Article

Cite This: Langmuir 2018, 34, 366−375 pubs.acs.org/Langmuir

New Aspects of the Gold Nanorod Formation Mechanism via Seed-

Mediated Methods Revealed by Molecular Dynamics Simulations
Jose ́ Adriano da Silva and Mario R. Meneghetti*
Grupo de Catálise e Reatividade QuímicaGCaR, Instituto de Química e Biotecnologia da Universidade Federal de Alagoas, Av.
Lourival de Melo Mota, s/n, Cidade Universitária, CEP, 57072-970 Maceió-AL, Brazil
*
S Supporting Information

ABSTRACT: New aspects of the formation and growth

mechanism of gold nanorods (AuNRs) during seed-mediated
colloidal synthesis are revealed from the results of molecular
dynamics simulation. The model systems consist of
cetyltrimethylammonium bromide (CTAB) units adsorbed
on low-index [Au(110), Au(100), and Au(111)] and high-
index [Au(250)] gold surfaces. The CTAB units are adsorbed
as adjacent cylindrical micelles when the relative number of
adsorbed bromide ions is small. At later AuNR growth stages,
the number of bromide ions increases as the [AuBr2]− species
pass through the channels between the adsorbed micelles on
the gold surface. Thus, the mature AuNRs have a high concentration of bromide ions at their surface, which appears to change
the organization of the CTAB units on the particle surface from adsorbed micelles to a compact CTAB bilayer.

■ INTRODUCTION
Anisotropic metal nanoparticles are characterized by several
unique properties that originate from nanoparticle size effects
because of their high surface areas and electron confinement.
In particular, gold nanorods (AuNRs) exhibit remarkable
properties and are promising for numerous applications.1
The most common and successful strategy for synthesizing
AuNRs is thought to be a seed-mediated colloidal method,
which was originally used by Murphy et al. in 2001 to produce
pentatwinned AuNRs.2 This method was later modified by El-
Sayed and Nikoobakht in 20033 to produce single-crystal
AuNRs in higher yields (see Table 1).4 The crystallographic
facet indices of the AuNRs obtained by both methodologies
are depicted in Figure 1A.5,6
Briefly, in the seed-mediated synthesis of AuNRs, the growth
of these anisotropic nanoparticles is mediated by the addition
of metallic gold atoms at the surface of previously prepared
small gold nanoparticles (seeds), by a controlled reduction of
Au(I) species at the surface of the seeds that grow in an
anisotropic way due to the presence of cetyltrimethylammo-
nium bromide (CTAB) as a growth-driving agent.2,3,7 Indeed,
many studies of these standard synthesis methods and
adaptations thereof have appeared in the literature. In
particular, the effects of the seed size,8 cosurfactants,9
additives,10 temperature,11,12 surfactant chain length,13 and
headgroup structure14 have been investigated.
Because the properties of AuNRs depend on their shape, the
particle symmetry breaking and anisotropic growth mechanism
must be understood to optimize the synthesis conditions and
thus improve the shape and size uniformity of the particles.
Accordingly, several research groups are focused on under-
standing the synthesis mechanism. Despite advances in
elucidating the formation mechanism of AuNRs, especially
the development of mechanistic models that are consistent
with the experimental data, some gaps in understanding still
remain.4
In 2005, Murphy and co-workers15 proposed the first model
explaining the origin of the anisotropic growth mechanism of
colloidal AuNRs, that is, the zipping-like growth mechanism. It
states that the CTAB surfactants preferentially adsorb on the
lateral facets of AuNRs. An AuNR begins to develop
anisotropy when a CTAB bilayer forms on the lateral sides
of the growing particle. The bilayer hinders the access of the
Au(I) species to the gold surface, where they are reduced,
whereas the Au(I) species can still diffuse into the tips of the
AuNR (Figure 1B).
Jana16 proposed another model for the anisotropic growth of
AuNRs, namely, the soft template model. In this model,
elongated CTAB micelles in the growth solution generate a
template into which seeds with diameters of 1−3 nm can
penetrate. Then, the shape of the micelle, that is, the soft
template, induces the anisotropy (Figure 1C). According to
this model, the temperature and CTAB concentration during
the synthesis must be within a certain range to generate
elongated micelles that induce the formation of AuNRs.
Additionally, additives that can promote micellar transitions to
more elongated CTAB micelles, for example, salicylate
aromatic additives,10 can be used to fabricate AuNRs with a
Received: October 26, 2017
Revised: December 13, 2017
Published: December 15, 2017

