Article

Cite This: Langmuir 2017, 33, 12254-12259 pubs.acs.org/Langmuir

Iodide-Switched Deposition for the Synthesis of Segmented Pd−Au−

Pd Nanorods: Crystal Facet Matters
Siyu Liu,† Wenxin Niu,‡ Shaik Firdoz,‡ and Weiqing Zhang*,†
†
Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies,
School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China
‡
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117576, Singapore
*
S Supporting Information
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ABSTRACT: Segmented metallic nanorods with well-defined shapes

and controllable components play an important role on the systematic
Downloaded via CAPES ADMIN ACCOUNT on April 5, 2020 at 15:31:17 (UTC).

investigation of their shape-dependent catalytic, electric, and plasmonic

properties of metal nanostructures. Unfortunately, the shape and
composition of segmented nanorods are difficult to be precisely
controlled via colloidal methods. Here, we reported the growth of Pd−
Au−Pd bimetallic heterostructures by using Au 5-fold twinned
bipyramids (BPs) as seeds, with KI as a structure-directing reagent.
Through a series of control experiments we revealed that two
parameters were identified as critical factors for the growth of
segmented Pd−Au−Pd nanorods. First, 5-fold twinned Au BPs with
low-index end facets and high-index side facets function as a unique
template for directed growth. Second, iodide can switch the deposition
of Pd on the Au BPs. A high concentration of iodide is believed to block the high-index facets of the Au BPs and lower the
reaction kinetics to promote the selective growth of two Pd segments on the Au BPs. As a result, uniformed segmented Pd−Au−
Pd nanorods were obtained. The segmented nanorods exhibit intense extinction in the near-IR range and could be a potential
candidate for plasmon-based biological applications such as thermal therapy.

■ INTRODUCTION
One dimensional (1D) metal nanostructures have attracted
considerable attention because of their aspect-ratio-dependent
optical and electric properties.1−3 The aspect ratio of 1D
nanostructures is of paramount importance to finely tune the
longitudinal surface plasmon resonance wavelength (LSPR)
and dramatically enhance the polarizability of metals. As a novel
type of 1D metal nanostructures, segmented nanorods with
orderly assembled different metal segments provide richer
properties for desirable applications. For example, Park et al.
synthesized two-component segmented nanorods consisting of
Au and Ni components and observed that Ni segments play a
relaying role in the surface plasmon coupling of Au segments.4
Later they found intraparticle surface plasmon coupling in Au−
Ag segmented nanorods, which shows two independent
transverse modes from the Au and Ag segments and the
collective appearance of longitudinal surface plasmons (LSP)
modes.5 The exceptionally tunable properties of segmented
nanorods render them useful candidates for practical
technology applications, such as in situ testing of catalytic
reactions, ultrasensitive detection,6,7 biochemical sensors,8−10
and optoelectronic devices.11,12
While segmented metal nanorods have drawn considerable
attention due to their potential applications, the controllable
synthesis of segmented metal nanorods with precisely
controlled components is still very challenging. To date,
segmented metal nanorods can be precisely fabricated via
selective electrodeposition using AAO template but limited
with low yield.4,5,13 To obtain segmented nanorods with large
scale, developing an alternative method with wet chemistry is
essential.14−16 Very recently, Wang et al. realized anisotropic
overgrowth of metals on Au nanorods with the help of site-
selective silica coating.16 Liang et al. also reported the selective
growth of AgCdSe at one end and both ends or on the side
surface of Au nanorods by changing the pH value of the
reaction solution.14 Unfortunately, the shape and facets of
segments grown on Au nanorods are not well defined in these
works, which may play an important role on the systematic
investigation of the shape- and composition-dependent
catalytic, electric, and plasmonic properties of these nanostruc-
tures.17−23 Therefore, it is highly desirable to develop an
effective colloidal approach for the synthesis of segmented
nanorods with well-defined facets. In this work, Pd−Au−Pd
segmented nanorods with well-defined facets have been
obtained from Au bipyramids (BPs) in the presence of KI
and hexadecyltrimethylammonium bromide (CTAB). By
adding different amounts of KI, the Pd−Au bimetallic
nanostructures evolved from core−shell nanostructures to
Received: July 18, 2017
Revised: August 29, 2017
Published: October 6, 2017

© 2017 American Chemical Society 12254 DOI: 10.1021/acs.langmuir.7b02497

Langmuir 2017, 33, 12254−12259
Langmuir Article

segmented nanorods. The formation mechanisms of the

segmented Pd−Au−Pd nanorods were investigated, with a
focus on the unique crystal structure of the BP seeds and the
facets-selective deposition enabled by iodide.

