Article

pubs.acs.org/cm

Competitive Effect in The Growth of Pd−Au−Pd Segmental

Nanorods
Li Xu, Kai Wang, Bo Jiang, Wei Chen, Fangyan Liu, Hui Hao, Chao Zou, Yun Yang,*
and Shaoming Huang*
Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027, P. R. China
*
S Supporting Information

ABSTRACT: Growing other metals on decahedral nanoparticles (NPs) is an important

approach to synthesize segmental multimetallic nanorods (NRs) with a penta-fold twinned
(PFT) structure. So far, only limited such structures, e.g., Ag−Au−Ag and Pd−Ag or Pd−
Cu PFT NRs, can be realized by this approach. To explore more multimetallic structures is
important for both synthesizing more multimetallic NRs with a PFT structure for various
potential applications and understanding their formation mechanism. Herein, we report
the synthesis of Pd−Au−Pd segmental NRs with controlled sizes by growing Pd atoms on
Au decahedra using hexadecyltrimethylammonium bromide (CTAB) and I− as growth
modifiers. The growth mechanism of Pd−Au−Pd PFT NRs was investigated
systematically. It was figured out that the growth of Pd−Au−Pd NRs was determined
by two competitions (CTAB competes with I− in complexing with H2PdCl4 and in
adsorbing on Au decahedra). It is also demonstrated that Au−Pd−Au NRs had higher
activity than commercial Pd/C catalyst in electrocatalytic oxidization of formic acid.

1. INTRODUCTION In practice, seeded growth is affected by all the above factors

Noble nanomaterials attract much attention due to their
potential applications in catalysis, biosystems, and optics.1−7
Their properties are remarkably dependent on compositions
and structures,8−12 which are related to their synthetic
methods. Numerous methods have been developed for
synthesizing nanostructures with controlled compositions and
structures.13−20 Among them, seeded growth is one of the most
effective ways and used extensively.13−20 In seeded growth, the
nature of the final products is primarily determined by several
factors including capping agent, growth kinetics, thermody-
namics, the structure of seed, and lattice mismatch.21−31 A
capping agent usually facilitates the preferential growth along a
given orientation through selectively adsorbing on some
facets.21−25 Growth kinetics affects the growth rate along
various directions, and therefore, its modification can change
the product shape.29−31 In the growth determined mainly by
thermodynamics, products always have low surface free energy;
that is to say, they are generally coated by three low index facets
({111}, {100}, {110}), for example, {111}-faceted decahedron
and octahedron.19,31 The effect of seed is always crucial, and
mostly it only allows forming a nanostructure with the same
crystalline feature as itself.32,33 For example, single-crystalline
Au NPs seeds cause the formation of single-crystalline Au
NRs,24 and PFT Au NPs seeds facilitate the growth of PFT Au
NRs.34 Lattice mismatch has vital roles when seed and
deposited metal are chemically different.33 It determines the
interface area connecting two metals. Large lattice mismatch
favors a small interface area, and therefore, dumbbell-like
nanostructures are always generated in this case. Core@shell
nanostructures usually form when lattice mismatch is small.33
together and one factor may be dominant under certain
conditions.
PFT nanostructure is one important family of nanomateri-
als.34−60 It has been demonstrated that noble nanocatalysts
with PFT structures exhibit high selectivity in some organic
reactions.40 Four PFT nanostructures (NR, nanowire, decahe-
dron, and icosahedron) are commonly observed.34−50 Among
them, PFT NRs and decahedra generate extensive interest
owing to their unique structure and property in the past several
decades.34−47 Decahedron and PFT NRs are similar structur-
ally. Decahedron can be considered as a PFT NR with 0
longitudinal length. For this reason, decahedral NPs often serve
as seeds to induce selective growth along ⟨110⟩ for preparing
PFT NRs.34−48 For example, Song and co-workers prepared
PFT Au NRs by using Au decahedra as seeds.36 Kitaev’s group
used Ag decahedra as seeds and prepared PFT Ag NRs.19,34,35
More interestingly, this strategy also allows preparing bimetallic
segmental PFT NRs. Song’s group first reported the synthesis
of segmental Ag−Au−Ag PFT NRs, and then other groups
achieved similar results.37,38,41−46 Wang’s group and others also
reported the syntheses of segmental NRs by using PFT Au NRs
and nanobipyramids as seeds.42,43,45,49 Using Au decahedra as
seeds, our group also synthesized Ag−Au−Ag and Ag−Au
segmental NRs via growth kinetics control.45
So far, the studies of PFT segmental NRs were mainly
focused on Au and Ag due to their similar growth behavior.40
Received: July 16, 2016
Revised: September 16, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.chemmater.6b02871

