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The role of halide ions in the anisotropic growth

of gold nanoparticles: a microscopic, atomistic
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2016, 18, 13246 perspective†

Santosh Kumar Meena,a Sirin Celiksoy,b Philipp Schäfer,‡b Andreas Henkel,b
Carsten Sönnichsenb and Marialore Sulpizi*a

We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold
nanorods through a combined computational and experimental study. Atomistic molecular dynamics
simulations unveil that Br adsorption is not only responsible for surface passivation, but also acts as the
driving force for CTAB micelle adsorption and stabilization on the gold surface in a facet-dependent
way. The partial replacement of Br by Cl decreases the difference between facets and the surfactant
Received 17th February 2016, density. Finally, in the CTAC solution, no halides or micellar structures protect the gold surface and
Accepted 8th April 2016 further gold reduction should be uniformly possible. Experimentally observed nanoparticle’s growth in
DOI: 10.1039/c6cp01076h different CTAB/CTAC mixtures is more uniform and faster as the amount of Cl increases, confirming
the picture from the simulations. In addition, the surfactant layer thickness measured on nanorods
www.rsc.org/pccp exposed to CTAB and CTAC quantitatively agrees with the simulation results.

1 Introduction (chloride, bromide or iodide) are present in water in addition to

stabilizing surfactants or polymers.6–20 In fact, halide anions
Anisotropic metal nanoparticles have been and still are the significantly influence the morphology of gold nanoparticles,21,22
subject of great attention and investigation due to their shape thanks to their strong tendency to adsorb on metallic surfaces.
and size-dependent physical and chemical properties.1 The The growth of the nanoparticles takes place in a rather complex
rational control of their size and shape during the synthesis mixture of salts and surfactants in water.23 A microscopic,
process is one of the main targets of ongoing research.2 The atomistic picture of the growing solution would help to under-
gold nanorods are usually prepared using a seed mediated growth stand the mechanism and to rationally control the synthesis.
technique. In this technique, ascorbic acid (a mild reducing Some recent theoretical studies have tried to rationalize the role
agent) is added to an aqueous cetyltrimethylammonium bromide of halides. In particular density functional theory (DFT)-based
(CTAB) solution of HAuCl4 for the selective reduction of Au3+ to calculations have been used to show that surfactants, bromide,
Au+ (growth solution), followed by the addition of small gold and silver preferentially adsorb on some facets of the seeds.24
seeds that catalyze the reduction of Au+ on their surface.3–5 The This is certainly an interesting first step in the direction of
addition of silver nitrate to the growing solution can increase the microscopically understanding the role of interfacial interactions
yield of short gold nanorods (aspect ratio circa 6) to nearly 100%.4 in shaping the growth, however the cost of DFT calculations is
In most of the synthesis recipes for gold nanoparticles, halide ions still preventing us from studying systems including more than
a few molecules. Force field-based molecular dynamics (MD)
simulations have proven to be an effective tool to consider larger
a
Institute of Physics, Johannes Gutenberg University Mainz, Staudingerweg 7, systems at the nanometric scale, including the electrolyte
55099 Mainz, Germany. E-mail: sulpizi@uni-mainz.de; Fax: +49 6131 39 25441;
solution and therefore accounting for the effect of temperature
Tel: +49 6131 39 23641
b
Institute of Physical Chemistry, University of Mainz, Duesbergweg 10-14,
and dynamics on the nano- to microsecond timescale.
D-55128 Mainz, Germany In particular MD simulations have been used to address
† Electronic supplementary information (ESI) available: Solvation structure of metal nanoparticle/liquid interfaces and to accurately describe
halides, electrostatic potentials at the interface, halide ions on the Au(111) the adsorption of peptides and organic molecules.25–27 A recent
surface in water, density profiles and electrostatic potential profiles for different
simulation study on ionic liquids interacting with various
CTAB/CTAC systems and conversion of the plasmon shift to the layer thickness.
See DOI: 10.1039/c6cp01076h
facets of gold has shown good correlations with experimentally
‡ Present address: Max Planck Institute for Polymer Research, Ackermannweg 10, observed nanorod growth.28 There, the stabilization of the
55128 Mainz, Germany. different facets was found to be mediated by ammonium ions

