Current Applied Physics 19 (2019) 1187–1194

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Current Applied Physics

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The morphology control on the preparation of silver nanotriangles T

a,1 b,1 a a a
Guansong Hu , Wen Zhang , Yuanzhi Zhong , Guorun Liang , Qingyuan Chen ,
Wanzhong Zhanga,*
a
Guangdong Provincial Key Laboratory of New Drug Screening, School of Pharmaceutical Sciences, Southern Medical University, Guangzhou, 510515, PR China
b
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: A seed-mediated growth method was commonly applied to prepare one-dimension nanomaterials. However,
Silver nanotriangle some associated particles were unavoidable in the formation of target nanoparticles. Herein, we reported a
Seed modified method to prepare silver nanotriangles with higher uniform shape and particle size. The size and
Size and morphology morphology of the formed nanoparticles could be controlled by regulating reaction conditions. The results
Cetyl trimethyl ammonium bromide
showed that cetyl trimethyl ammonium bromide (CTAB) concentration and seed concentration were related with
Preparation
both the morphology and the particle size. The NaOH concentration, AgNO3 concentration, and the mole ratio of
Vc/Ag+ mainly affected the particle size of the formed nanotriangles. The formation of silver nanotriangles may
be due to the selective stacking of the new tiny nanoparticles and the oriented growth of silver seed crystals. The
oxidizing action of Br−/O2 existing in the CTAB system should be responsible for the final morphology of
truncated triangular silver nanoplates.

1. Introduction reducing agent [25]. Murphy's report represented a milestone in the

Nanomaterials, including silver-based nanomaterials, are widely
used and their production is closely related to people life [1–7]. Since
the application domain and reaction activity of silver nanoparticles
(AgNPs) are associated with their morphology [8–13], it has great
significance for preparing AgNPs with high regularity. In recent years,
there has been a great development in preparing AgNPs and it could be
divided into three methods according to the reaction conditions: phy-
sical method, biological method, and chemical method. Chemical
method is the most widely used method, including chemical reduction
[14–17], electrochemical reduction [18], irradiation-assisted chemical
reduction [19], and pyrolysis [20]. The chemical reduction generally
requires three factors: silver precursor, reducing agent, and stabilizer.
Silver nitrate (AgNO3) is a frequently used precursor to provide silver
ions (Ag+). The common reducing agents include sodium borohydride,
the sodium citrate, vitamin C (Vc), glucose and glycol, which possess
the different reducing ability for reduction of Ag+. The common sta-
bilizer include polyvinylpyrrolidone (PVP), sodium dodecyl sulfate
(SDS), polyacrylic acid (PAA), CTAB, and so on, which are used to
prevent the aggregation of AgNPs [21–24].
In 2001, Murphy prepared silver nanorods and nanowires through a
seed-mediated growth method, using CTAB as stabilizer and Vc as
colloidal synthesis of shape-controlled metallic nanostructures and it
clearly pointed out the possibility of anisotropic metal nanostructures
formation by a seed-mediated growth method [26]. After Murphy's
study, many anisotropic metal nanoparticles were prepared by this
method. Especially, there were a large number of document reports on
the seed-mediated growth of gold nanostructures published in recent
decades [27]. For the preparation of gold nanoparticles, the size control
of seed crystals was the key role to obtain gold nanoparticles with
various shapes and aspect ratios and the big seed crystals could grow
into nanorods in the CTAB rod-like templates (by e.g. Catherine Mur-
phy's group). However, the effects of seed crystals on the shapes and
aspect ratios are mainly concentrated on gold nanostructures, especially
for the formation of gold nanorods.
Compared with the control of the aspect ratio of gold nanorods, the
morphology control of AgNPs may be more difficult to achieve.
Preparing AgNPs by a seed-mediated growth method has two contents:
One is the preparation of silver seed crystals and the other is the growth
of seed crystals in the growth solution. The morphology and size of
silver seed crystals play an extremely vital role in the final morphology
formation of AgNPs. Xia et al. prepared AgNPs in the polyol system and
found truncated cubes and tetrahedrons were formed only when twined
crystals turned into single crystals [28]. Sau et al. thought that the

*
Corresponding author.