■ EXPERIMENTAL SECTION
Chemicals. Diethylene glycol (DEG, Sigma-Aldrich), ethylene
glycol (EG, Sigma-Aldrich), poly(diallyldimethylammonium chloride)
(PDDA, 20 wt %, Mw = 200 000−350 000, Sigma-Aldrich), 1,5-
pentanediol (PD, Aldrich), chloroauric acid trihydrate (HAuCl4·3H2O,
Alfa Aesar), silver nitrate (AgNO3, Sigma-Aldrich), palladium(II)
chloride (PdCl2, Alfa Aesar), hydrochloric acid (HCl, 37%, Merck),
hexadecyltrimethylammonium bromide (CTAB, TCI), polyvinylpyr-
rolidone (PVP, average Mw = 55 000, Sigma-Aldrich), L-ascorbic acid
(AA, Sigma-Aldrich), potassium iodide (KI, Fluka), and sodium
borohydride (NaBH4, Sigma-Aldrich) were used without further
purification. H2PdCl4 solution (10 mM) was prepared by dissolving
17.73 mg of PdCl2 in 10 mL of HCl solution (20 mM) at 100 °C.
Synthesis of Au Seeds. Au BPs were synthesized according to a
literature report.24 In a typical synthesis, PDDA (0.2 mL) and EG (10
mL) were added into a 20 mL vial and mixed under magnetic stirring
at room temperature for 5 min. Then HAuCl4 (18.8 μL, 0.5 M),
AgNO3 (10 μL, 0.5 M), H2PdCl4 (62.5 μL, 10 mM), and deionized
(DI) water (430 μL) were subsequently added into the above mixture.
After 10 min this mixture was capped tightly and heated in an oil bath
at 140 °C for 12 h under constant stirring. The resulting Au BPs were Figure 1. (a) Growth of Pd−Au−Pd segmented nanorods with flat
washed with acetone and DI water. The synthesis details of 5-fold tips from Au BPs with the help of KI. (b−d) TEM and FESEM of Pd−
twinned and single-crystalline Au nanorods can be found in the Au−Pd segmented nanorods with a flat tip obtained by adding 0.5 mL
Supporting Information. of 0.1 M KI solution. (e−g) HAADF-STEM image and EDX mapping
Synthesis of Au−Pd Bimetallic Nanostructures. In a typical a single Pd−Au−Pd segmented nanorod. (h) UV−vis extinction
synthesis, 0.5 mL of 0.1 M KI solution was added to 5 mL of 0.1 M spectra of (i) Au BPs seeds and (ii) Pd−Au−Pd segmented nanorods.
CTAB solution kept at 60 °C. A 125 μL amount of 10 mM H2PdCl4
solution and 15 μL of as-synthesized seed Au BPs solution were then
added. Finally, 50 μL of freshly prepared 0.1 M ascorbic acid solution length of the segmented nanorods is 213 nm. The average
was added. The solution was mixed thoroughly and then left width of the Pd end, which is 34 nm, is smaller than the
undisturbed in a water bath at 60 °C for 12 h. The reaction was equatorial width of the Au BPs, which is 37 nm (Figure S1 in
terminated by centrifugation at 6000 rpm for 5 min. The precipitates Supporting Information). In addition, there is an apparent joint
were washed twice with DI water and redispersed in DI water. Control between Pd parts and Au BP, which is close to the boundary of
experiments were also conducted using different amounts of KI. high-index side facets and low-index end facets. SEM images in
Similar synthetic procedures were conducted for the coating of Pd on Figure S2 and Figure 1d show that the middle part of the
5-fold twinned Au nanorods and single-crystalline Au nanorods.
segmented nanorods is wider than its two ends, which indicates
Characterization. Transmission electron microscopy (TEM)
images, high-resolution TEM (HRTEM) images, energy-dispersive the selective deposition of the Pd atom on the low-index end
X-ray spectroscopy (EDX) spectra, high-angle annular dark field facets over the high-index side facets. In some Au−Pd
(HAADF), and selected-area electron diffraction (SAED) were segmented nanorods, the shape of Au BPs is not axisymmetric
acquired using a JEOL JEM-2100F and Talos F200X operating at because the twin boundary of Au BPs is not fully symmetric
200 kV. Scanning electron microscopy (SEM) images were taken and parallel to the growth axis.27,28 The segmented structure is
using a JEOL JSM-6700F operating at 20 kV. UV−vis spectra were also confirmed with EDX analysis, which reveals that each
recorded using a Shimadzu UV-1601 spectrometer with plastic nanorod is composed of a center BP and two segmented Pd
cuvettes of 1 cm path length at room temperature.