© 2017 American Chemical Society 366 DOI: 10.1021/acs.langmuir.7b03703

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Table 1. General Details for Preparing AuNRs via Seed-Mediated Synthesis

aspect ratio selectivitya
synthesis method seed solution seed shape growth solution crystallinity of the AuNRs (AR) (%)
Murphy and co- NaBH4, HAuCl4, and decahedral ascorbic acid, HAuCl4, and pentatwinned with pentagonal 6−20 ca. 15
workers2 citrate CTAB cross section
El-Sayed and NaBH4, HAuCl4, and cuboctahedral ascorbic acid, HAuCl4, CTAB, single crystal with octagonal 1.5−5.0 ca. 90
Nikoobakht3 CTAB and AgNO3 cross section
a
Relative to the number of nanoparticles formed.

higher AR. Thus, on the basis of this model, seeds with
diameters larger than 3.5 nm cannot generate AuNRs,
explaining the observation that AuNRs cannot be fabricated
from large seeds because they are larger than the micelle
template.
It is essential to determine how CTAB is adsorbed and
structurally organized on the surfaces of growing and mature
AuNRs to understand the nanoparticle growth mechanism.
Analogous CTAB surfactants with a shorter alkyl chain
(CnTAB, 10 ≤ n < 16) were used to drive growth in the
pentatwinned AuNR synthesis and led to AuNRs with smaller
ARs. Using the zipping-like mechanism, these results were
explained by the different capacities of these surfactants to
generate a stable bilayer structure on the lateral surfaces of the
AuNRs; the longer chains provided greater stability and thus
generated AuNRs with higher ARs.13
Hafner and co-workers used surface-enhanced Raman
spectroscopy to confirm the existence of Au−Br− interactions
and show that the arrangement of the adsorbed CTAB on the
gold surface depends on its concentration.17 They verified that
the adsorbed CTAB forms a “collapsed bilayer” at relatively
low CTAB concentrations by detecting the interactions
between the alkane chains of the CTA+ moiety and the
AuNR surface. In contrast, an organized bilayer pattern was
proposed to exist at higher CTAB concentrations. It should be
noted that separating and redispersing the AuNRs generated in
this system in a dilute aqueous solution of CTAB resulted in
the formation of a “collapsed bilayer” of CTAB on the
particles.
Gómez-Graña and co-workers used transmission electron
microscopy, small-angle neutron scattering (SANS), and small-
angle X-ray scattering to measure the thickness of the CTAB
structure adsorbed on the single-crystal AuNR. The measured
value of 3.2 ± 0.2 nm is significantly smaller than twice the
extended surfactant chain length (4.34 nm), suggesting
significant tilting or interdigitation of the hydrocarbon chains
of the surfactants.18
In both seed-mediated synthesis protocols,2,3 the concen-
tration of CTAB in the growth solution is generally 0.1 M;
however, the CTAB second critical micelle concentration in an
aqueous solution is 0.27 M,19 meaning cylindrical micelles are
not present in the growth solution. Walsh and co-workers20
showed that when a standard synthesis protocol for single-
crystal AuNRs is employed, that is, when silver is present, the
symmetry breaking only occurs in seeds that are 4−6 nm in
diameter. In a 0.1 M CTAB solution, the micelles are

Figure 1. (A) Crystallographic facets of different types of AuNRs: (1) intermediate growth stage of a single-crystal AuNR, (2) mature single-crystal
AuNR, and (3) mature pentatwinned AuNR. (B) Illustration of the AuNR zipping-like growth mechanism. (C) Illustration of the role of the soft
template during the growth process.