E-mail address: zhangwz6@smu.edu.cn (W. Zhang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cap.2019.08.002
Received 23 August 2018; Received in revised form 18 June 2019; Accepted 1 August 2019
Available online 01 August 2019
1567-1739/ © 2019 Korean Physical Society. Published by Elsevier B.V. All rights reserved.
G. Hu, et al. Current Applied Physics 19 (2019) 1187–1194

smaller seed crystals were, the lower size limitation desired nano- Table 1
particles had [29]. The parameters of the reaction for the formation of silver nanotriangles.
As for the development of silver nanotriangles synthesis, varieties of AgNO3 concn. Mole ratio CTAB concn. Seed concn. NaOH concn.
methods have been used, including photochemical method, seed- /mM of Vc/Ag+ /M /mM /mM
mediated method, electrochemical method and thermally induced
3.1. 0.405 5:1 0.02–0.2 0.022 0.90
method [30,31]. Mirkin et al. firstly introduced photochemical route to
3.2. 0.405 5:1 0.075 0.022 4.5–18.0
prepare nanotriangles effectively, although the reaction was under the 3.3. 0.09–0.45 5:1 0.075 0.022 0.90
strict condition and it was expensive [32]. Tang et al. reported that 3.4. 0.405 40:1–5:1 0.075 0.022 0.90
nanotriangles obtained by using silver seeds and sunlight [19]. How- 3.5. 0.405 5:1 0.075 0.0022–0.045 0.90
ever, it is difficult to control the natural sunlight, especially lighting
power. Murphy studied the kinetic control of the formation of trian-
gular silver nanoplates in seed-mediated method [29], which had a stirring for 30 s, it was preserved as seed collosol. Second was the
profound impact on researches followed. Due to the competitive growth preparation of growth solution contained 0.5 mL AgNO3 (0.01 M),
on the crystal faces of seed, it is always difficult to control the mor- 1.0 mL Vc (0.1 M), 0.25 mL seed colloidal solution and different vo-
phology of the formed nanoparticles precisely. lumes of CTAB solutions. After adding 1.0 mL NaOH (0.2 M) and stir-
In the simple and facile soft-template technique, some associated ring for 10 s, the mixture solution was reacted for 10 min under 25 °C to
particles are unavoidable in the formation of target nanoparticles, prepare AgNPs colloidal solution. The parameters of the growth solu-
especially in the preparation of AgNPs. As a result, systematic studies of tion for the formation of silver nanotriangles are shown in Table 1.
reliable size and shape control, along with scalability and polydispersity
of the synthesis are invaluable tools for researchers working on the 2.3. Separation of AgNPs
applied side of nanoparticles and nanostructures. Although the research
on preparing AgNPs in cetrimonium bromide (CTAB) system has been Surfactant-assisted shape separation method was used to separate
reported for a long time, some influence factors on the morphology and the formed AgNPs [35]. First, the colloidal solution was centrifuged at
size are not clear. There are still some uncertainties in the preparation 10,000 rpm for 10 min to get the precipitation of AgNPs. Second, the
of AgNPs in CTAB system and the regularity of prepared AgNPs in the precipitation was dissolved with different concentration CTAB and then
morphology and size is not uniform [33,34]. Especially, much work has the solution was aged for about 4 h to obtain the supernatant and
not been focused on investigating the preparation of silver nano- precipitation by aging treatment. According to the separation result, the
triangles in CTAB system through a seed-mediated growth method. separation process can be repeatedly carried out to achieve the se-
In this study, we improved the preparation method of silver seeds to paration of AgNPs with different morphologies.