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which were also acting as the solvent. Walsh and coworkers have experiments are performed in different CTAB/CTAC mixtures
also recently shown how peptide sequences can discriminate which correspond to the relative concentration of halides as
between gold facets under aqueous conditions offering a investigated in the simulations. Moreover, a measure of the
promising route to control the growth and organisation of surfactant layer thickness is provided through measurements
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bio-mimetically synthesized gold nanoparticles.27 In our recent of the surface plasmon resonance from nanorods immersed in
work,29 we have performed MD simulations of different gold CTAB or CTAC solutions. The experiments provide a validation
facets in contact with an electrolyte solution containing CTAB of the simulation predictions showing a quantitative accord
surfactants in order to understand the microscopic/molecular between the simulated and measured thickness of the surfactant
origin of the anisotropic growth. Our simulations showed, for layer. The combined approach of atomistic molecular dynamics
the first time, that on all the surfaces CTAB forms distorted simulations and corresponding experiments provides a general
cylindrical micelles spaced by water channels containing bromide framework to investigate the complex processes occurring
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ions, which can provide a path for the diffusion of the gold during nanocrystal formation linking properties at the solid/
reactants toward the gold surface.29 liquid interface to the morphology of the growing solid.
Here, we want to investigate the influence of the halides
on the growth mechanism of gold nanorods in CTAB/CTAC
solutions using a combination of simulations and experiments.
2 Methods
We aim to understand how the structure of the gold/surfactant/ 2.1 Computational section
electrolyte interface changes when Cl replaces Br at different 2.1.1 Models and simulation details. We first studied the
concentrations. The key question we want to address is how the adsorption of halides at the gold/water interface without
halides affect the surfactant assembly at the surface and conse- surfactants. A 4  4  1.26 nm3 gold slab is solvated with a
quently the interface structure and properties of different facets. water slab of about 5 nm thickness. The details of the simulation
For this purpose, we built a simple model of the nanorod surface models for the Au(111) surface/water interface in the presence of
in contact with the growing solution and we simulate the different halides are reported in Table 1, including box sizes and
microscopic mechanism of adsorption of CTAB/CTAC surfactant the number of atoms. We have considered three different
mixtures with different ratios on three gold surfaces namely the halides, namely Cl , Br and I in combination with the same
native Au(111), Au(110) and Au(100). Our surfaces are treated as number of Na+ counterions in order to keep the system neutral.
infinite planes in the periodic boundary condition, and therefore Ions are added to the system randomly replacing water molecules.
our analysis is especially relevant to the growth stage in which In Table 2, the details of the model systems for the gold/
the different facets of the nanorod are already formed and have electrolyte interface containing different types of surfactants
sizes of a few nanometers. In this regime it is possible to isolate are described. In particular box sizes and the number of atoms
the role played by the different facets (different planes) with for the 100% CTAB, 50% CTAB 50% CTAC, 25% CTAB 75%
respect to that of the edges. In particular, we analyze the surface CTAC and 100% CTAC systems for the three surfaces Au(111),
passivation by halide ions, the packing density of CTA+, the Au(110) and Au(100) are reported. The thickness of the gold
compactness of the surfactant layer and the potential difference slab is 1.26, 1.45 and 1.43 nm for the Au(111), Au(110) and
between the bulk and the surfactant layer. Our model systems Au(100) surface models, respectively. We would like to mention
include pure CTAB, pure CTAC, a mixture of 50% CTAB and 50% here that only the native surfaces are considered. The Au(100)
CTAC and a mixture of 25% CTAB and 75% of CTAC in the surface can reconstruct in the Au(100)-hex, in aqueous solution,
growth solution. We want to mention here that, for the moment, while the Au(110) surface can reconstruct in the missing row.30
we do not include silver cations in our simulation models. However this represents a further element of complication
Indeed, although it is well established that the addition of a which will be addressed in future work along with higher index
small amount of silver nitrate during the synthesis has an
important effect on the growth,5 this is a further element of
Table 1 Model details of the Au(111) surface in contact with a sodium
complication that we plan to address in a further study.
halide solution (1.81 M, 3.87 and 7.78 M)
We find that the degree of binding of the different halides
to the gold surfaces has a strong impact on the structure of the Name of No. of halide No. of water Box dimensions X [nm],
surfactant layer at the interface. Replacing Br with Cl causes surfaces ions molecules Y [nm] Z [nm]
an important structural rearrangement of the surfactant layer 1.81 M
which becomes less compact. Also, the difference between Au(111) 90 Cl 2761 4.02, 4.02, 7.04
Au(111) 90 Br 2761 4.02, 4.02, 7.03
different facets in terms of surface density of surfactants and Au(111) 90 I 2761 4.02, 4.02, 7.04
ions becomes less pronounced as the CTAB/CTAC ratio
decreases. Finally when all Br is replaced by Cl only a few 3.87 M
Au(111) 180 Br 2581 4.01, 4.01, 7.03
disordered CTA+ molecules can bind to the gold surface, Au(111) 180 I 2581 4.01, 4.01, 7.02
confirming that CTAC is unable to exert a protecting action
on the gold surface and is unable to inhibit the growth of 7.78 M
Au(111) 360 Cl 2221 4.02, 4.02, 7.03
any gold surface. The simulations are then compared to the Au(111) 360 Br 2221 4.02, 4.02, 7.03
experiments to validate our findings. In particular growth Au(111) 360 I 2221 4.01, 4.01, 7.02