367 DOI: 10.1021/acs.langmuir.7b03703

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ellipsoidal, with minor and major axes of 2.6 and 4.4 nm,
respectively.21 Then, the micelles in the solution under
standard synthesis conditions are smaller than or at least
approximately the same size as the seed particles and cannot
serve as templates during growth. Thus, evidence supporting
the soft template mechanism is lacking, and it is not currently
accepted as an explanation of the anisotropic growth.
Vaia and co-workers mapped the crystallographic facets
formed during single-crystal AuNR growth and divided the
growth process of the particles into five stages based on the
results.22 Thus, using the zipping-like growth mechanism as the
main model, it is assumed that a bilayer exists on the lateral
facets of the growing AuNR in all the stages. It should be
noted, however, that this assumption is supported by
experimental studies of mature AuNRs. In fact, the existence
of a bilayer coating during all the growth stages has not been
verified experimentally. The existence of a compact bilayer
during the entire growth process conflicts with the
experimental results because growth occurs at the side facets,
although to a lesser degree than at the tips, in the early
stages.22 However, in the later stages of the growth process, the
formation of a compact bilayer on the lateral facets appears to
occur, making it difficult for the most abundant source of gold,
that is, [AuBr2]−, to pass through the hydrophobic core of the
CTAB bilayer.23
Sulpizi and co-workers24−26 used molecular dynamics (MD)
simulations to identify the CTAB adsorption modes on low-
index and high-index gold surfaces. They observed adjacent
cylindrical micelles on all the surfaces, as well as channels
(called intermicellar channels), that allow the molecular gold
source to flow to the surface of the AuNRs. According to these
researchers, the width of these channels depends on the facet
on which the micelles are adsorbed and decreases in the
following order: Au(111) > Au(110) > Au(100) > Au(250).
Thus, the Meena−Sulpizi growth mechanism states that a
series of cylindrical CTAB micelles, not a CTAB bilayer,
adsorb on all facets of the gold surface, resulting in the
formation of channels filled with water molecules. Indeed, the
presence of these channels is consistent with the growth
process during the early stages of AuNR formation because
both the lateral facets and the tips of the AuNRs grow,
although at different rates. However, the adsorption of adjacent
cylindrical CTAB micelles observed in the simulations is
contradictory to the experimental results,17,27,28 which confirm
the existence of a bilayer structure. Nevertheless, it should be
noted that all the experimental data confirming the presence of
a compact bilayer of CTAB units were obtained using mature
AuNRs.
Furthermore, the number of bromide ions adsorbed on the
surfaces in the Meena and Sulpizi simulations (a Br/Au ratio of
ca. 0.10) is smaller than that measured experimentally for
AuNRs.24−26 Using X-ray photoelectron spectroscopy, Zhang
and co-workers29 found that the Br/Au ratio on AuNR surfaces
is ca. 0.17. This difference in the simulated and experimental
Br/Au ratios motivated this study to determine the influence of
this ratio on the formation of a bilayer of CTAB in MD
simulations.
Therefore, the adsorption of CTAB on gold surfaces is
reexamined using MD simulations.30 Previous theoretical