obtain silver nanotriangles other than silver nanorods by using the
seeds. The effects of some key factors on the morphology and particle 2.4. Characterization
size of the formed nanoparticles had been studied systematically. It was
found that CTAB concentration and seed concentration were related A U-3010 UV–vis spectrophotometer (Hitachi) was used to record
with both the morphology and the particle size and the NaOH con- the absorbance of the formed AgNPs colloidal solution. An FEI trans-
centration, AgNO3 concentration and mole ratio of Vc/Ag+ mainly af- mission electron microscope (TEM, Tecnai G2 20, an accelerating vol-
fected the particle size of the formed nanotriangles. Some evidence tage of 200 kV) and a scanning electron microscope (SEM, ZEISS Ultra
implied that the new tiny nanoparticles selectively stack and the or- 55) were used to observe the morphologies of the pre-prepared AgNPs.
iented growth of silver seed crystals gradually changed to truncated
triangular silver nanoplates. We suggested that the silver seeds pre- 3. Results and discussion
pared by this study existed stacking faults and thus substantially caused
the selective adsorption of CTAB molecules on the special crystal facets. 3.1. The effect of CTAB concentration on the morphology
The formation of silver nanotriangles was due to the selective stacking
of silver seeds along with the special crystal planes without or with little Silver nanotriangles have three characteristic peaks on their UV–vis
adsorption of surfactant molecules and the oriented growth with Ag+ absorption: in-plane dipole plasmon resonance, in-plane quadrupole
reduction. resonance, and out-of-plane quadrupole resonance. The ~350 nm ab-
sorption peak is due to the out-of-plane quadrupolar resonance, the
2. Experimental section ~420 nm peak is due to the in-plane quadrupole resonance, and the
over 500 nm peak is due to the in-plane dipole plasmon resonance
2.1. Materials [36–39]. UV–vis absorption peaks around at 420 nm are due to the
mixed plasmon resonance of nanospheres and nonspherical nano-
Silver nitrate (AgNO3, 99.9%) and ascorbic acid (Vc, 99.7%) were particles [40]. In this experiment, we thought they were mainly at-
purchased from Alfa Aesar (Tianjin) Chemical Co. Ltd. Trisodium ci- tributed to the plasmon resonance of nanospheres and the in-plane
trate dihydrate (Na3C6H5O7·2H2O, 99.0%), cetrimonium bromide quadrupole resonance of nanotriangles.
(CTAB, 99.0%) and sodium borohydride (NaBH4, 96.0%) were of ana- Because the resonance absorption at 420 nm is related with different
lytical grade (AR) and purchased from China Medicine (Group) nanoparticles, it is better to determine the formation of nanotriangles
Shanghai Chemical Reagent Corp. All chemical reagents were used as mainly depending on the appearance of absorbance peaks at 350 nm
received without further purification. Deionized water was used for all and over 500 nm other than 420 nm. The av. particle size is also related
experiments. to the position of the long wave absorption peak. The red-shift of long-
wave peak means the size of nanotriangles increasing [41]. Although
2.2. Preparation of AgNPs there are a few reports about the effect of CTAB in preparing AgNPs, its
role on morphology formation of AgNPs is not clear. What's more, there
First was the preparation of silver seed colloidal solution by a is an argument with the role of CTAB in the preparation of anisotropic
modification method. The reducing agent (NaBH4) was 10 times nanoparticles in CTAB system. For example, Rabia et al. reported that
equivalent of the precursor of silver ions. The typical process was as CTAB played an important role on the morphology in the formation of
follows: 20 mL solution contained 0.25 mM AgNO3 and 0.25 mM so- AgNPs [42], while Zaheer et al. found that the different CTAB con-
dium citrate and 0.6 mL of NaBH4 (0.10 M) was added. After vigorous centration did not affect the final morphology of AgNPs [43].

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G. Hu, et al.
Fig. 1. UV–vis spectra of AgNPs prepared with different CTAB concentration.
We prepared AgNPs with different CTAB concentration and their
UV–vis spectra were as shown in Fig. 1. CTAB concentration obviously
affects AgNPs morphology in our experiment. When CTAB concentra-
tion is 0.2 M, the colloidal solution shows a weak absorbance peak at ca.
