methods only involve simple redox reactions, we have been working diligently to understand the complex nucleation and growth mechanisms leading to the formation of metal nanocrystals with desired shapes and related properties. We hope this review will inspire new ideas and concepts in the general area of nanomaterial synthesis, expand our ability to engineer the properties of metals for various applications, and contribute to the realization of sustainable use for some of the scarcest materials.
Localized surface plasmon resonances (LSPR), collective electron oscillations in nanoparticles, are being heavily scrutinized for applications in chemical and biological sensing, as well as in prototype nanophotonic devices. This phenomenon exhibits an acute dependence on the particle’s size, shape, composition, and environment. The detailed characterization of the structure-function relationship of nanoparticles is obscured by ensemble averaging. Consequently, single-particle data must be obtained to extract useful information from polydisperse reaction mixtures. Recently, a correlated high resolution transmission electron microscopy (HRTEM) LSPR technique has been developed and applied to silver nanocubes. We report here a second generation of experiments using this correlation technique, in which statistical analysis is performed on a large number of single particles. The LSPR dependence on size, shape, material, and environment was probed using silver right bipyramids, silver cubes, and gold cubes. It was found that the slope of the dependence of LSPR peak on size for silver bipyramids increases as the edges become sharper. Also, a plasmon shift of 96 nm was observed between similar silver and gold cubes, while a shift of 26 nm was observed, for gold cubes, between substrates of refractive index (RI) of 1.5 and 2.05.
The interaction of light with free electrons in a gold or silver nanostructure can give rise to collective excitations commonly known as surface plasmons. Plasmons provide a powerful means of confining light to metal/dielectric interfaces, which in turn can generate intense local electromagnetic fields and significantly amplify the signal derived from analytical techniques that rely on light, such as Raman scattering. With plasmons, photonic signals can be manipulated on the nanoscale, enabling integration with electronics (which is now moving into the nano regime). However, to benefit from their interesting plasmonic properties, metal structures of controlled shape (and size) must be fabricated on the nanoscale. This issue of MRS Bulletin examines how gold and silver nanostructures can be prepared with controllable shapes to tailor their surface plasmon resonances and highlights some of the unique applications that result, including enhancement of electromagnetic fields, optical imaging, light transmission, colorimetric sensing, and nanoscale waveguiding.
This article provides a brief account of solution-phase methods that generate silver and gold nanostructures with well-controlled shapes. It is organized into five sections: The first section discusses the nucleation and formation of seeds from which nanostructures grow. The next two sections explain how seeds with fairly isotropic shapes can grow anisotropically into distinct morphologies. Polyol synthesis is selected as an example to illustrate this concept. Specifically, we discuss the growth of silver nanocubes (with and without truncated corners), nanowires, and triangular nanoplates. In the fourth section, we show that silver nanostructures can be transformed into hollow gold nanostructures through a galvanic replacement reaction. Examples include nanoboxes, nanocages, nanotubes (both single- and multi-walled), and nanorattles. The fifth section briefly outlines a potential medical application for gold nanocages.We conclude with some perspectives on areas for future work.
We have demonstrated a variety of solution-phase approaches for the synthesis of 1- dimensional nanostructures from chalcogens such as Se and Te. These nanostructures include uniform, single crystalline nanowires and nanorods (lateral dimensions from 10 to 1000 nm, and lengths ranging from 2 to >100 νm). These nanostructures grew via a solid-solution-solid transformation mechanism, in which Se and Te atoms were transported from the less stable source (amorphous colloids) into the more stable product (trigonal phase nanocrystallites). The nanocrystallites (or seeds) were formed either through temperature driven homogeneous nucleation or by sonochemical cavitation. As directed by the highly anisotropic crystal structure, the growth could be confined to one particular direction. These nanowires could be prepared both as dispersions in various solvents or as networked arrays on solid supports.