studies typically employed an initial configuration of the
CTAB species in which the CTA+ cations are perpendicular to
the gold surface and the bromide anions are on top of the
CTA+ bilayer, dispersed in the aqueous solution.24−26 During
368
Article
the simulations, the migration of bromides to the gold surfaces
is monitored. In this study, systems with a number of bromides
inserted at the gold/CTA+ interface were constructed. In
particular, the Br/Au ratio found by Meena and Sulpizi (0.1
Br/Au) and a slightly larger ratio than that measured
experimentally (0.2 Br/Au) were employed.
The systems were constructed with CTAB adsorbed on
different surfaces, namely, the low-index Au(110), Au(100),
and Au(111) surfaces and the high-index Au(250) surface,
with bromides at the gold/CTA+ interface in ratios of 0.1 Br/
Au (low concentration of bromides) and 0.2 Br/Au (high
concentration of bromides).
In this work, we demonstrate that the adsorption patterns
observed in the simulations are consistent with the
experimental measurements and the results are used to
propose the growth mechanisms of the pentatwinned and
single-crystal AuNRs.
It should be noted that the role of silver, which is present
during the production of single-crystal AuNRs, was not
investigated in this study (silver was not included in the
simulation models), which focuses on the gold surface/
bromide/surfactant/bromide/water interactions. This analysis
is reasonable because Funston and co-workers demonstrated
that the presence of silver nitrate in the medium during the
synthesis of single-crystal AuNRs only affects the symmetry-
breaking event.31
■ COMPUTATIONAL METHODOLOGY
System Setup. The topology and atomic parameters for
the CTA+ and Br− units32 used in the simulations were
validated in our previous work;30 they were shown to lead to
structures exhibiting CTAB/gold surface interactions and
CTAB micelles in aqueous solution and to predict the
counterion dissociation degree. The parameters for the gold
surface33 were used in previous simulations (Table 2).24−26,30
Table 2. Lennard-Jones Parameters Used for the Bromide
Ions and Gold Atoms
species C6 (kJ·mol−1·nm6) × 10−2 C12 (kJ·mol−1·nm6) × 10−5
−
Br 5.8243749 5.10031
Au 2.92057 0.964326
The initial configurations (input) for all the simulations
included: (i) a gold surface, which could be any of the different
facets, (ii) a specific number of CTAB units, with the bromide
ions distributed below or above of the CTA+ bilayer (Br-1 and
Br-2, respectively), and (iii) a suitable number of water
molecules (see Figure 2). More specifically, for the simulations
of the Au(250) surface, two different amounts of Br-1 (Br-1/
Au molar ratios of 0.2 and 0.1) were placed on the gold
surface. For the low-index Au(110), Au(100), and Au(111)
surfaces, a 0.1 Br-1/Au ratio was employed, and for the
Au(100) surface, a 0.2 Br/Au ratio was also used. The CTA+
packing density in the simulations was slightly higher than that
calculated from the cross-sectional area of the CTA +
headgroup (0.32 nm2).34 Each system was filled with SPC
water molecules35 and the number of the bromide ions (Br-2)
required to neutralize the charged polar groups of the bilayers.
The characteristics of the systems are summarized in Table 3.
Simulation Procedures. The energies of the initial
configurations were minimized by running 5000 steps of a
steepest descent procedure. The systems were simulated under
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■ RESULTS AND DISCUSSION