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The growth of Ag on Au decahedra can be well controlled
easily, and no strict growth conditions are needed. For example,
Ag−Au−Ag NRs can be prepared at temperatures ranging from
room temperature to 260 °C and various capping agents work
well in the growth of Ag−Au−Ag PFT NRs, such as CTAB,
poly(vinylpyrrolidone) (PVP), or poly(diallyldimethyl-
ammonium chloride) (PDDA).41−46 For the deposition of
other metals on Au decahedra, it is rarely studied. It is relatively
difficult to achieve similar growth with the above procedure
because metal change can lead to a significantly different
growth mode.46 We tried to prepare segmental PFT Pd−Au−
Pd NRs with the same method used for synthesizing Ag−Au−
Ag NRs, but failed.45
To achieve the synthesis of segmental M−Au−M PFT NRs
(M is non-Ag) using Au decahedra as seeds, growth conditions
should be adjusted with metal change accordingly, particularly
the substances used to induce preferential growth because their
affinity with the metal atom varies with metal. For example,
AgNO3 is always introduced for controlling the growth of Au
nanostructures because Ag-based substances can selectively
adsorb on a given facet.36,45,49,61 However, this strategy is
ineffective to non-Au nanostructures owing to the lack of
affinity between them. As another example, halide ions (Cl−,
Br−, I−) are widely used in the preparations of noble
nanostructures because they have affinity with noble atoms
and ions.62−69 For different metals, they favor forming various
shaped nanostructures. For example, I− often facilitates the
formation of {100}-faceted Pd nanostructures because of its
selective adsorption on Pd(100).58 However, I− favors the
growth of Au nanoplates bounded by small {110} facets and
large {111} facets because it selectively adsorbs on Au
(111).70,71 This demonstrates that the facet on which I−
selectively adsorbs changes with the metal. Recently, Xia and
co-workers reported that Pd decahedra acted as seeds and Pd−
Ag NRs could be prepared under high temperature.47 Very
recently, they further reported an interesting result that this
protocol could also be used to grow segmental PFT Pd−Cu
NRs.48 The synthetic conditions of Pd−Ag NRs and Pd−Cu
NRs are considerably different, although decahedral Pd seeds
used in two cases have no clear difference, indicating that the
growth environment should be adjusted accordingly when the
deposited metal changes.
In short, the growth mode on a decahedron varies with metal
and growth environment. Investigating the growth of different
metals on decahedra is very desirable and important for both
synthesizing various metals heterostructures and revealing the
growth law of such structures. Furthermore, detailed study
about their growth mechanism is helpful for designing and
optimizing synthetic conditions for preparing nanostructures as
required. In this study, the growth of Pd on Au decahedra was
systematically investigated and segmental PFT Pd−Au−Pd
NRs were successfully prepared. The result shows that the
growth mechanism of Pd−Au−Pd PFT NRs is significantly
different from that of Ag−Au−Ag PFT NRs. The growth of
Ag−Au−Ag PFT NRs is mainly governed by kinetics.45
However, for the growth of Pd−Au−Pd NRs, it is mainly
determined by two competitions (CTAB competes with I− in
complexing with H2PdCl4 and in adsorbing on Au decahedra).
Au NPs are often used as seeds for constructing various
nanostructures.62,63 Besides, CTAB and KI are widely used
growth-directing agents in the preparations of noble nanoma-
terials.58,64,65 Therefore, the mechanistic study herein is
significant to the design of both Pd/Au nanostructures and
B DOI: 10.1021/acs.chemmater.6b02871
Article
other metal nanomaterials. Besides, this strategy also allows
synthesizing a variety of Pd/Au nanostructures (Pd−Au−Pd
NRs with controlled length, Pd nanocubes, Au@Pd NPs). The
catalytic performance of Pd−Au−Pd NRs was also tested. In
comparison with commercial Pd/C and carbon-supported Pd
nanocubes, they exhibited high catalytic activity and might be
used as potential anode catalysts in fuel cells.