420 nm and a shoulder at ca. 350 nm, which means the formation of a
few quasi-spherical nanoparticles. When CTAB concentration decreases
to 0.1 M, the colloidal solution displays three absorption peaks (348,
427 and 629 nm), which means the appearance of silver nanotriangles.
With a decrease of CTAB concentration from 0.075 to 0.05 M, the ab-
sorption peak in the red region is red-shifted from 687 to 736 nm,
which indicates an increase in the size of silver nanotriangles. When
CTAB concentration decreases to 0.035 M, the absorption peak in the
red region is blue-shifted to 691 nm oppositely and it means a decrease
in size of the nanotriangles. With a decrease in the concentration of
CTAB to 0.02 M, the colloidal solution shows two peaks and the strong
absorption peak at ca. 420 nm, which means that main ingredients of
AgNPs are big nanospheres besides a few silver nanorods in this case.
For CTAB solution, the first critical micelle concentration of CTAB
(CMC1) was 7.6 × 10−4 mol/L, while the second critical micelle con-
centration of CTAB (CMC2) was 7.0 × 10−3 mol/L [44]. In our ex-
periment, the concentration of CTAB was over CMC2, indicating that
CTAB molecules formed rod-like micelles in the growth system. The
rod-like micelles in the collosol of AgNPs were over 89%, while the
monomeric ones were about 6% [45]. The stern layer in CTAB micelles
provides a reaction site and the aggregation of CTAB molecules in-
dicates the contact of reactants [46]. For the rod-like micelles, it is the
template for the formation of one-dimensional nanoparticles, e.g., silver
nanorods and nanowires. In our cases, the shapes of the formed nano-
particles change from big nanospheres to nanotriangles and quasi-
spherical nanoparticles with the increase in the CTAB concentration
from 0.02 to 0.2 M.
We think that the formation of silver nanotriangles may be attrib-
uted to the selective adsorption of monomeric surfactant molecules on
the special crystal planes of silver seed other than the template effect of
CTAB rod-like micelles. In the case of less CTAB (i.e., 0.02 M), the silver
seeds grew up and formed big nanospheres due to the selective ad-
sorption, and the template effect of the rod-like micelles induced the
formation of a few silver nanorods. In the case of more CTAB (i.e.,
0.2 M), the selective adsorption of CTAB should disappear due to the
excessive monomeric molecules on the crystal planes of silver seed and
thus there were quasi-spherical nanoparticles formed.
3.2. The effect of NaOH concentration on the morphology
NaOH is used to control the reaction pH level and it affects the
reducing ability of Vc by affecting its hydroxyl groups. AgNPs are
formed according to equation (1) as follow:
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Current Applied Physics 19 (2019) 1187–1194
Fig. 2. UV–vis spectra of AgNPs prepared with different NaOH concentration.
2Ag++C6H8O6→2Ag0+C6H6O6+2H+ (1)
Fig. 2 shows the NaOH effect in preparing AgNPs. When NaOH
concentration is 4.5 mM, the reaction solution is clear and the intensity
of its corresponding absorption peak is so weak, indicating subtle
chemical reaction proceeding in solution. Vc is a weak reductant and it
is difficult to reduce Ag+ in low alkalinity condition due to the pH of
the growth solution lower than the pKa1 of Vc.
With a concentration of 9.0 mM NaOH, AgNPs colloidal solution
displays three absorbance peaks (343, 430 and 623 nm), which means
the appearance of silver nanotriangles. It is generally known that the
increase of alkaline concentration promotes the ionization and thus
enhances the reducing ability of Vc [47]. As a result, the reduction of
silver ions can occur to form AgNPs corresponding to equation (1). In
the case, the increase in NaOH concentration provides a suitable re-
duction rate of silver ions to facilitate the formation of big silver na-
notriangles.