■
RESULTS AND DISCUSSION
Recently, Au BPs are popular as growth seeds to synthesize
bimetallic nanostructures because they possess not only the 5-
fold twinned crystalline structure but also high-index side facets
and low-index end facets.1,24−26 This unique structure of BPs
may favor the selective deposition of the second metal on their
facets if the deposition on different facets can be controlled.
When Au BPs are used as seeds to grow the Pd atoms in the
presence of CTAB and KI, Pd atoms reduced by ascorbic acid
(AA) selectively deposit on the twin boundary of low-index end
facets of Au BPs rather than the lateral facets of BPs and then
grow along the twin plane of the Au BP seeds (as shown in
Figure 1a). TEM images clearly show that Pd−Au nanorod is
composed of a Au BP in the center and two segmented Pd
nanorods on two ends (Figure 1b and 1c). When 125 μL of 10
mM H2PdCl4 is added into the growth solution, the average
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ends (Figure 1e−g). The low-magnification TEM and SEM
images show the segmented nanorods were obtained with good
monodispersity and high yield (Figure S2a and Figure 1b).
UV−vis extinction spectra show that LSPR of Au BPs strongly
red shifted from 690 to 1060 nm after the formation of Pd−
Au−Pd segmented nanorods (Figure 1h). This is because the
selective deposition of Pd atoms along the longitudinal
direction increases the aspect ratio.26,29
TEM and the corresponding HAADF-STEM images in
Figure 2a and 2b clearly reveal the overall segmented structure
as well as the nanoscale distribution of the Pd and Au in a
nanorod. The HAADF-STEM image shows a distinct
segmented nanorod structure: the bright and gray parts are
attributed to the Au and Pd elements, respectively. Pd−Au
joints are very obvious and evidenced by HRTEM and
HAADF-STEM images obtained from area i labeled in Figure
2c and 2d. The inset in Figure S2b shows that the Au−Pd
segmented nanorods are terminated with flat end facets. The
DOI: 10.1021/acs.langmuir.7b02497
Langmuir 2017, 33, 12254−12259
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Figure 2. (a,c) TEM and (b,d) HAADF-STEM images of a Pd−Au segmented bimetallic nanorod with a flat tip. (c1) HRTEM of Pd−Au
connection part obtained at the area i in c). (c2) HRTEM image of Pd segment obtained at the area ii in c). The measured d spacing of 0.14 nm
matches with that of the (220) plane of Pd. (d1) HAADF image of Pd-Au connection part obtained at the area i in d).

Figure 3. TEM images of Pd−Au−Pd segmented nanorods obtained by terminating reaction at different reaction times: (a and b) 15 min, (c and d)
1 h, (e and f) 2 h, and (g and h) 6 h.

