Sara E. Skrabalak

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.

Gold Nanocages: Synthesis, Properties, and Applications

Noble-metal nanocages comprise a novel class of nanostructures possessing hollow interiors and porous walls. They are prepared using a remarkably simple galvanic replacement reaction between solutions containing metal precursor salts and Ag nanostructures prepared through 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 HAuCl(4) as the metal precursor, the resultant Au is deposited epitaxially on the surface of the Ag nanocubes, adopting their underlying cubic form. 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 is versatile, with a wide range of morphologies (e.g., nanorings, prism-shaped nanoboxes, nanotubes, and multiple-walled nanoshells or nanotubes) available upon changing the shape of the initial Ag template. In addition to Au-based structures, switching the metal salt precursors to Na(2)PtCl(4) and Na(2)PdCl(4) allows for the preparation of Pt- and Pd-containing hollow nanostructures, respectively. We have found that changing the amount of metal precursor added to the suspension of Ag nanocubes is a simple means of tuning both the composition and the localized surface plasmon resonance (LSPR) of the metal nanocages. Using this approach, we are developing structures for biomedical and catalytic applications. Because discrete dipole approximations predicted that the Au nanocages would have large absorption cross-sections and because 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 materials 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 and photoacoustic tomography, with improved performance observed in each case. Because the Au nanocages have large absorption cross-sections, they are also effective photothermal transducers; thus, they might provide a therapeutic effect through selective hyperthermia-induced killing of targeted cancer cells. Our studies in vitro have illustrated the feasibility of applying this technique as a less-invasive form of cancer treatment.

Facile synthesis of Ag nanocubes and Au nanocages

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 Na2S. 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 Na2S 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.

Chemical Synthesis of Novel Plasmonic Nanoparticles

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.

Rapid synthesis of silver nanowires through a CuCl- or CuCl2-mediated polyol process

The presence of various ions has been shown to have a strong impact on the shape and size of silver nanostructures produced via the polyol reduction of AgNO3. Here we report a simple and rapid (reaction time ∼1 h) route to Ag nanowires, in which ethylene glycol serves as the solvent and a precursor to the reducing agent. The reaction could be performed in disposable glass vials, with all the reagents being delivered using pipettes. In addition to the use of poly(vinyl pyrrolidone) as a stabilizer, copper (I) or copper (II) chloride had to be added to the reaction to reduce the amount of free Ag+ during the formation of initial seeds and scavenge adsorbed oxygen from the surface of the seeds once formed. In doing so, Ag nanowires were grown preferentially.

On the polyol synthesis of silver nanostructures: glycolaldehyde as a reducing agent.

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.

Octopods versus Concave Nanocrystals: Control of Morphology by Manipulating the Kinetics of Seeded Growth via Co-Reduction

Au/Pd octopods and concave core@shell Au@Pd nanocrystals have been prepared by coupling for the first time a seed-mediated synthetic method with co-reduction. The integration of these two methods is central to the formation of these binary Au/Pd nanocrystals wherein the kinetics of seeded growth are manipulated via the co-reduction technique to control the final morphology of the nanocrystals. Significantly, the synthesis of these structures under similar reaction conditions illustrates that they are structurally related kinetic products. Detailed characterization by STEM-EDX analysis highlights the unique structural features of these nanocrystals and indicates that Pd localizes on the higher-energy features of the nanocrystals. Optical and electrocatalytic characterization also demonstrates their promise as a new class of multifunctional nanostructures.

Gold nanocages for cancer detection and treatment

Gold nanocages represent a novel class of biocompatible vectors with potential applications in drug delivery, tumor/tissue imaging and photothermal therapy. They are prepared through the galvanic-replacement reaction between Ag nanostructures and HAuCl(4). By controlling the amount of HAuCl(4) added, we can tune the surface-plasmon resonance peaks of the Au nanocages into the near-infrared, where the attenuation of light by blood and soft tissue is relatively low. Here, we highlight recent advances in the synthesis and utilization of Au nanocages for cancer detection and treatment. We have tailored the optical properties of Au nanocages for use as contrast agents in optical coherence tomography and as transducers for the selective photothermal ablation of cancer cells. Our results show improved optical coherence tomography image contrast when Au nanocages are added to tissue phantoms as well as the selective photothermal destruction of breast cancer cells in vitro when immunotargeted Au nanocages are used.

Excitation enhancement of CdSe quantum dots by single metal nanoparticles

We study plasmon-enhanced fluorescence from CdSe∕CdS∕CdZnS∕ZnS core/shell quantum dots near a variety of Ag and Au nanoparticles. The photoluminescence excitation (PLE) spectrum of quantum dots closely follows the localized surface plasmon resonance (LSPR) scattering spectrum of the nanoparticles. We measure excitation enhancement factors of ∼3 to 10 for different shapes of single metal nanoparticles.

A facile, water-based synthesis of highly branched nanostructures of silver.

We report a facile and environmentally friendly method of preparing highly branched silver nanostructures. By reducing AgNO 3 with l-ascorbic acid in an aqueous solution, silver particles having a coral-like morphology were formed in a few minutes. A mechanistic study of the growth process revealed that the silver branches grew from a bulbous seed formed through aggregation, and that by changing the concentrations of the reagents, the degree of particle branching could be altered. With their potentially high surface areas, these branched structures could find use as catalysts or as substrates for surface-enhanced Raman scattering applications.