Gold Nanoearbuds: Seed-Mediated Synthesis and the Emergence of Three Plasmonic Peaks.

We demonstrate the first successful synthesis of reasonably monodisperse and single-crystalline gold nanoearbuds (Au NEBs) using a binary surfactant mixture of cetyltrimethylammonium chloride (CTAC) and benzyldimethylhexadecylammonium chloride (BDAC) in seed-mediated growth method. We have focused on the key chemical parameters behind the formation and growth of Au NEBs to result in tunable dimensions (length, 37-77 nm; width, 4-6 nm; aspect ratio, 7-19), as a consequence of which the longitudinal surface plasmon resonance (LSPR) peak could be tuned beyond 1200 nm. The achievement of LSPR beyond 1200 nm while maintaining the dimension well below 100 nm is a challenging accomplishment in the realm of one-dimensional (1D) Au nanostructures. This earbud-like morphology additionally exhibits three plasmonic peaks, rather uncommon for 1D nanostructures, which were analyzed theoretically based on the finite element method. The new resonance peak of the Au NEB was assigned as an additional longitudinal mode intensified by the bulbous ends as well as the high aspect ratio, thereby providing conclusive evidence that it is indeed a new morphology.

Facile Synthesis of Concave Cuboid Au NCs with Precisely Tunable Dimensions and Mechanistic Insight.

Concave cuboid (CCB) nanostructure is a member of the high-index facet (HIF) nanocrystals (NCs) family, geometrically derived from regular cuboid-excavation of each face. CCB NCs hold some additional characteristics such as surface cavity and sharp edges and corners as compared to its convex counterpart that makes it relatively more active in applications like electrochemical catalysis, surface enhanced Raman spectroscopy (SERS), and plasmonics. To date, there are only few reports available on the synthesis of CCB Au NCs where Br- containing surfactants have been used as a shape directing and stabilizing agent. However, none of them led to decent yield and size tunability. Herein, we report a robust seed mediated growth strategy where cetyltrimethylammonium chloride (CTAC) and tannic acid (TA) have been used as shape-directing/stabilizing and mild reducing agents, respectively. Our method not only allows the high yield fabrication of CCB Au NCs with uniform shape and size but also precise control over dimensions and degree of surface concavity. Moreover, the investigation of growth mechanism revealed that the evolution of CCB Au NCs from cylindrical nanorods (NRs) take place via arrow-headed nanorods and truncated CCB nanostructures. Furthermore, it has been observed that the presence of excess of Cl- is indeed playing a decisive role despite the headgroup of counter cationic part of surfactant. We anticipate that our findings may pave the path to design new synthetic strategies and understand the evolution of new nanostructures.

High-index faceted Au nanocrystals with highly controllable optical properties and electro-catalytic activity.

We introduce a new and naturally abundant mild reducing agent, tannic acid, to improve the seed-mediated growth method for the synthesis of elongated tetrahexahedral Au nanocrystals enclosed with high-index (730) planes, at room-temperature. The control of the dimensions, plasmonics and electro-catalysis of such high-index faceted nanocrystals is remarkable.