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Table 2 Model details of different concentrations of CTAB/CTAC surfactant Table 3 Lennard-Jones parameters of Au, Cl , Br and I
in water on the gold(111), (110) and (100) surfaces
1
Name C6 [kJ mol nm6] C12 [10 5
kJ mol 1
nm12]
Name of No. of No. of water Box dimensions X [nm],
surfaces CTAB/CTAC molecules Y [nm], Z [nm] Au37 0.029227046 0.9650000
Cl 35
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0.01380625 10.6915600
100% CTAB Br 40 0.027655690 6.5480464
Au(111) 180/0 4982 4.07, 4.07, 15.47 I 41 0.044452000 18.8618000
Au(110) 180/0 4936 4.08, 4.08, 15.90
Au(100) 180/0 4884 4.1, 4.1, 15.61
CTA+ is such that the three methyl groups in the head group
50% CTAB 50% CTAC
Au(111) 90/90 4802 4.06, 4.06, 15.44 and the methylene group adjacent to the nitrogen carry a
Au(110) 90/90 4802 4.08, 4.08, 15.54 partial positive point charge of +0.25e each and the central
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Au(100) 90/90 4802 4.1, 4.1, 15.61 nitrogen atom is neutral.36 The Lennard-Jones parameters for
25% CTAB 75% CTAC gold and halide ions are reported in Table 3. The Lennard-Jones
Au(111) 45/135 4982 4.07, 4.07, 15.49 parameters for gold from the study of Heinz et al.37 were
Au(110) 45/135 4936 4.08, 4.08, 15.92 employed for the metal description. They quantitatively reproduce
Au(100) 45/135 4884 4.11, 4.11, 15.64
the density, surface tension, and interface tension with water38 and
100% CTAC they have been extensively used also to investigate noncovalent
Au(111) 0/180 4982 4.07, 4.07, 15.47 adsorption of organic and biomolecules,38 including also single
Au(110) 0/180 5651 4.14, 4.14, 15.75
Au(100) 0/180 4884 4.11, 4.11, 15.65 CTAB surfactant molecules, hexadecylammonium chloride
(HDAC), amino acids on Au(111)39 and peptides38 on Au(111)
and Au(100) in aqueous solution. The same parameters had
been already used in our previous work.29 The combination of
planes. The 100% CTAB model described here is the same as we
the CTAB force field from ref. 36 and the gold parametrization
have already used in our previous work.29
from ref. 37 has been discussed in our previous work.29 In
Further details about the initial configuration are reported
particular we verified that for the CTAB parameters from ref. 36
in the ESI† (see Fig. S5).
the single molecule binding geometry and adsorption energy to
All MD simulations have been performed using the GRO-
Au(111) in aqueous solution are in close agreement with those
MACS package (version 4.5.5).31–34 Periodic boundary conditions
obtained using the all-atom CHARMM-METAL force field. The
were applied in all three directions. Energy minimization was
Lennard-Jones parameters for bromide ions are from ref. 40.
conducted after the addition of water and ions to keep the
The Lennard-Jones parameters for iodide ions are from the
maximum force on any atom below 1000 kJ mol 1 nm 1.
study of Reif and Hunenberger.41 They are compatible with