2. EXPERIMENTAL SECTION
Chemicals. Silver nitrate (AgNO3), potassium iodide (KI),
chloroauric acid (HAuCl4), diethylene glycol (DEG), and PDDA
(MW = 400 000−500 000, 20 wt % in H2O) were bought from Sigma-
Aldrich. PVP (MW = 58 000), CTAB, ascorbic acid (AA), and
palladium chloride (PdCl2) were obtained from J&K Chemicals. No
further purifications were needed before all of these chemicals were
used.
Preparation of Segmental Pd−Au−Pd NRs. The preparations
of H2PdCl4 solution and Au decahedra with different sizes followed
the methods reported previously (details can be seen in the
Supporting Information).46,66
In a typical preparation of Pd−Au−Pd NRs, 1 mL of purified Au
decahedra was mixed with 2.5 mL of CTAB aqueous solution (0.1 M).
0.5 mL of H2PdCl4 (0.01 M), 0.5 mL of KI (0.04 M), and 0.5 mL of
AA (0.02 M) were then successively introduced into the above
solution. In order to keep the solution volume (5 mL) constant in
each preparation, a calculated amount of water was added. After the
resulting solution was stirred variously for 5 min, it was sealed and
then put into a 90 °C water bath. After 30 min, the solution was
cooled down to about 30 °C. A similar procedure to Au decahedra was
used to purify the Pd−Au−Pd NRs under 2000 rpm centrifuging
speed (see the Supporting Information for details).45
Characterization. For transmission electron microscopy (TEM),
high-resolution transmission electron microscopy (HRTEM), energy-
dispersive spectroscopy (EDS), high-angle annular dark-field
(HAADF), and scanning transmission electron microscopy EDS
(STEM-EDS) characterizations, the purified colloid was deposited on
copper grids with thin carbon film, which was then dried for 20 min
under an infrared lamp. After water was removed completely, the dried
sample was observed with a 200 kV JEOL 2100F with an attached
EDS and STEM detector. Scanning electron microscopy (SEM) (FEI
Helios nanolab 600i) was used to obtain high-resolution SEM images.
A Shimadzu 2450 UV−vis spectrophotometer was used to record the
UV−vis spectra of solutions at room temperature. For X-ray
photoelectron spectroscopy (XPS) analysis, the purified colloid was
dropped on a clean wafer and dried fully at 50 °C. XPS data were
obtained with an ESCALab220i-XL electron spectrometer from VG
Scientific using 300 W Al Kα radiation. The base pressure was about 3
× 10−9 mbar. The binding energies were referenced to the C 1s line at
284.6 eV from adventitious carbon.
3. RESULTS AND DISCUSSION
The structure of Au decahedral seeds has been described in
detail previously.46 Through adjusting growth kinetics, it was
easy to achieve the selective growth of Ag or Au on Au
decahedra along ⟨110⟩, resulting in the formation of PFT Ag−
Au−Ag NRs or Au nanobipyramids, respectively.45,46 However,
the preparation of segmental Pd−Au−Pd NRs was not realized
with the same procedure. We noticed that the growth of {100}-
faceted Pd nanostructures always needed introducing I−
because it can selectively adsorb on Pd(100).58 For PFT
NRs, their sides are coated by 5 {100} facets. Possibly, I− might
be helpful to the growth of segmental Pd−Au−Pd PFT NRs.
Therefore, I− was introduced, and the result shows that I− is
effective in facilitating the growth of PFT Pd−Au−Pd NRs.
After synthetic optimization, segmental Pd−Au−Pd PFT NRs
with high quality were prepared successfully (Figure 1A,B). The
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Figure 1. (A, B) HAADF images of Pd−Au−Pd PFT NRs prepared in
a standard procedure (inset in (B) is the HAADF image of Au
decahedra). (C) SEM image of NR’s end. (D) Schematic illustration of
growing Pd−Au−Pd PFT NR.
HAADF images give a clear segmental structure because of the
contrast difference between Au and Pd. For PFT Ag−Au−Ag
NR and other PFT one-dimensional nanostructures, two ends
are bounded by 5 {111} facets in most cases.45,46 However, the
large-magnification SEM image clearly shows that the ends of
Pd−Au−Pd NRs are bounded by 15 {111} facets (Figure
1C,D). The crystal edges on the ends are highly broadened.
HRTEM images show that the {111} facets are curved rather