Furthermore, the redox potential of silver ions is influenced by the
difference in complexing action between silver ion with the monoanion
and dianion of Vc. That is, the reduction rate of silver ions is controlled
to a high degree by the acidity-basicity of the solution. In other words,
the reduction rate of silver ions will increase with NaOH concentration
[47]. In the case, a high nucleation rate derived from the fast reduction
of silver ions facilitates to form small silver nanotriangles. In addition,
excessive OH− could bind Ag+ to form a precipitate in strong alkalis
conditions, which directly decreases the amount and size of the formed
nanotriangle. As a result, when NaOH concentration increases to
13.5 mM, the absorption peak in the red region is blue-shifted to
~570 nm and its intensity becomes weaker, which means that the na-
notriangle's size becomes small. Similarly, the long-wave peak further
blue shifts to 554 nm with an increase of NaOH concentration to
18.0 mM.
3.3. The effect of AgNO3 concentration on the morphology
Fig. 3 shows the effect of different AgNO3 concentration on AgNPs
morphology by keeping the same excess Vc concentration. While AgNO3
concentration is 0.09 mM, the typical absorbance peaks of nano-
triangles are inconspicuous and it may indicate that only a few nano-
triangles have formed. With an increase of AgNO3 concentration from
0.18 to 0.36 mM, the corresponding long-wave absorbance peak ex-
hibits a red-shift from 531 to 641 nm, which implies the size of nano-
triangles increasing. When AgNO3 concentration increases from
0.36 mM to 0.405 or 0.45 mM, the absorption peak in the red region is
blue-shifted from 641 to 617 nm and the 420 nm peak intensity be-
comes stronger. It may be explained that quite a part of the Ag+ sur-
rounding the seed crystals is reduced to form nanospheres rather than
G. Hu, et al.
Fig. 3. UV–vis spectra of AgNPs prepared with different AgNO3 concentration.
grow on the surfaces of the crystals to form nanotriangles at high
AgNO3 concentration. In these cases, the size of the silver nanotriangles
becomes smaller slightly.
3.4. The effect of the mole ratio of vc/Ag+ on the morphology
The theoretical mole ratio of Vc to AgNO3 is 2:1 according to the
above equation (1). What is the impact of the change in the mole ratios
of Vc to AgNO3 on the morphology? We prepared AgNPs with different
Vc concentration by holding the same AgNO3 concentration and their
UV–vis spectra are shown in Fig. 4. Some AgNPs colloidal solutions do
not display the absorbance peak at ~350 nm in Fig. 4, which is similar
to the absorption peaks of silver nanorods. The difference in spectra can
attribute to a close side-by-side arrangement of the formed nano-
triangles [48] and it can be observed that some silver nanotriangles are
arranged side by side in a close fit rather than a loose array in Fig. 6(d).
When the mole ratio of Vc to AgNO3 is high (25:1–40:1), the wave-
length of the long wave absorbance peaks red-shifts gradually with a
decrease of the mole ratio and it may indicate that the size of silver
nanotriangles is increased. While their mole ratios are low (5:1–20:1),
both the absorption peaks appear in the long-wave region and their
corresponding half-peak breadths are similar. It may imply that the
prepared nanotriangles have similar size and size distribution, and
there are significant differences comparing to the case of high mole
ratios of Vc to AgNO3.
The formation of silver nanotriangles belongs to anisotropic growth.
Fig. 4. UV–vis spectra of AgNPs prepared with different mole ratios of Vc to
AgNO3: (1) 40:1, (2) 35:1, (3) 30:1, (4) 25:1, (5) 20:1, (6) 15:1, (7) 10:1, (8)
5:1.
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Current Applied Physics 19 (2019) 1187–1194
When the mole ratio of Vc to AgNO3 is high (25:1–40:1), many active Vc
molecules promote the reaction rate, which is not good for the aniso-
tropic growth of seed crystals. In this case, the particle size of the na-
notriangles is comparatively small. The reaction rate gets slow with a
decrease of the mole ratio, which is favorable to form bigger nano-
triangles. Thus, the UV–vis spectra as shown in Fig. 4 (Line 1–4) show
an obvious red shift with the decrease of the mole ratio. While their
ratios are low (5:1–20:1), there are relatively few active Vc molecules
and the reaction rate becomes slow, which is beneficial to anisotropic
growth. In this case, the decreased mole ratio does not much affect the
size or shape of the nanoparticles efficiently and the formed nano-
triangles have similar UV–vis spectra as shown in Fig. 4 (Line 5–8).