A constant temperature of 300 K and a constant pressure of
ionic polarizability and are calibrated to reproduce single-ion
1 bar were maintained by the Berendsen and Parrinello–Rahman
hydration free energies derived from the experimental conven-
coupling scheme. A time step of 2 fs was employed and trajec-
tional hydration free energies along with a standard intrinsic
tories were stored at every 2 ps. The system was first equilibrated
hydration free energy of the proton. A description of the halide
in the NVT ensemble (constant number of particles, volume, and
solvation structure is reported in the ESI† (Fig. S1).
temperature) for 100 ps, and subsequently NPT (constant number
of particles, pressure, and temperature) ensemble simulations
were performed. MD production runs were extended for at least 2.2 Experimental section
200 ns for the 100% CTAB models. Longer simulations up to 2.2.1 Materials. Deionized water from a Millipore system
1000 ns were considered for the CTAB/CTAC mixtures and for the (418 MO, Milli Q) was used in all experiments. All chemicals
100% CTAC systems (Table 2) in order to achieve convergence for were purchased from Sigma-Alldrich and used without any
the structure of the surfactant layer at the interface. Convergence further purification.
of the surface density of CTA+ and Br as a function of time has 2.2.2 Synthesis of gold nanorods. Gold nanorods were
been carefully checked and reported in Fig. S6 of the ESI.† prepared using a two-step process according to the literature.5
Trajectories from the last 50 ns were used for the calculation First, seeds were prepared as follows: 50 mL of 0.1 M tetrachloro-
of the properties reported in Table 4. In the case of the metal/ auric acid (HAuCl4) are added to 5.0 mL of Milli Q water and
electrolyte interfaces without surfactants (models in Table 1) a mixed with 5.0 mL of 0.2 M cetyltrimethylammoniumbromide
shorter simulation time can already provide good statistical (CTAB) solution. During vigorous shaking, 0.60 mL of ice-cold
sampling. In this case, MD production runs of 50 ns were 0.020 M sodium borohydride (NaBH4) was added resulting in the
performed and trajectories from the last 10 ns were used for formation of a brownish-yellow or yellow suspension of seeds.
analysis. The seed suspension was kept at 30 1C and used within one day.
2.1.2 Force-field parameters. The GROMOS96 53a6 force- In a second step, seeds were grown to nanorods in the following
field35 was employed for all our MD simulations. In particular way: 10 mL of growth solution containing 5.0  10 4 M HAuCl4,
the cetyltrimethylammonium cation (CTA+) model proposed (0.10-X) M CTAB, X M CTAC, 8.0  10 5 M silver nitrate (AgNO3)
and validated by Wang and Larson36 has been used in combi- and 5.5  10 4 M ascorbic acid (AA) was prepared. X was varied
nation with the SPC water model. The charge assignment for between 0 and 0.1. AA changes the growth solution from dark