than planar (Figures S1 and S2). More experiments are needed
to understand how this morphology formed, and further study
is underway.
The structure of Pd−Au−Pd NRs was further investigated
with TEM and STEM-EDS. The TEM and HRTEM images of
segmental Pd−Au−Pd NRs are shown in Figure 2A−D.
Clearly, the transverse length of Pd−Au−Pd NRs is almost
equal to that of Au decahedra, demonstrating that Pd growth
occurred almost only along ⟨110⟩ (Figure 2A,B). The HRTEM
images show that the Pd segment has good crystal features
(Figure 2C,D). Besides, the corresponding fast Fourier
transform pattern demonstrates that the Pd NR has a PFT
structure (inset in Figure 2C).46 In order to confirm the
segmental structure, STEM-EDS technology was used to
analyze the elemental distribution of NRs (Figure 2 E−H).
In Figure 2E, the Au segment is lighter than the Pd ones
because it has a higher atomic number than Pd. Elemental
mapping also gives a similar result (Figure 2F,G). The
compositional line profiles of a single Pd−Au−Pd NR further
confirm the above structure (Figure 2H).
Effect of Seed. Au decahedra are decisive in the growth of
Pd−Au−Pd NRs. In a comparative experiment, no Au
decahedra were introduced and other conditions were kept
unchanged. Only monodispersed Pd nanocubes formed, and no
rodlike products were observed (Figure S3A,B). The HRTEM
image shows that the interplane distance is 0.200 nm, which is
assigned to Pd(100) (Figure S3C,D). It is well-known that the
Pd nanocube is coated by 6 {100} facets, so it can be known
that I− selectively adsorbs on Pd(100). Previously, two groups
reported the syntheses of PFT Pd NRs using foreign ions (Ag+
or Cu2+).40,58 In our system, no such foreign metal ions were
used. Therefore, the formation of Pd−Au−Pd PFT NRs is
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Article
Figure 2. (A−D) TEM and HRTEM images of segmental Pd−Au−Pd
NRs (inset in (C) is the corresponding fast Fourier transform pattern).
(E−G) HAADF image and elemental mapping patterns of a single
Pd−Au−Pd NR. (H) Cross-sectional compositional line profiles of a
single Pd−Au−Pd NR.
owing to the PFT Au decahedral seeds. Single-crystalline Au
NRs and truncated Au octahedral NPs were also employed as
seeds, which induced the formation of {100}-faceted nano-
cuboids and nanocubes, respectively (Figures S4−S7). No PFT
Pd−Au−Pd NRs were observed. This further demonstrates the
importance of Au decahedral seeds in the growth of PFT Pd−
Au−Pd NRs.
The effect of seed size was also investigated. Herein, Au
decahedra with 30, 40, and 60 nm edges were used as seeds.
Although all of them could induce selective growth along
⟨110⟩, only seeds with edges smaller than 40 nm were effective
in inducing the formation of uniform Pd−Au−Pd NRs (Figure
3A,B). For seeds with 60 nm edges, the length of NRs distinctly
reduced, and meanwhile, pure Pd NPs formed due to self-
nucleation (Figure 3C). LaMer theory can be applied to
account for this.46 Because the mass of Au decahedra is equal in
three cases, the total surface atom number reduces with size,
increasing due to the size effect; that is, the active sites on
which Pd atoms deposit decrease with size increasing. As a
result, Pd atoms are overmany relative to the active sites when
large decahedra acted as seeds. Therefore, self-nucleation
occurred and pure Pd NPs formed because active sites were
relatively insufficient. For small-sized seeds, their active sites are
enough for the deposition of Pd, and therefore, self-nucleation
can be avoided.46 Besides, the activity of large-sized seeds is
low, compared with small-sized ones (Figures S8 and S9). This
reduces the tendency that Pd atoms deposit on large-sized
seeds, and relatively increases self-nucleation. Therefore, when
60 nm Au decahedra acted as seeds, Pd NPs formed.
Effect of H2PdCl4 Amount. It is well-known that growth
kinetics allows adjusting product shape and structure.28−31 For
example, the structure of Ag/Au NRs can be tuned by
modifying the growth kinetics of Ag on Au decahedra.46 Core@
shell and dumbbell-like NPs can be prepared through
controlling the growth kinetics of Ag or Au on Pd NPs.29,30