3.5. The effect of seed concentration on the morphology
Fig. 5 is the UV–vis spectra and TEM images of AgNPs prepared with
different seed concentrations. From Fig. 5(a), when the concentration of
seed colloidal solution is 0.045 mM, the formed colloidal solution
mainly displays a strong absorption peak centered at ca. 420 nm, which
indicates the prepared nanoparticles are mainly nanospheres. While the
seed concentration decreases to 0.023 mM, the main absorption peak is
also a single peak with unsymmetrical peak profiles but the λmax of the
absorption peak red-shifts to 458 nm, which means the formed nano-
particles are bigger nanoparticles but there is asymmetric spherical
structure in shape, which are called as near nanospheres or quasi-
spherical nanoparticles [47]. The shoulder peak centered at ca. 350 nm
is the characteristic absorption peak of silver bulk materials, implying
the formation of lots of silver quasi-spherical nanoparticles [49]. With
the seed concentration of 0.011 mM, the strong absorption peak (i.e.,
the long-wave peak) red-shifts to ca. 500 nm and a new absorption peak
centered at ca. 420 nm appears beside the 350 nm peak, which implies
some nanotriangles have formed. The corresponding TEM image shows
the sizes of the prepared nanotriangles are in the range of 70–80 nm as
shown in Fig. 5(b). When the seed concentration reduces from 0.011 to
0.0055 mM, the λmax of the absorption peak at long-wave direction red-
shifts from 496 to 550 nm. It means the formation of bigger nano-
triangles and its corresponding TEM image in Fig. 5(c) shows that the
sizes of nanotriangles are of 110–120 nm. With a very low concentra-
tion of seed concentration, i.e., 0.0022 mM, the long-wave peak red-
shifts to 622 nm and the half-peak breadth is relatively wide, which
shows the formation of polydisperse AgNPs. In Fig. 5(d), the nano-
triangles size obtained at this seed concentration is larger than that of
other concentrations and some other associated nanoparticles, such as
quasispherical nanoparticles and nanorods, can be found. The TEM
images confirm that the formed AgNPs are composed of big and small
nanotriangles as well as some nanoparticles with other morphologies.
3.6. Separation of silver nanotriangles from the mixed AgNPs
As a simple and facile technique, the seed-mediated growth method
is commonly applied to prepare nanomaterials on a large scale.
However, some associated particles are unavoidable in the formation of
target nanoparticles. As a result, the nanoparticles prepared by a seed-
mediated growth method must proceed separation treatment to obtain
the target nanoparticles with higher uniform morphology. Some effec-
tive methods were introduced to separate gold or silver triangle-like
nanoparticles [35,50]. The mixed nanoparticles were separated with
our method to obtain silver nanotriangles.
In a typical case, AgNPs were prepared by adding 0.0022 mM seed
colloidal solution and then were separated by our previously published
method [35]. In Fig. 6(a), the original colloidal solution displays three
peaks (~350, ~420 and ~630 nm) and the characteristics of these
three peaks are in accordance with the absorbance peaks derived from
silver nanotriangles. From Fig. 6(a), it was observed that the intensity
of the absorption peak at ~ 420 nm was higher, which means that there
was additional contribution derived from the associated nanoparticles,
G. Hu, et al.
Fig. 5. (a) UV–vis spectra of AgNPs prepared with different seed concentrations and typical TEM images of silver nanotriangles corresponding three seed con-
centrations: (b) 0.011 mM, (c) 0.0055 mM, (d) 0.0022 mM.
that is, the resonance absorption of silver nanospheres and the trans-
verse plasmon resonance of silver nanorods [51].