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yellow to colorless. After the addition of 12 mL of seeds, the

solution changes color to blue or grayish-red within 10–20 min.
2.2.3 Growth kinetics. Growth solutions with the same
concentrations as for the synthesis of gold nanorods and a
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reduced total volume of 3 mL were prepared in a cuvette. After

the addition of 7.2 mL of seed solution and rapid mixing, UV/VIS
transmission spectra were recorded every 3 seconds.
2.2.4 TEM. TEM images were recorded on a Philips EM420
using an operating voltage of 120 kV. TEM samples were prepared
from about 1 mL of nanoparticle solution, and centrifuged twice
for 10 minutes at 9870g (10 000 rpm). The supernatant solution
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was first replaced by 1 mL and the second time by 300 mL of fresh

water. A drop (5 mL) of this concentrated solution was deposited Fig. 1 (a) A characteristic of noble metal nanoparticles is the appearance
of particle plasmons upon excitation with light: the conduction electrons
on a 200 mesh formvar-coated copper grid and dried in air at
follow the electromagnetic field of the incoming wave. The resulting
room temperature. The particle sizes were measured using the surface charges generate a restoring force which causes an oscillation. If
TEM image manually and – when possible – using an automatic excited at the eigenfrequency of this oscillation, the oscillation amplitude
sizing tool by using the Image Processing Toolbox of MATLAB. becomes very large and causes strong light absorption and/or scattering,43
We cross-checked the reliability of the automatic count manually (b) sketch of the light scattering spectra of a gold nanorod embedded
in water (n = 1.33) and with an additional surfactant layer on the surface
for every image series.
(n = 1.4, inset). The surfactant layer causes a resonance wavelength shift
2.2.5 Single nanoparticle spectroscopy (NanoSPR). We Dlres. (c) Original data (uncorrected) for the measurement shown in Fig. 4
determined the change in resonance wavelengths Dlres of gold (see the text for details). Each dot represents the spectral shift of the
nanorods induced by the coverage of CTAB or CTAC to verify plasmon resonance of an individual nanoparticle.
the theoretical prediction of a thicker surfactant layer in the
presence of bromide ions. This experiment was performed on
redshift and the following blueshift are considerably more
a homebuilt dark-field microscope system that allows the
pronounced (Fig. 1c). Because our primary interest is to compare
automatic determination of many single nanoparticle spectra
the surface coverage of CTAC and CTAB, we corrected the shift
of gold nanorods immobilized at the bottom of a microfluidic
caused by the charging effect by using the mean of step 2 as the
flow cell.42 The flow cell allows the exposure of the nanoparticles
baseline for step 1 and the mean of step 4 as the baseline for step 3.
to different solutions. Before immobilizing gold nanorods in the
The resulting corrected plasmon shifts are shown in Fig. 4c and
flow cell by the addition of a 1 M sodium chloride solution,
used for the analysis of surface coverage and layer thickness.
we cleaned the cell by rinsing with 300 mL of Hellmanex II,
a commercial cleaning concentrate followed by 3 mL of ultrapure
water. The plasmon resonance wavelength lres (see Fig. 1a) of 3 Results and discussion
about 40 individual nanoparticles within the field of view was
automatically recorded before and after rinsing with different 3.1 Adsorption of halides on the gold surface
solutions. Generally, the plasmon resonance wavelength changes Before describing the more complex electrolyte solution containing
to larger wavelength if the particle environment’s refractive index the surfactants, we focus on the adsorption of the halide ‘alone’ at
increases (due to the adsorption of molecules, cf. Fig. 1b). To the interface. For this purpose, we have simulated the Au(111)
confirm the different adsorption properties of CTAB and CTAC surface in contact with a 1.81 M solution containing NaCl, NaBr or
predicted by the simulation, we performed the following sequence NaI, respectively. Snapshots from the simulation trajectories are
of experiments: the initial resonance position of the nanoparticles reported in Fig. 2 (a, b, c for NaCl, NaBr, and NaI solutions,
was recorded after extensive washing with pure water. These respectively). The simulations reproduce the expected difference
resonance positions serve as the baseline for the following steps in propensity for the gold surface,44,45 with comparable strong
and we display only the shift with respect to this initial position in binding for Br and I .
Fig. 1c and b. In a first step, we flushed in 300 mL of 0.01 M CTAC The likelihood to find the halides on the gold surface can
and recorded the resonance positions again (see Fig. 1c, step 1). also be expressed in terms of surface concentration, calculated
On average, the resonance positions shifted towards larger wave- as the number of ions in the first layer divided by the surface
length by about 0.7 nm. In a second step, we washed again with area. The number of ions in the first layer is calculated from the
3 mL of pure water and recorded the resonance positions (Fig. 1c, integral number (I.N.), namely the integral of the first peak in
step 2). The spectral positions shifted towards lower wavelength, the ion density profile (see the dotted lines in Fig. S2a–c in the
as expected for the removal of bound CTAC molecules. However, ESI†). The surface concentration of Cl ions (0.26 ions per nm2)
to our surprise, the resonance position was slightly blue shifted by is negligible as compared to that of Br and I (2.06 and
about 0.4 nm compared to the initial baseline. This blue shift is 2.07 ions per nm2), showing that Cl ions preferentially remain
most likely caused by a charging effect induced by halide ion in the solution, in contrast to Br and I ions which are
adsorption. The steps three and four repeat the same procedure strongly adsorbed on the gold surface. Our data can be com-
as steps one and two – only replacing CTAC with CTAB. Both the pared to the experimental ion adsorption data obtained using

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Fig. 2 Snapshots from simulations for (a) NaCl, (b) NaBr and (c) NaI in water on the Au(111) surface. Ion density as a function of distance from the Au(111)
surface for (d) NaCl, (e) NaBr and (f) NaI. Water molecules are represented with sticks, where red and white are used for oxygens and hydrogens,
respectively. The different shades of the same color are used to provide a 3D projection.

