Ultrathin gold nanoframes through surfactant-free templating of faceted pentagonal silver nanoparticles.

Ultrathin gold nanoframes (up to 1.6 nm) were prepared via templating upon well-defined faceted silver morphologies. Starting with silver decahedra, small quantities of gold (1-10 mol% relative to the amount of silver) were selectively deposited on the nanoparticle edges under optimized reducing conditions. Silver dissolution in hydrogen peroxide yielded well-defined gold frames that retained their structural integrity in the ultrathin nanowire regime below 2 nm. The frame formation protocol was also successfully applied to other silver nanoparticle shapes featuring pentagonal twinning and (111) facets (e.g., pentagonal faceted rods and icosahedra). The demonstrated approach can be applied in the controlled preparation of ultrathin metal nanowires complementary to lithography and in the production of ultrafine noble-metal nanostructures for catalytic applications.

High-resolution friction force microscopy under electrochemical control.

We report the design and development of a friction force microscope for high-resolution studies in electrochemical environments. The design choices are motivated by the experimental requirements of atomic-scale friction measurements in liquids. The noise of the system is analyzed based on a methodology for the quantification of all the noise sources. The quantitative contribution of each noise source is analyzed in a series of lateral force measurements. Normal force detection is demonstrated in a study of the solvation potential in a confined liquid, octamethylcyclotetrasiloxane. The limitations of the timing resolution of the instrument are discussed in the context of an atomic stick-slip measurement. The instrument is capable of studying the atomic friction contrast between a bare Au(111) surface and a copper monolayer deposited at underpotential conditions in perchloric acid.

Chiral thiol-stabilized silver nanoclusters with well-resolved optical transitions synthesized by a facile etching procedure in aqueous solutions.

A novel approach of cyclic reduction in oxidative conditions has been developed to prepare a single dominant species of chiral thiol-stabilized silver nanoclusters (AgNCs). Such AgNCs, which are stable in solution for up to a few days, have been obtained for the first time. The generality of the established procedure is proven by using several enantiomeric water-soluble thiols, including glutathione, as protective ligands. The prepared AgNCs featured prominent optical properties including a single pattern of UV-vis absorption with well-resolved peaks. The chirality of the clusters has been investigated by circular dichroism (CD) spectroscopy. CD spectra displayed strong characteristic signatures in the visible range. Tentative identification of the cluster composition is discussed.

Synthesis of size-controlled faceted pentagonal silver nanorods with tunable plasmonic properties and self-assembly of these nanorods.

Monodisperse size-controlled faceted pentagonal silver nanorods were synthesized by thermal regrowth of decahedral silver nanoparticle (AgNPs) in aqueous solution at 95 degrees C, using citrate as a reducing agent. The width of the silver nanorods was determined by the size of the starting decahedral particle, while the length was varied from 50 nm to 2 mum by the amount of new silver added to the growth solution. Controlled regrowth allowed us to produce monodisperse AgNPs with a shape of elongated pentagonal dipyramid (regular Johnson solid, J(16)). Faceted pentagonal particles exhibited remarkable optical properties with sharp plasmon resonances precisely tunable across visible and NIR. Due to the narrow size distribution, faceted pentagonal silver nanorods readily self-assembled into the 3-D arrays similar to smectic mesophases. Hexagonal arrangement in the array completely overrode five-fold symmetry of the nanorods. Overall, our findings highlight the importance of pentagonal symmetry in metal nanoparticles and offer a facile method of the preparation of monodisperse AgNPs with controlled dimensions and plasmonic properties that are promising for optical applications and functional self-assembly.