Figure 2. Initial configurations of the surfactant bilayer on the gold
surfaces. (A) 0.1 Br/Au and (B) 0.2 Br/Au. Gold atoms (yellow),
nitrogen atoms (blue), hydrophobic tail (gray), Br-1 (magenta), and
Br-2 (green). The water molecules were omitted for clarity.
isothermal−isobaric NPT conditions, and periodic boundary
conditions were applied to the rectangular boxes in all
directions. During the equilibration and production phases,
the leap-frog algorithm was used to integrate Newton’s
equations of motion with a time step of 0.002 ps. Each
simulation trajectory was 200 ns long. The center of mass
motion was removed every five steps. The Berendsen
thermostat was used to maintain the system temperature at
300 K by independently coupling the temperatures of the
solute and solvent using a time constant of 0.4 ps.36 The
pressure was maintained using the Parrinello−Rahman
barostat by weakly coupling the particle coordinates and box
dimensions to a pressure bath of 1.0 bar.37 Anisotropic
coordinate scaling was used with a relaxation time of 0.4 ps and
a compressibility of 4.5 × 10−5 bar−1, which is appropriate for
water. No bond constraints were applied during the
simulations. A generalized reaction field correction and a
cutoff of 1.4 nm were used for both the van der Waals and
long-range electrostatic interactions, and the permittivity
(dielectric constant) was 66.38 In all the simulations, the pair
lists for the short-range nonbonded and long-range electro-
static interactions were updated every five time steps. The
configurations of the trajectory were recorded every 1 ps.
The time-dependent distributions of nitrogen, bromide-1,
bromide-2, the last carbon of the hydrophobic tail, and the
water molecules were derived from the MD simulations and
analyzed. GROMACS 4.5.5 was used for all the MD
simulations and trajectory analyses.39 The VMD software
version 1.9.1 was used to visualize the trajectories and prepare
the figures.40
Simulation of CTAB Adsorption on the Au(250)
Surface with 0.1 Br/Au. In this simulation, the initial
configuration has a relatively low number of bromide ions (Br-
1) near the gold surface, compared to the total number of
bromide ions (Br-1 + Br-2). After the simulation begins,
adjacent cylindrical micelles of CTAB are formed on the gold
surface and these structures are observed until the end of the
simulation (see Figure 3A). Figure 3B shows the water
molecule arrangement near the gold surface. Clearly, the space
between the adsorbed CTAB micelles, that is, the intermicellar
channels, is filled with water molecules.
The densities of nitrogen, bromide-1, bromide-2, the last
carbon of the hydrophobic tail, and the water molecules were
measured along the axis perpendicular to the surface
(estimated for the last 50 ns of the simulation). These results
are presented in Figure 3C. A density peak is observed for the
last carbon of the CTA+ chain (indicated by the black circle),
suggesting a constant carbon-tail adsorption on the gold
surface. This interaction was experimentally detected by
Hafner and co-workers,17 and the related adsorption structure
corresponds to the formation of adjacent cylindrical CTAB
micelles at the surface, which the authors referred to as a
“collapsed bilayer”. The distribution of nitrogen atoms
permeates the intermicellar channel walls. The Br-1 ions
remain close to the surface, whereas the channel is filled with
the Br-2 ions (Figure 3A,C).
Simulation of CTAB Adsorption on the Au(250)
Surface with 0.2 Br/Au. In the simulation of CTAB
adsorption on the Au(250) surface with a relatively high
number of bromide ions on the gold surface, a bilayer structure
of CTAB units is observed on the gold surface (see Figure 4A).
Figure 4B shows that only a few water molecules reach the
gold surface. This bilayer adsorption pattern of the CTAB
units is described in the literature.17,27,28
In this simulation, the densities of nitrogen, bromide-1,
bromide-2, the last carbon of the hydrophobic tail, and the
water molecules were measured along the axis perpendicular to
the surface (estimated for the last 50 ns of the simulation). The
distributions of these elements are shown in Figure 4C. The
general distributions of the two types of bromide ions (Br-1
and Br-2) are nearly the same as those in the initial
configuration (see Figure 2 and Table 3), that is, no migration
occurs between the two layers of bromide ions.
On the basis of the difference between the two highest
densities of nitrogen atoms indicated in Figure 4C, the
thickness of the adsorbed surfactant bilayer is estimated to be
3.20 nm. This value is in agreement with the thickness on the
surface of AuNRs measured by SANS (3.2 ± 0.2 nm).18