the chronocoulometric technique.44 In particular, since in our 1.5 M CTAC) and finally 100% CTAC (2 M solution). Fig. 3a
simulation we do not apply any external potential we can shows a snapshot of a simulation box containing the Au(111)
assume that we provide a simplified model of the open circuit surface, the CTAB layer, and the water layer after 200 ns. The
conditions where, additionally, our model also assumes zero CTAB headgroups favorably attach to the gold surface and form
charge density on the gold surface. Under such conditions we a distorted cylindrical micelle, where the CTAB headgroups
quantitatively agree with the experimental data at zero applied arrange in the outer layer of the micelle and the CTAB tails
voltage, which suggest negligible Cl adsorption with a surface arrange in the core of the micelle. A similar behaviour is
density of 0.25 ions per nm2 and a significant Br adsorption observed on Au(110) and Au(100) as well, although with some
with a surface density of 2.7 ions per nm2. differences in the ion densities (see ESI,† Fig. S7a–c).
Looking more in detail, we find that Br ions form two layers The synergic co-adsorption of the anionic and cationic com-
next to the gold surface with a higher number of ions in the ponents of a model quaternary ammonium bromide surfactant
first layer. In particular Br can be directly adsorbed on the (although with a shorter hydrophobic tail) had been also experi-
gold surface competing with the water molecules in the first mentally measured using the thermodynamics of an ideally
adsorbed layer. The ion density profiles are reported in Fig. 2d–f. polarized Au(111) or Au(100) electrode.49,50 The ion density
On the other hand for the NaCl solution, the first adsorbed layer profiles of CTA+ and Br are reported in Fig. 3e as a function
on the gold surface is only formed by water (as can be observed of the distance from the Au(111) surface. The surface density of
from the water density profile in Fig. S2a–c in the ESI†). The first Br and CTA+ is calculated in our simulations as the number of
(weak) peak in the Cl density profile only appears around the ions in the first layer divided by the surface area (Fig. S7a–c in
water second layer (see e.g. Fig. S2a in the ESI†). The results for the ESI†). The surface density of Br is higher on Au(110) and
the NaCl solution are in agreement with the pioneering work of Au(100) (1.41 and 1.40 ions per nm2, respectively) than on
Spohr on the molecular simulation of the electrochemical double Au(111) (1.09 ions per nm2) resulting, in the case of Au(110)
layer.46 The halide propensities at the gold/water interface follow and Au(100), in the passivation of a larger surface area (Table 4).
a similar trend to those observed at the air/water interface in the The lower surface passivation on Au(111) could translate
simulations by Jungwirth and Tobias47 and at the hydrophobic into a higher reduction rate of gold species (such as AuCl2 ) on
solid surfaces in the simulations by Horinek and Netz.48 Au(111). The anisotropic Br density also influences the CTA+
surface density, which is higher on Au(110) and Au(100)
3.2 Adsorption of CTAB/CTAC surfactants on Au(111), Au(110) (1.49 molecules per nm2) than on Au(111) (1.31 molecules per nm2)
and Au(100) (Table 4). The less compact surfactant layer on Au(111) could
To understand how the different surface affinity of Cl and provide easier access to gold species in solution promoting a more
Br affects the structure of the surfactant layer, we simulate efficient growth on such a surface. Additional insight into the
electrolyte solutions containing 100% CTAB (2 M solution), interfacial properties can be provided by the interfacial electro-
a mixture of 50% CTAB and 50% CTAC (1 M CTAB, 1 M CTAC), static potential, defined as the difference in the potential between
a mixture of 25% CTAB and 75% of CTAC (0.5 M CTAB, the bulk solution and the CTAB layer. Such an electrostatic

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Fig. 3 Snapshots from the simulations for (a) 100% CTAB, (b) 50% CTAB 50% CTAC, (c) 75% CTAB 25% CTAC and (d) 100% CTAC. Ion density as
a function of the distance from the Au(111) surface for (e) 100% CTAB, (f) 50% CTAB 50% CTAC, (g) 75% CTAB 25% CTAC and (h) 100% CTAC (see ESI,†
Fig. S7–S10 for Au(110) and Au(100)).

potential difference is higher across the Au(111) interface than In turn this could result in an additional factor promoting faster
across the Au(110) and Au(100) interfaces (see ESI,† Table S4 and growth of gold nanorods at the Au(111) surface.
Fig. S7e), providing a stronger driving force for the migration In order to study the influence of Cl on the surface properties
of the negatively charged AuCl2 species toward the gold slab. we performed new simulations where 50% of Br are replaced by

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Table 4 Surface density of CTA+, Br and Cl with different concentration Au(111) and Au(100) and 2.4 nm on Au(110) surfaces (Table S5
ratios of CTAB/CTAC on different gold surfaces. The maximum standard in the ESI†). In such a scenario, the thin surfactant layer will be
error in the surface densities is 0.01 ions per nm2
unable to inhibit the growth of gold nanoparticles in any
Au(100) direction, explaining an isotropic, faster growth rate.
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Name of surface Au(111) Au(110) [ions per nm2] We would like to comment here that the simulation results
CTA+ 100% CTAB 1.31 1.49 1.49 which we present for the 50% CTAB and 25% CTAB systems do
CTA+ 50% CTAB 50% CTAC 1.08 0.90 0.85 not possibly represent the most stable equilibrium state for
CTA+ 25% CTAB 75% CTAC 0.97 1.18 0.78
CTA+ 100% CTAC 0.66 0.67 0.65 the mixture. They suggest a trend, namely the micellar layer
destabilization. The real scenario is certainly more complex and
Br 100% CTAB 1.09 1.41 1.40 we also expect that some degree of anisotropy would characterize
Br 50% CTAB 50% CTAC 0.76 0.74 0.77
the gold nanorod surface, where the CTAB micellar layer is not
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Br 25% CTAB 75% CTAC 0.56 0.84 0.82