The deductions on the morphology of the formed nanoparticles are
confirmed by the further SEM and TEM analysis directly. The SEM
image of original AgNPs in Fig. 6(b) shows that the obtained nano-
particles consist of truncated triangular AgNPs and a few quasi-sphe-
rical and rod-like nanoparticles. The supernatant colloidal solution
contains 30–50 nm nanospheres as shown in Fig. 6(c), and it is con-
sistent with its UV–vis spectrum that has only one absorbance peak at
about 420 nm. Fig. 6(d) is the SEM image of precipitate and it shows
that the nanotriangles are in a loose arrangement to expose their edges,
which may be the reason that precipitate displays three absorbance
peaks.
From Fig. 6(d), the nanoparticles in the precipitate are mainly na-
notriangles with higher uniform shape and particle size, although fewer
associated quasi-spherical and rod-like nanoparticles emerge in the
target nanotriangles. TEM image as shown in Fig. 6(d) displays that
nanotriangles are in the size of 52–64 nm and the average size of the
total particles in the image is about 60 nm (the particle size is analyzed
by the software of Digital Micrograph Demo).
3.7. The possible formation mechanism of silver nanotriangles
The role of CTAB can be roughly divided into two aspects: One is a
template role and the other is selective adsorption on seed crystals. In
the case of the selective adsorption on seed crystals, seed crystals
should break their face-centered cubic symmetry firstly and then grow
in an anisotropic way with CTAB selective adsorption on crystal facets.
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Current Applied Physics 19 (2019) 1187–1194
Johnson et al. prepared gold nanorods in CTAB system and reported
that CTAB molecules were bound more strongly to the {100} edge than
the {111} end face of seed crystals, with the consequence of the for-
mation of rod-like nanoparticles [52]. It was also found that reporter
molecules could be selectively immobilized at the tip of gold nanorods
[53].
When preparing AgNPs by using the improved seed crystals, we
found the surface plasmon resonance of the formed nanoparticles
showing three typical absorption peaks (~350, ~420 and ~630 nm, as
shown in Fig. 6(a)), corresponding to the out-of-plane quadrupolar re-
sonance, the in-plane quadrupole resonance and the in-plane dipole
resonance of silver nanotriangles, respectively. The formed nano-
particles were triangular silver nanoplates (nanotriangles) by the sur-
factant-assisted shape separation (as shown in Fig. 6(d)). From the UV
spectra shown in Figs. 1 and 5(a), the shapes of the formed nano-
particles change from nanospheres to quasi-spherical nanoparticles and
to nanotriangles finally. Thus, we think that the intermediate structure
of silver nanotriangles should be the quasi-spherical nanoparticles.
In Fig. 7(a), the formed nanoparticles are mainly quasi-spherical
nanoparticles prepared at the seed concentrations of 0.023 mM, besides
a few silver nanorods. In addition, a few truncated triangular silver
nanoplates can be observed in this case. Only by decreasing the seed
concentrations, should the main ingredients of AgNPs be silver nano-
triangles, as shown in Fig. 5(b)–(d). In addition, there was a stacking of
tiny nanoparticles around the intermediate as shown in the red circles
and the tiny nanoparticles, derived from the reduction of Ag+ in the
growth solution, are available to the formation of silver nanotriangles
by the stacking of tiny nanoparticles and selective growth of silver seed
G. Hu, et al.
Fig. 6. (a) UV–vis spectra of the original colloidal solution of AgNPs, (b) SEM image of original AgNPs, (c) TEM image of AgNPs in the supernatant, and (d) SEM
image of AgNPs in the precipitate.
Fig. 7. (a) TEM image shows that the formed nanoparticles are mainly quasi-
spherical nanoparticles at the seed concentrations of 0.023 mM, (b) Magnified
TEM image shows that formed triangle-like nanoparticles are composed of
many tiny nanoparticles.
crystals. In Fig. 7(b), the magnified TEM image shows that formed
triangle-like nanoparticles are composed of many tiny nanoparticles
(there is a difference in grayscale for the nanotriangles as shown in the
blue circles) other than silver monocrystals.