Table 3. Parameters of the Simulated Systems

type of number of gold numbers of bromide-1 and number of water CTA+ box dimensions x/y/z thickness of the gold surface
surface atoms bromide-2a molecules units (nm) (nm)
Au(250) 1310 40 and 156 4141 196 4.00/4.07/16.39 1.59
Au(250) 1310 80 and 116 4181 196 4.00/4.07/16.39 1.59
Au(100) 1600 40 and 156 3785 196 4.10/4.10/15.61 1.43
Au(100) 1600 80 and 116 3785 196 4.10/4.10/16.61 1.43
Au(111) 1332 40 and 156 3955 196 4.10/4.10/15.60 1.26
Au(110) 1400 40 and 156 3782 196 4.08/4.08/15.90 1.45

a
The total number of bromide ions in all the calculations was 196.

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Figure 3. (A) Snapshot of the MD simulation of CTAB adsorption on the Au(250) surface with 0.1 Br/Au. The yellow and dark blue spheres
represent gold and nitrogen atoms, respectively. The gray lines are the apolar tails. The bromide-1 and bromide-2 ions are represented by magenta
and green spheres, respectively. The water molecules were omitted for clarity. (B) Snapshot of the MD simulation of water molecules on the
Au(250) surface. (C) Measurements of the densities of nitrogen (blue), the last carbon of the hydrophobic tail (gray), bromide-1 (magenta),
bromide-2 (green), and the water molecules (red and white spheres) relative to the gold surface.

Simulation of CTAB Adsorption on the Au(110),
Au(100), and Au(111) Surfaces with 0.1 Br/Au. In these
simulations of a relatively low concentration of bromide ions
on the gold surfaces, the adsorbed CTAB units are organized
as adjacent cylindrical micelles and intermicellar channels are
observed between them. These channels are filled with water
molecules, as shown in Figure 5.
Indeed, a similar pattern of CTAB adsorption was also
described by Meena and Sulpizi on low-index gold surfaces.24
They also observed a similar Br/Au ratio on the gold surfaces
after simulation. Moreover, they observed that the channel
thickness depends on the facet; it decreases in the following
order: (110) > (100) > (111). In these simulations, alkyl chain
interactions on the gold surface, which were not detected in
previous studies, are observed (see the distribution of the last
carbon of the hydrophobic tail along the axis perpendicular to
the surface for the last 50 ns of the simulation in Figure S1).
Simulation of CTAB Adsorption on the Au(100)
Surface with 0.2 Br/Au. A relatively high number of
bromide ions were placed on the gold surface in the initial
configuration for this simulation. Consequently, the CTAB
units are arranged in a bilayer structure on this gold surface
(see Figure 6A). As shown in Figure 6B, the water molecules
do not reach the gold surface because of the formation of a
compact bilayer of CTAB units. This pattern is also observed
for the Au(250) system with a relatively high content of
bromide ions (see Figure 4).
The distributions of nitrogen, bromide-1, bromide-2, the last
carbon of the hydrophobic tail, and the water molecules along
the axis perpendicular to the surface (estimated for the last 50
370
ns of the simulation) are presented in Figure 6C. The general
distribution of the Br-1 ions indicates that they remain at the
gold/CTA+ interface, and likewise, the Br-2 ions remain near
the CTA+/aqueous solution interface (see Figure 6A,C).
Furthermore, as shown in this figure, the difference between
the two nitrogen peaks indicates that the thickness of the
adsorbed surfactant bilayer is 3.43 nm in this case. This
distance is slightly larger than that observed in the simulation
of the Au(250) surface under similar conditions. Figure 6C
also shows that the nitrogen distribution relative to the gold
surface exhibits two main peaks in the number density at
approximately 0.5 and 3.9 nm and a third, smaller density peak
at approximately 1.0 nm (indicated by the black circle). These
features might be attributed to the weaker binding interactions
between the Br-1 ions and the Au(100) surface, if compared
with these interactions with the Au(250) surface (see Table S1
and Figures S2 and S3), which enable greater mobility of the
CTA+ polar groups. Thus, it is suggested that the density of the
bilayer depends on the strength of the bromide interaction
with the gold surface.
Proposed Growth Mechanism for the Pentatwinned
AuNR. Figure 7 shows a model of the evolution of the
crystallographic facets during pentatwinned AuNR growth.6 In
stage I, the seed symmetry breaks and anisotropy develops.
Here, the pentatwinned AuNR must grow by the mechanism
described by Meena and Sulpizi,24 in which adjacent cylindrical
micelles are adsorbed on the lateral and tip facets. The
[AuBr2]− species reach the surface through the intermicellar
channels.
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Figure 4. (A) Snapshot of the MD simulation of CTAB adsorption on the Au(250) surface with 0.2 Br/Au. The yellow and dark blue spheres
represent gold and nitrogen atoms, respectively. The gray lines are the apolar tails. The bromide-1 and bromide-2 ions are represented by magenta
and green spheres, respectively. The water molecules were omitted for clarity. (B) Snapshot of the MD simulation of water molecules on the
Au(250) surface. (C) Measured densities of nitrogen (blue), the last carbon of the hydrophobic tail (gray), bromide-1 (magenta), bromide-2
(green), and the water molecules (red and white spheres) relative to the gold surface.

