Gabriella Metraux

Controlling anisotropic nanoparticle growth through plasmon excitation

Inorganic nanoparticles exhibit size-dependent properties that are of interest for applications ranging from biosensing and catalysis to optics and data storage. They are readily available in a wide variety of discrete compositions and sizes. Shape-selective synthesis strategies now also yield shapes other than nanospheres, such as anisotropic metal nanostructures with interesting optical properties. Here we demonstrate that the previously described photoinduced method for converting silver nanospheres into triangular silver nanocrystals—so-called nanoprisms—can be extended to synthesize relatively monodisperse nanoprisms with desired edge lengths in the 30–120 nm range. The particle growth process is controlled using dual-beam illumination of the nanoparticles, and appears to be driven by surface plasmon excitations. We find that, depending on the illumination wavelengths chosen, the plasmon excitations lead either to fusion of nanoprisms in an edge-selective manner or to the growth of the nanoprisms until they reach their light-controlled final size.

Colloidal Gold and Silver Triangular Nanoprisms

It is now well-known that the size, shape, and composition of nanomaterials can dramatically affect their physical and chemical properties, and that technologies based on nanoscale materials have the potential to revolutionize fields ranging from catalysis to medicine. Among these materials, anisotropic particles are particularly interesting because the decreased symmetry of such particles often leads to new and unusual chemical and physical behavior. Within this class of particles, triangular Au and Ag nanoprisms stand out due to their structure- and environment-dependent optical features, their anisotropic surface energetics, and the emergence of reliable synthetic methods for producing them in bulk quantities with control over their edge lengths and thickness. This Review will describe a variety of solution-based methods for synthesizing Au and Ag triangular prismatic structures, and will address and discuss proposed mechanisms for their formation.

Mechanistic Study of Photomediated Triangular Silver Nanoprism Growth

This article presents a mechanistic study of the photomediated growth of silver nanoprisms. The data show that the photochemical process is driven by silver redox cycles involving reduction of silver cations by citrate on the silver particle surface and oxidative dissolution of small silver particles by O2. Bis(p-sulfonatophenyl)phenylphosphine increases the solubility of the Ag(+) by complexing it and acts as a buffer to keep the concentration of Ag(+) at 20 microM. The silver particles serve as photocatalysts and, under plasmon excitation, facilitate Ag(+) reduction by citrate. Higher Ag(+) concentrations favor a competitive thermal process, which results in increased prism thickness.