In our case, the seed crystals were prepared by a high concentration
of reduction. As a result, the seed crystals should not have a relatively
complete crystallographic plane and face-centered cubic symmetry re-
sulting from the stacking faults and thus substantially caused the se-
lective adsorption of CTAB molecules on the special crystal facets. The
characteristics of the seed crystals induce the new formed tiny nano-
particles stacking around the seed crystals for their selective growth on
the special crystal planes without or with little adsorption of surfactant
molecules. Along with Ag+ reduction and the selective growth of silver
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Current Applied Physics 19 (2019) 1187–1194
crystals, silver seed crystals grow into silver nanotriangles with the help
of the CTAB selective adsorption.
From Fig. 6(d), it is also observed that the formed nanotriangles are
truncated triangular silver nanoplates that are mixed up with few as-
sociated quasi-spherical and rod-like nanoparticles. It is believed that
the three ends of silver nanotriangles might be oxidized to form silver
ions by the oxidizing action of Br−/O2 existing in the CTAB reaction
system [54], due to the relative higher specific surface area. As a result,
the nanotriangles obtained from the selective stacking of the new tiny
nanoparticles and the oriented growth of silver seed crystals gradually
changed to truncated triangular silver nanoplates.
A few quasi-spherical may be from the irregular stacking and non-
oriented growth without the catalysis of silver seed crystals and a few
rod-like nanoparticles may be from the template effect of CTAB rod-like
micelles for the longitudinal oriented growth of the seed crystals. Based
on experimental results observed in our experiments and the existing
reports, a possible formation mechanism of silver nanotriangles by
using the improved silver seed crystals is proposed as shown in Fig. 8.
4. Conclusions
In this work, a facile and effective seed preparation strategy has
been proposed to prepare silver nanotriangles by a modified seed-
mediated growth method in CTAB system. The effects of some key
factors on the morphologies and particle sizes of the formed nano-
triangles have been studied systematically. The morphology and the
particle size of silver nanotriangles were easily controlled by adjusting
the corresponding reaction conditions. It was found that CTAB
G. Hu, et al.
Fig. 8. A schematic illustrating the possible formation mechanism of silver nanotriangles by using our silver seed crystals.
concentration and seed concentration were related with both the
morphology and the particle size and NaOH concentration, AgNO3
concentration and the mole ratio of Vc/Ag+ mainly affected the particle
size. Silver nanotriangles were easily formed at following conditions:
the concentrations of CTAB, NaOH, AgNO3 and silver seeds were be-
tween 0.10 and 0.035 M, 0.90 and 18.0 mM, 0.27 and 0.45 mM, 0.011
and 0.0022 mM, respectively. The mole ratio of Vc to AgNO3 was be-
tween 20:1 and 5:1. The optimum conditions were found to be 0.05 M
CTAB, 0.90 mM NaOH, 0.405 mM AgNO3 and 0.022 mM seed as well as
the mole ratio of Vc to AgNO3 was 5:1.
Silver tiny nanoparticles were observed to stack around the triangle-
like nanoparticles in the formation process of silver nanotriangles. We
suggested that the silver seeds prepared by this study existed stacking
faults and thus substantially caused the selective adsorption of CTAB
molecules on the special crystal facets. The formation of silver nano-
triangles was due to the selective stacking of the new tiny nanoparticles
and the oriented growth of silver seed crystals gradually changed to
truncated triangular silver nanoplates. As associated nanoparticles ap-
peared in the target nanoparticles prepared by the seed-mediated
growth method, some AgNPs with other morphologies were also ob-
served. The formation of associated nanoparticles may be due to the
irregular stacking and non-oriented growth or longitudinal oriented
growth of silver seed crystals.
Acknowledgment
The project was supported by the National Natural Science
Foundation of China (Grant no. 81071254) and the Natural Science
Foundation of Guangdong Province, China (Grant
no.10451051501004706).
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