A general approach involved template-engaged, galvanic replacement reactions has been developed to prepare metallic nanostructures with hollow interiors by reacting solutions of appropriate salts with metallic solid nanoparticles. The reaction between aqueous chloroauric acid and silver nanoparticles was used as a typical example to demonstrate the synthesis of gold nanoshells. The morphology, void space, and wall thickness of these hollow structures were all determined by the silver templates, which were completely converted into soluble species during the replacement reaction. The extinction peaks of these gold nanoshells were considerably redshifted as compared to solid gold colloids having approximately the same dimensions. In addition, the surface plasmon resonance of gold nanoshells exhibited a much more sensitive response toward environmental changes even when compared with solid colloids with a mean size much smaller than that of gold nanoshells.
Monodispersed colloidal spheres with dimensions in the range of 100 nm to 10 μm can be used as building blocks to fabricate highly ordered 3D micro- and nanostructures. For example, they can be self-assembled into closely packed lattices, which can be subsequently used as templates to generate 3D porous structures. Here we present the recent progress in our group regarding this approach.
A procedure was developed for large-scale fabrication of nanometer-sized structures of single crystalline silicon with well-defined dimensions and shapes. Near-field optical lithography was used to define the nanostructures in a thin film of positive-tone photoresist with an elastomeric phase mask. The nanostructures were then transferred into the underlying silicon-on-insulator (SOI) substrate through a reactive ion etching (RIE) process. With this method, we can routinely generate silicon nanostructures ∼130 nm in lateral dimension. They can be supported on the surface of a solid substrate as a patterned array, or released into a freestanding form. The lateral dimension of these silicon structures could be further reduced to as small as ∼40 nm using stress-limited oxidation at elevated temperatures. The flexibility of this approach was demonstrated by fabricating nanoscale wires, rods, rings, and interconnected triangles of silicon. Using a two-step exposure method, the silicon nanowires can be precisely “cut” into silicon nanorods with specific lengths.
Micromolding in capillaries has been used to generate patterned microstructures of ZrO2 or SnO2 from its polymeric precursor. After patterning, the amorphous precursor was converted into the desired polycrystalline ceramic material by calcination in air at 460 °C. The final phase for each ceramic material was determined by powder x-ray diffraction. The shrinkage of the precursor material during pyrolysis was investigated by scanning electron microscopy and atomic force microscopy. These ceramic microstructures could be either supported on solid substrates or released as freestanding fibers and membranes. Their lateral dimensions could be as small as approximately 500 nm.
This presentation describes a simple and practical method for self-assembling meso- and nanoparticles into three-dimensionally ordered lattices (opals) over large areas, and the use of these lattices as templates in fabricating highly ordered porous structures such as inverse opals. This method has been applied to a variety of colloidal particles, including silica colloids and polymer beads with diameters in the range of˜50 nm to ˜50 μm. Templating against the 3D opaline lattices provides an effective route to inorganic-organic composite materials and inverse opals having 3D periodic structures.
Two methods are presented which have been successfully used to fabricate highly ordered 2D and 3D arrays of nano-scale particles. The first method uses a combination of microcontact printing (μCP) and surface-templated reactions to form 2D patterned arrays of nanoparticles on silicon substrates. The second method uses confined self-assembly to crystallize colloidal particles into 3D cubic-close-packed (ccp) arrays (or opaline structures).
This paper describes a procedure based on the Tollens' process for preparing crystalline nanoparticles of silver with well-controlled, uniform sizes. The starting reagents are similar to those commonly used for electroless deposition of silver and are commercially available from the Peacock Laboratories (Philadelphia, PA). Only under appropriate conditions, mixing of these reagents was able to generate stable dispersions of silver colloids, rather than thin films of silver coated on surfaces of objects immersed in the solution (including the inner surface of the container). We have demonstrated the capability and feasibility of this method by forming stable dispersions of highly monodispersed, single crystalline colloids of silver with dimensions in the range of 20-50 nm.
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