uniformly covering the surfaces, but would probably form
Cl 50% CTAB 50% CTAC 0.06 0.03 0.01 patches. Larger box dimensions as well as enhanced sampling
Cl 25% CTAB 75% CTAC 0.17 0.15 0.12
Cl 100% CTAC 0.12 0.07 0.01 techniques would indeed be necessary to explore in a more
systematic way such a possibility. The case of the 100% CTAC
system is certainly more simple. The clear message from the
Cl (Fig. 3b). The ion density profiles of CTA+, Br and Cl are simulations is that the CTAC micelle prefers to be in the
reported in Fig. 3f as a function of the distance from the Au(111) solution and does not stick onto gold, although some CTA+
surface. The surface density of halides on all the three surfaces molecules can adsorb onto the gold surface. Again the exact
is lower than that in the 100% CTAB case (Table 4 and ESI,† details of the CTA+ adsorption cannot be directly inferred by a
Fig. S8a–c), resulting in a reduced surface passivation and single trajectory. However, in the 100% CTAC system the
possibly in an increased reduction rate. Interestingly, the lower thickness of the surfactant layer formed by the disordered
Br density at the gold/water interface has a remarkable effect CTA+ adsorbed on gold must certainly be much smaller than
on the structure of the surfactant layer, which appears more the thickness of a full micelle (see Table S5 in the ESI†).
stretched (and less compact) as compared to the 100% CTAB
case (Fig. 3b). The CTA+ surface density is reduced and the 3.3 Validating our prediction: the experimental results
difference between facets becomes less pronounced (1.08, 0.90 The simulations predict several properties that can be tested
and 0.85 ions per nm2 for Au(111), Au(110) and Au(100), experimentally: an increasing amount of chloride ions should
respectively). This finding would support the idea that, in the lead to faster and more isotropic nanoparticle growth and
mixture of CTAB/CTAC, the surfactant layer is not capable of CTAC should form a considerably thinner layer on gold than
significantly blocking the growth along any particular direction, CTAB. We tested the first aspect by a series of nanoparticle
resulting in a more isotropic growth. The interface electrostatic syntheses where we varied the ratio of CTAC and CTAB in
potential between the surfactant layer and the bulk solution (see the growth solution. Transmission electron microscopy (TEM)
ESI,† Fig. S8e and Table S4) is also pointing to an isotropic images of the resulting particles are displayed in Fig. 4a. The
behaviour along the three considered directions. TEM images show the expected trend towards more isotropic
As the CTAB fraction is further reduced to 25%, the CTA+ particles with decreasing bromide concentration. A quantitative
surface density decreases and the surfactant layer becomes analysis of many TEM images, where we determined the fraction
even less compact (ESI,† Fig. S9), and its structure even more of rods versus spheres (see Fig. S13 in the ESI†), confirms the
stretched along the z direction (Fig. 3c, see Fig. S12 and Table S5 trend as well (Fig. 4b). In addition, we monitored the speed of
in the ESI†). the nanoparticle growth by following the optical absorption in
The most striking results are certainly obtained for the 100% the interband region at 450 nm (see Fig. S14 in the ESI†) which
CTAC solution (Fig. 3d, h and Fig. S10 in the ESI†). For such is a measure of the nanoparticle volume. We extract an apparent
a system the initial configuration is prepared with a CTAC rate constant from these volume growth curves using a Boltzmann-
micelle adsorbed on the gold surface (Fig. S11a in the ESI†). function (for resource limited growth). The reaction speed
However, as the simulation proceeds, the CTAC micelle becomes decreases when the amount of CTAB is increased (blue dots
more and more stretched in the z direction (which is the in Fig. 4b) which confirms again the trend expected from the
direction orthogonal to the surface) (a picture of the system at simulation.
t = 300 ns is provided in Fig. S11b of the ESI†) and finally detaches To test the second prediction from the simulation, the thicker
from the gold surface moving into the bulk after 600 ns (the final surfactant layer on the gold surface in the presence of bromide
equilibrated system is reported in Fig. 3d). Such a behaviour is ions, we exploit the sensitivity of the plasmon resonance
certainly driven by the low propensity of Cl for the surface. In frequency of gold nanoparticles to the adsorbed layer of the
the final configuration (Fig. 3d) a few surfactant molecules, which material.43 Using a homebuilt dark-field microscope in combi-
are left on the gold surface, tend to lay flat so as to maximize the nation with a scanning stage and a spectrometer,42 we determine
interaction between their hydrophobic tail and the gold surface, the plasmon resonance position lres of about 40 gold nano-
while their headgroup orients towards the bulk solution. The particles before and after exposure to a solution containing either
thickness of this remaining surfactant layer is about 1.8 nm on 0.01 M CTAB or CTAC. The exposure to CTAB/CTAC leads to a