flat end facet of Pd−Au−Pd segmented nanorod is further
proved by SAED. Since Au BPs have a 5-fold twinned structure
along the ⟨110⟩ growth direction,27,28 the flat end facets of the
segmented nanorods should be {110} facets of fcc Pd.26 The
SAED recorded from one end of the nanorod in Figure S3
exhibits a ⟨110⟩ growth direction. The lattice planes along the
growth direction of the nanorod obtained from area ii in Figure
2c also show a d spacing of 0.14 nm, matching well with the
(220) plane of fcc Pd (Figure 2c). On the basis of these results,
including SEM, HRTEM, and SAED studies, it can be
concluded that the as-synthesized segmented nanorods are
enclosed by {110} end facets. The appearance of {110} end
facets of the segmented nanorods can be attributed to the
stabilization effect of CTAB and KI. It has been reported that
the {110} Pd facets are more stable relative to the {111} Pd
facets in the presence of CTAB and KI.30 However, Huang et
al. recently reported the synthesis of Pd−Au nanorods using Au
decahedron seeds in the presence of CTAB and KI. In their
work, the ends of Pd−Au nanorods are terminated by 15 {111}
facets.2 The different observation could be explained by the
structure difference of Au BP and decahedron seeds. To
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investigate further, Au decahedra are used as growth seeds in
our growth system. SEM and TEM images show that the Pd−
Au nanorods are formed and their ends are also bounded with
15 {111} end facets (Figure S4). This result confirms the effect
of the seed structures on the final morphologies of bimetallic
nanoparticles. For the 5-fold twinned Pd segmented ends, the
side facets can be indexed to {100} facets, which are parallel to
the growth axis. Once nascent {100} facets appeared, I− prefers
to adsorb on these {100} facets of Pd nanocrystals to stabilize
them.2,31 In addition, the CTA+ cationic head groups can also
form a stable bilayer on an iodide adlayer because of
electrostatic attraction. Therefore, the adsorption of CTA+
cations plays a synergistic effect on the stability of Pd {100}
side facets.32,33
The structural evolution of the Pd−Au−Pd segmented
nanorods was followed by a terminating reaction at different
reaction times. In the early reaction period, the deposition of
Pd atoms started at the end facets (Figure 3a and 3b). With the
reaction proceeding, Pd atoms continue to deposit at the ends
of Au BPs, leading to irregular particles connected to the ends
of Au BPs (Figure 3c and 3d). When additional Pd atoms are
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deposited, the size and shape of Pd particles at the ends of Au
BPs became larger and more regular (Figure 3e and 3f). At this
stage of reaction the Pd atoms start to cross the boundary of
high-index side facets and low-index end facets. This may be
ascribed to either the deposition of Pd with a slow rate or the
diffusion of Pd atoms during the reaction. Eventually, Pd−Au−
Pd segmented nanorod with the two regular Pd ends on a Au
BP was formed (Figure 3g and 3h). The regular Pd ends are
finally bounded by {110} facets perpendicular to the growth
axis.29,32
The formation mechanisms of the segmented Pd−Au−Pd
nanorods were investigated with a focus on the selective
deposition enabled by facets preferential adsorption of I− and a
slow reaction kinetics caused by the strong complexing capacity
of I− with H2PdCl4. It is well known that halide ions (I−, Br−,
and Cl−) are used extensively to control the shapes of noble
metal nanoparticles due to their different facet affinity.34,35 In
addition, halide ions, especially I− ions, are strong complexing
agents. When I− ions complex with H2PdCl4, the reaction
kinetics of Pd2+ ions reduction is largely decreased due to the
low reduction potential of Pd/PdI42−.2,31 A slow reaction
kinetics usually facilitates the preferential deposition on a
specific facets of growth seeds.36,37 To understand the effects of
I− ions on the formation of segmented nanorods, the structural
evolution of the Au−Pd bimetallic nanostructures was followed
by adding different amounts of KI to the growth solution. A
clear shape evolution of as-synthesized nanocrystals with
different KI concentration was observed (Figure 4). In the
Figure 4. TEM images of Au−Pd bimetallic nanorods obtained by
adding different amounts of KI: (a) 0 μL, (b) 25 μL, 1 mM, (c) 25 μL,
0.1 M, and (d) 0.5 mL, 0.1 M.
absence of KI, Au@Pd core−shell nanorods were obtained
(Figure 4a). In this case, the deposition of Pd occurred on all
surfaces of Au BP seeds. When 25 μL of 1 mM KI solution was
added (KI/H2PdCl4 = 1:50), peanut-like nanocrystals were
obtained (Figure 4b). It can be seen clearly that with the
introduction of I− ions the selective deposition of Pd on the
{111} end facets gradually started. As the concentration of KI is
very low, the effects of I− ions on both the facet surface energies
and the reaction kinetics are not significant. With more KI
solution introduced into growth solution (KI/H2PdCl4 = 2:1),
dumbbell-shaped nanocrystals were obtained (Figure 4c). In
this case, more newly reduced Pd atoms are deposited on the
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Article
end of BPs and more defined facets of Pd appeared compared
with the structures as shown in Figure 4b. Once 0.5 mL of 0.1
M KI was added (KI/H2PdCl4 = 40:1), the Pd−Au−Pd
segmented nanorods with well-defined facets were obtained