Figure 5. Intermicellar channels observed in the MD simulations of low-index surfaces with 0.1 Br/Au. The yellow spheres represent gold atoms.
(A) Au(100), (B) Au(111), and (C) Au(110). The water molecules are represented by red and white spheres.

Previous studies of CTAB adsorption patterns on
pentatwinned AuNRs revealed the presence of a bilayer.27
Our simulation model shows that a higher concentration of
bromides on the gold surface is necessary for the formation of
371
a bilayer on the lateral (100) facet of mature pentatwinned
AuNRs (Figure 6). Thus, it is suggested that bromide must
accumulate on the gold surface during the growth of the
particle. An increase in the number of bromides on the gold
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Figure 6. (A) Snapshot of the MD simulation of CTAB adsorption on the Au(100) surface with 0.2 Br/Au. The yellow and dark blue spheres
represent gold and nitrogen atoms, respectively. The gray lines are the apolar tails. The bromide-1 and bromide-2 ions are represented by magenta
and green spheres, respectively. The water molecules were omitted for clarity. (B) Snapshot of the MD simulation of water molecules on the
Au(100) surface. (C) Measurements of the densities of nitrogen (blue), the last carbon of the hydrophobic tail (gray), bromide-1 (magenta),
bromide-2 (green), and the water molecules (red and white) relative to the gold surface.

surface induces the rearrangement of the CTAB units on the
gold particle, causing the adsorbed cylindrical micelles (stages
II−III) to transform into a compact bilayer (stage IV). This
hypothesis is reasonable because the continuous reduction of
the Au(I) ions of the [AuBr2]− species on the gold surface
releases bromide ions in loco.23
Proposed Growth Mechanism for the Single-Crystal
AuNR. Figure 8 shows the single-crystal AuNR growth
stages.22 The growth begins with seed symmetry breaking
(stage I) and the adsorption of the CTAB units via the
bromide ions on the Au(100) and Au(111) surfaces.
Vaia and co-workers22 reported growth on the lateral facets
of AuNRs during the early growth stages, which is consistent
with the presence of intermicellar channels on the lateral facets
(stages II−IV). Thus, at these stages, because of the low
concentration of bromide ions on the gold surfaces, the
adsorbed CTAB molecules form adjacent cylindrical micelles
on all the facets, based on the results of Meena and Sulpizi24
and this study (see Figure 5).
Again, because the flux of [AuBr2]− to the tips of the AuNR
and their subsequent rate of reduction are higher, many
bromide ions are released at the tips. This excess of bromide
ions must move from the surface of the tips [Au(111) facets]
to the sides of the rods [Au(100) facets] because of the higher
affinity of the latter facet for bromide ions.41 The increasing
concentration of bromide ions on the lateral facets causes the
372
intermicellar channels to close, which sustains the anisotropic
growth (stages II−IV). This event is caused by the
reorganization of the CTA+ ions as the concentration of
bromide ions, on the gold surface, increases. Finally, the
formation of the high-index Au(250) facet is induced in stage
V. This transition from the Au(100) to the Au(250)
crystallographic facet is probably due to the reorganization of
the gold atoms at the surface to generate a crystalline facet with
a greater ability to stabilize bromide ions.
Studies of the CTAB arrangement on mature single-crystal
AuNRs reported the presence of a CTAB bilayer.17,28 The
simulation results indicate that this structure appears when the
concentration of bromides on the gold surface is high (Figure
4). Therefore, the viability of the proposed growth mechanism,
which assumes that a transition from cylindrical micelles to a
bilayer occurs, relies on the assumption that bromide
accumulates at the gold/CTA+ interface. This assumption
must be verified by experimental evidence to confirm the
proposed mechanism.
It should be noted that in the synthesis of single-crystal
AuNRs, the majority of the Au(I) ions present during the
growth is not completely reduced. This result must be due to
the formation of a compact bilayer of CTAB units on all the
facets of mature AuNRs, thus preventing the Au(I) species
from accessing the surface of the gold particle.42
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Figure 7. Illustration of the growth stages of a pentatwinned AuNR during seed-mediated colloidal synthesis.