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 View Article Online

Paper PCCP

4 Conclusions
We have presented here a detailed atomistic investigation of
the gold nanoparticle surface in contact with the surfactant/
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

electrolyte solution, which addresses the role of the halides in

the formation of the protective layer of surfactants. Our simula-
tions show that CTAB is able to form a compact micellar layer
on the gold surface which is actually denser on Au(100) and
Au(110) with respect to Au(111). The key element in the micelle
adhesion to the surface is bromide propensity for the gold
surface. When bromide is partially (eventually fully) replaced by
Open Access Article. Published on 08 April 2016. Downloaded on 7/11/2023 1:36:47 PM.

chloride the micelles prefer to diffuse into the electrolyte

solution leaving the gold surface unprotected. Indeed, for the
CTAC system only a few surfactant molecules are sticking to the
gold surface, leaving the surface itself more easily accessible
to further gold reduction. Two sets of experiments, particle
synthesis and plasmon shift measurements, confirm the trends
expected from the simulations and agree quantitatively with
the predicted values for the surfactant layer thickness. These
experimental confirmations let us strongly believe that the
atomistic simulations provide an accurate description of the
underlying processes. The role of certain halide ions (bromide)
in mediating, in a strongly crystal facet dependent way, the
Fig. 4 Experimental data. (a) Representative transmission electron micro-
adhesion of cationic surfactant molecules, provides a better
scopy (TEM) images of gold nanorods synthesized with different percentages
of CTAB in the growth solution, keeping the total CTAB+ CTAC concentration understanding of the way, additives direct nanocrystal growth
constant. (b) Quantitative results of the percentage of rods over spheres towards specific shapes. Moreover, the combined computational
extracted from TEM images as a function of the CTAB percentage (red dots) and experimental approach provides a template for understanding
and the corresponding apparent reaction rates determined by optical the nanocrystal growth dynamics in general, which is a major step
absorption (blue dots), and (c) plasmon resonance wavelength shifts Dlres
in the rational design of nanostructure formation from solution. In
of many individual gold nanoparticles immobilized in a water filled glass
capillary, after exposure to 0.01 M CTAC (green dots) and CTAB (red dots). a next step, this approach should incorporate actual reaction steps
The gray points show the same particles after exposure to water. In the to elucidate the intricate electrochemical and diffusive processes
latter case, the observed shifts are an indication of the measurement in this highly dynamical process.
accuracy. The black symbols show the mean values of their standard error
bars (statistics over about 40 particles).

Acknowledgements
small but clearly measurable shift Dlres in the plasmon resonance We thank Condensed Matter Theory Group KOMET 331 for
(Fig. 4c, see Fig. 1). As expected, the shift for CTAB is much larger providing access to its computational facilities and the Deutsche
than that measured after CTAC exposure (2.6 nm versus 1.1 nm). Forschungsgemeinschaft for financial support under grant no.
Since the plasmon resonance shift Dlres is a function of layer SU 752/1. All the simulations were performed on the Mogon ZDV
thickness t and its refractive index, we have converted the cluster. The experiments were supported by the ERC through the
measured values to a layer thickness. For this conversion, we project 259640 (SingleSense). We thank Jan-Philipp Günther for
use published values for the refractive index of CTAB and CTAC of help with the conversion of the plasmon shift to the surfactant
about n = 1.451,52 and simulation results for the plasmon reso- layer thickness.
nance of gold nanoparticles in different media we obtained using
the boundary element method53 (see Fig. S15 in the ESI†). This
calculation resulted in a layer thickness of t = 1.6 nm and References
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