(Figure 4d). In the presence of a high concentration of KI, the
growth of Pd atoms rarely occurred on the high-index facets of
Au BPs, suggesting the high-index facets of Au BPs are more
inert for Pd deposition than that of {111} end facets. Besides,
the full complexing of I− with H2PdCl4 gives rise to very slow
reaction kinetics, which plays an important role on the Pd-
selective deposition. These results demonstrate that the
introduction of KI in the growth solution can block the high-
index facets of Au BPs and slow down the reaction kinetics to
promote the selective deposition of Pd on the low-index facets
of BP seeds.38
The unique structure of Au BPs also plays an important role
on the selective deposition of Pd atoms on the seeds. To
demonstrate the importance of seeds, 5-fold twinned Au
nanorods and single-crystalline nanorods (Figure S5 and S6)
were also explored as seeds for the growth of Au−Pd bimetallic
nanostructures. When 5-fold twinned nanorods enclosed only
by low-index {111} and {100} facets were used as growth seeds
and other reaction conditions were kept the same, the obtained
heterostructures were Au@Pd core−shell nanorods. The TEM
image clearly shows the formation of Au@Pd core−shell
nanostructures, confirming that Pd deposited on the whole
surface of 5-fold twinned nanorods (Figure 5a and 5b). This
Figure 5. TEM images of Au@Pd nanorods obtained by using other
Au nanocrystals as growth seeds. Volume of 0.1 M KI solution was
kept at 500 μL: (a and b) 5-fold twinned nanorods and (c and d)
single-crystalline nanorods.
result demonstrates that the structure effect of Au BPs with
both low- and high-index facets is crucial for the selective
deposition of Pd. In addition, the Au@Pd core−shell nanorods
grew in length but maintained a constant width, which is the
same observation with Au−Pd segmented nanorods. In both
cases, the deposition of Pd along the twin plane rather than on
the lateral surface of 5-fold twinned Au nanocrystals will
minimize the lattice strain.39 Compared with 5-fold twinned Au
nanocrystals, single-crystalline Au nanocrystals may result in the
different deposition behavior of the second metal in order to
minimize the total strain energy. Once single-crystalline
nanorods were used as seeds instead of Au 5-fold twinned
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Langmuir
structures, the Au@Pd core−shell nanorods with a rectangular
shape were observed (Figure 5c and 5d). This deposition of Pd
occurred on both the end and the side facets of the single-
crystalline Au nanorods, which is different from that of Pd on
the 5-fold twinned Au nanocrystals.
Generally, the high-index side facets of Au BPs possess a high
lattice distortion energy, the second metal, like Ag, will
preferentially deposit on them. In this study, Pd atoms
selectively deposited on the low-index end facets of Au BPs
instead of the high-index side facets when Au BPs were used as
growth seeds in the presence of CTAB and KI. In short, the
formation of Pd−Au−Pd segmented nanorods with {110} end
facets can be primarily attributed to the following reasons: (1)
selective adsorption of I− ions on high-index side facets of Au
BPs reduces their surface energy and blocks the preferential
deposition of Pd atoms;26,40 (2) the complexing reaction of I−
ions with H2PdCl4 significantly lowers the reduction kinetics of
Pd2+ ions, which is beneficial for the preferential deposition of
Pd atoms;2,31,36,37 (3) selective adsorption of I− ions on nascent
{100} facets stabilizes the {110} end facets and {100} side
facets of Pd segmented parts;2,31 (4) the unique structure of Au
BP provides new variables for experimentally maneuvering the
deposition model of second metals on the surface of growth
seeds.26
■
CONCLUSION
In summary, Pd−Au−Pd segmented nanorods with flat tips
have been synthesized using Au BPs as growth seeds. Through
a series of control experiments we revealed that two parameters
were identified as critical factors for the growth of segmented
Pd−Au−Pd nanorods. It is found that in the presence of a high
concentration of I− ions Pd atoms selectively deposited on the
low-index end facets of Au BPs but not on the high-index side
facets, while Pd atoms grew on the whole surface of other Au
seeds including 5-fold twinned nanorods and single-crystalline
nanorods. The switched deposition of Pd atoms were attributed
to the unique structure of Au BPs, selective adsorption of I−
ions, and slow reaction kinetics. These results manifest the role
of seed structures on the growth modes of second metals,
which is important for gaining mechanistic insights into the
controlled synthesis of bimetallic heterostructures with control-
lable components and tailorable optical properties.
■
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.7b02497.
Experimental details for the synthesis of Au growth
seeds; additional TEM, HRTEM, and SAED images
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: zhangweiqing@tjut.edu.cn.
ORCID
Shaik Firdoz: 0000-0002-6821-174X
Weiqing Zhang: 0000-0002-1324-2944
Notes
The authors declare no competing financial interest.
12258
Article
■ ACKNOWLEDGMENTS
We are thankful for financial support from the Tianjin
Municipal Science and Technolo gy Comm ission
(16JCYBJC41600) and the Fundamental Research Funds of
Tianjin University of Technology.
■
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12259 DOI: 10.1021/acs.langmuir.7b02497

Langmuir 2017, 33, 12254−12259