Figure 8. Illustration of the growth stages of a single-crystal AuNR during seed-mediated colloidal synthesis.

■ CONCLUSIONS
An MD simulation model that captures the different
arrangements of CTAB units adsorbed on various crystallo-
graphic facets of AuNRs in an aqueous solution was
constructed. On the basis of the model, a detailed mechanism
for the colloidal AuNR formation in an aqueous phase that
accounts for the effect of the number of bromides at the gold
surface on the CTAB adsorption structure, which can be
anchored cylindrical micelles or a compact bilayer, was
proposed.
373
The formation of the adsorbed cylindrical micelles with
intermicellar channels allows the [AuBr2]− ions to reach the
gold surface and is therefore proposed to be the driving force
of the anisotropic growth, in accordance with the results of
previous theoretical studies.24,25 This mechanism is consistent
with the growth of the particles (length and width) in the early
stages and with the zipping-like growth mechanism in the later
stages of AuNR fabrication. The driving force that separates
the early and later stages of the AuNR growth process appears
to be related to the concentration of bromide ions adsorbed at
the gold surface. A relatively small number of bromide ions on
the gold surface leads to the formation of adsorbed adjacent
DOI: 10.1021/acs.langmuir.7b03703
Langmuir 2018, 34, 366−375
Langmuir
micelles of CTAB on it. As the concentration of bromide ions
at the gold surface increases during the later stages of particle
growth, the arrangement of CTAB units on the gold particle
changes to a bilayer structure. This mechanism can apply to
both methods of AuNR synthesis, that is, for the single-crystal
and pentatwinned methods.
It is concluded that the concentration of bromide ions at the
gold surface during the reduction of the [AuBr2]− species must
be known to understand the AuNR growth process in aqueous
solutions. Furthermore, the change in the CTAB adsorption
pattern during the growth process provides insight into the role
that the surfactant plays in causing anisotropic growth.
This work hopefully contributes to the understanding of the
growth mechanism of AuNRs and sheds more light on the
fascinating studies of nanoparticle growth.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.7b03703.
Graph of the overlap of the last carbon of the tail on low-
index surfaces with 0.1 Br/Au; MD simulations of
bromide adsorption on Au(250) and Au(100) surfaces;
and model details of the gold surface and sodium
bromide solution (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: mrm@qui.ufal.br.
ORCID
Mario R. Meneghetti: 0000-0002-0722-8599
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge Dr. Santosh Kumar Meena at
Johannes Gutenberg University, Germany, for kindly providing
the atomic coordinates of the gold surfaces and Prof. Dr. Paulo
A. Netz at Federal University of Rio Grande do Sul for
important contributions in solving technical problems with the
simulations, as well as, Prof. Dr. Thereza A. Soares at Federal
University of Pernambuco for encouraging us to carry out
theoretical studies in the field of nanoparticle syntheses. The
authors are grateful for the financial support of the Brazilian
funding agencies CNPq, Capes, Fapeal, and INCT-Catalise
and for the computational resources provided by the Cenapad-
Unicamp. M.R.M. thanks CNPq for the research fellowships.
■
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375 DOI: 10.1021/acs.langmuir.7b03703

Langmuir 2018, 34, 366−375