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. The aim of this article 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. Toward the end of this article, we highlight a number of applications that have been enabled and/or enhanced by the shapecontrolled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Conspectus Noble-metal nanocages represent a novel class of nanostructures with hollow interiors and porous walls. They are prepared using the remarkably simple galvanic replacement reaction between solutions containing metal precursor salts and Ag nanostructures prepared by polyol reduction. The electrochemical potential difference between the two species drives the reaction, with the reduced metal depositing on the surface of the Ag nanostructure. In our most studied example involving HAuCl4 as the metal precursor, the resultant Au epitaxially deposits on the surface of the Ag nanocubes, adopting their cubic structure. Concurrent with this deposition, the interior Ag is oxidized and removed, together with alloying and dealloying, to produce hollow and eventually porous structures that we commonly refer to as Au nanocages. This approach has proven versatile, with a wide range of morphologies – including nanorings, prism-shaped nanoboxes, nanotubes, and multiple-walled nanoshells or nanotubes – being produced by changing the shape of the initial Ag template. Besides Au-based structures, Pt- and Pd-containing hollow nanostructures have been prepared by switching the metal salt precursors to Na2PtCl4 or Na2PdCl4, respectively. Additionally, we have found it easy to tune both the composition and localized surface plasmon resonance (LSPR) of the metal nanocages by simply changing the amount of metal precursor added to the suspension of Ag nanocubes. In this way, we are developing these structures for biomedical and catalytic applications. As the Au nanocages are predicted by discrete dipole approximations (DDA) to have large absorption cross-sections and their LSPR can be tuned into the near-infrared where the attenuation of light by blood and soft tissue is greatly reduced, they are attractive for biomedical applications in which the selective absorption of light at great depths is desirable. For example, we have explored their use as contrast enhancement agents for both optical coherence tomography (OCT) and photoacoustic tomography (PAT), with improvements being observed in each case. As the Au nanocages have large absorption cross-sections, they are also effective photothermal transducers, which when targeted to cancer cells could provide a therapeutic effect by selectively killing them by hyperthermia. Our in vitro work illustrates the feasibility of this technique as a less invasive form of cancer treatment.

Colloidal synthesis offers a route to nanoparticles (NPs) with controlled composition and structural features. This Perspective describes the use of polyvinylpyrrolidone (PVP) to obtain such nanostructures. PVP can serve as a surface stabilizer, growth modifier, nanoparticle dispersant, and reducing agent. As shown with examples, its role depends on the synthetic conditions. This dependence arises from the amphiphilic nature of PVP along with the molecular weight of the selected PVP. These characteristics can affect nanoparticle growth and morphology by providing solubility in diverse solvents, selective surface stabilization, and even access to kinetically controlled growth conditions. This Perspective includes discussions of the properties of PVP-capped NPs for surface enhanced Raman spectroscopy (SERS), assembly, catalysis, and more. The contribution of PVP to these properties as well as its removal is considered. Ultimately, the NPs accessed through the use of PVP in colloidal syntheses are opening new applications, and the concluding guidelines provided herein should enable new nanostructures to be accessed facilely.

This protocol describes a method for the synthesis of Ag nanocubes and their subsequent conversion into Au nanocages via the galvanic replacement reaction. The Ag nanocubes are prepared by a rapid (reaction time < 15 min), sulfide-mediated polyol method in which Ag(I) is reduced to Ag(0) by ethylene glycol in the presence of poly(vinyl pyrrolidone) (PVP) and a trace amount of Na(2)S. When the concentration of Ag atoms reaches supersaturation, they agglomerate to form seeds that then grow into Ag nanostructures. The presence of both PVP and Na(2)S facilitate the formation of nanocubes. With this method, Ag nanocubes can be prepared and isolated for use within approximately 3 h. The Ag nanocubes can then serve as sacrificial templates for the preparation of Au nanocages, with a method for their preparation also described herein. The procedure for Au nanocage preparation and isolation requires approximately 5 h.

Under the irradiation of light, the free electrons in a plasmonic nanoparticle are driven by the alternating electric field to collectively oscillate at a resonant frequency in a phenomenon known as surface plasmon resonance. Both calculations and measurements have shown that the frequency and amplitude of the resonance are sensitive to particle shape, which determines how the free electrons are polarized and distributed on the surface. As a result, controlling the shape of a plasmonic nanoparticle represents the most powerful means of tailoring and fine-tuning its optical resonance properties. In a solution-phase synthesis, the shape displayed by a nanoparticle is determined by the crystalline structure of the initial seed produced and the interaction of different seed facets with capping agents. Using polyol synthesis as a typical example, we illustrate how oxidative etching and kinetic control can be employed to manipulate the shapes and optical responses of plasmonic nanoparticles made of either Ag or Pd. We conclude by highlighting a few fundamental studies and applications enabled by plasmonic nanoparticles having well-defined and controllable shapes.

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Nanostructured materials provide a promising platform for early cancer detection and treatment.Here we highlight recent advances in the synthesis and use of Au nanocages for such biomedical applications. Gold nanocages represent a novel class of nanostructures, which can be prepared via a remarkably simple route based on the galvanic replacement reaction between Ag nanocubes and HAuCl 4 . The Au nanocages have a tunable surface plasmon resonance peak that extends into the near-infrared, where the optical attenuation caused by blood and soft tissue is essentially negligible. They are also biocompatible and present a well-established surface for easy functionalization. We have tailored the scattering and absorption cross-sections of Au nanocages for use in optical coherence tomography and photothermal treatment, respectively. Our preliminary studies show greatly improved spectroscopic image contrast for tissue phantoms containing Au nanocages. Our most recent results also demonstrate the photothermal destruction of breast cancer cells in vitro by using immuno-targeted Au nanocages as an effective photo-thermal transducer. These experiments suggest that Au nanocages may be a new class of nanometer-sized agents for cancer diagnosis and therapy.

The polyol synthesis is a popular method of preparing metal nanostructures, yet the mechanism by which metal ions are reduced is poorly understood. Using a spectrophotometric method, we show, for the first time, that heating ethylene glycol (EG) in air results in its oxidation to glycolaldehyde (GA), a reductant capable of reducing most noble metal ions. The dependence of reducing power on temperature for EG can be explained by this temperature-dependent oxidation, and the factors influencing GA production can have a profound impact on the nucleation and growth kinetics. These new findings provide critical insight into how the polyol synthesis can be used to generate metal nanostructures with well-controlled shapes. For example, with the primary reductant identified, it becomes possible to evaluate and understand its explicit role in generating nanostructures of a specific shape to the exclusion of others.