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.
Wet-chemical
fabrication of a crystalline Ag-TCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane)
thin film on non-Ag substrate is challenging whereby the chemistry
was powered by photon energy and/or electrical energy. We report for
the first time, direct chemical growth of a Ag-TCNQ thin film on a
functionalized Au substrate by employing the layer-by-layer (LbL)
approach at ambient reaction conditions. Various Ag(I) salt precursors
previously realized to be unsuitable for the fabrication of Ag-TCNQ
thin films on non-Ag substrates ultimately gave rise to dense and
uniform thin films of Ag-TCNQ. The crucial knob regulating the direct
formation of the thin films of Ag-TCNQ was identified to be the pH
of the respective Ag(I) solutions.
Among
various factors playing pivotal roles in the typical seed-mediated
growth of Au nanocrystals (NCs), the role of Ag (AgNO3)
has remained debatable over time and seminal research efforts have
helped us in reaching a consensus, albeit from the standpoint of [Ag+] concentration. This study aims to provide an understanding
of the role of Ag+ from the perspective of time. Here,
we show that different Au NCs with tunable aspect ratios (ARs) can
be generated in one system in high yield simply by varying the time
of addition of Ag+ in the growth solution. The generality
of the method has been demonstrated in tuning the ARs of anisotropic
Au NCs like concave cuboid (CCB, AR = 2) and elongated tetrahexahedra
(AR = 2.5), where the delayed addition of Ag+ leads to
the formation of their isotropic counterpart concave cube (CC, AR
= 1) and tetrahexahedra (AR = 1), respectively. This work, apart from
establishing timed addition of Ag+ as a crucial parameter
in controlling the AR, may also help in the realization of a universal
growth mechanism of Au NCs. The Au NCs with varying ARs (CCB, AR =
2 and CC, AR = 1) have been further explored as potential substrates
for surface-enhanced Raman scattering (SERS) due to the presence of
their high-index facets and sharp tips.
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