Changing the concentration of the precursor is one approach to
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Figure 3. TEM and HRTEM images of Pd−Au−Pd NRs prepared
using Au decahedra with different sizes as seeds: (A1−A2) 30 nm;
(B1−B2) 40 nm; (C1−C2) 60 nm. The arrows in (C2) mark the pure
Pd nanocubes (KI/H2PdCl4 = 4; AA/H2PdCl4 = 2; H2PdCl4/Au = 8;
reaction temperature was 90 °C).
control growth kinetics.30 In our system, it was found that the
concentration of Pd precursor had little effect on product
structure. In three cases (the molar ratios of H2PdCl4 and Au
were 4, 8, and 12), only symmetrical Pd−Au−Pd NRs formed
and no core@shell NPs were observed (Figure 4A−C). The
Figure 4. TEM and HRTEM images of products prepared using
different ratios of H2PdCl4 and Au in a standard procedure (KI/
H2PdCl4 = 4; AA/H2PdCl4 = 2; reaction temperature was 90 °C):
(A1−A2) 4; (B1−B2) 8; (C1−C2) 12.
amount of Pd precursor mainly affected the longitudinal length
of NRs rather than shape. When the molar ratio of H2PdCl4
and Au was 4, Pd−Au−Pd NRs with 80 nm longitudinal length
formed (Figure 4 A1−A2). If the molar ratio of H2PdCl4 and
Au was raised to 8, the longitudinal length of products
increased to 140 nm (Figure 4B1−B2). With the molar ratio of
H2PdCl4 and Au increasing to 12, the length of Pd−Au−Pd
NRs became nonuniform (Figure 4C1−C2), indicating that the
growth on Au decahedra was inhomogeneous. Besides, self-
nucleation also occurred, and consequently, pure Pd NPs
formed. This is because the high concentration of Pd precursor
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accelerated the formation rate of Pd atoms, so the
concentration of Pd atoms increased. Therefore, active sites
became relatively insufficient and caused self-nucleation. This
shows that a right amount of H2PdCl4 is vital to product
monodispersity.
Effect of KI Amount. As discussed above, I− is often used
in the preparation of Pd nanostructures because it can
selectively adsorb on Pd(100).58 The result presented in
Figure S3 also clearly demonstrates this. When no Au
decahedral seeds were used, {100}-faceted Pd nanocubes
formed, indicating that I− selectively adsorbed on Pd(100).
Hence, the adjustment of KI should lead to product structure
and shape change. Therefore, the effect of KI amount was
further investigated. When no KI was added, only Au@Pd NPs
formed and no rodlike products were observed (Figure
5A1,A2). Besides, the products have no regular shape. This
Figure 5. TEM and HRTEM images of products prepared using
different molar ratios of KI and H2PdCl4 in a standard procedure
(H2PdCl4/Au = 6; AA/H2PdCl4 = 2): (A1−A2) 0; (B1−B2) 1; (C1−
C2) 2; (D1−D2) 4.
indicates that no preferential growth occurred and all surface
atoms on Au decahedra surface acted as nucleation sites when
without KI; that is, only CTAB was unable to induce selective
growth along ⟨110⟩. If the molar ratio of KI and H2PdCl4 was
0.5, Au@Pd NPs still dominated (Figure 5B1,B2). However,
some Pd−Au−Pd PFT NRs were clearly observed, implying
that the growth along ⟨110⟩ occurred. With the ratio of KI and
H2PdCl4 increasing to 2, most of the products were Pd−Au−
Pd NRs and a few were Au@Pd NPs (Figure 5C1,C2). Further
raising the KI concentration (KI/H2PdCl4 = 4), the yield of
Pd−Au−Pd PFT NRs further increased (Figure 5D1,D2). The
above observations clearly demonstrate that I− preferentially
adsorbs on Pd(100) and favors the Pd growth along ⟨110⟩. If
the ratio of KI and Pd was increased to 6, the reduction of
Pd(II) to Pd(0) became very slow and no Pd growth on Au
decahedra occurred within 3 h (Figure S12).67 This will be
discussed later in the Mechanistic Study section.
As is well-known, growth selectivity is often determined by
the surface free energy distribution on the seed surface. The
atoms on a facet with high surface free energy act as nucleation
sites and induce preferential growth here. Theoretically, a Au
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decahedron is bounded by 10 {111} facets. In fact, it also has 5

small {100} facets due to the imperfect crystal shape.
Compared with {100}, {111} is relatively inactive, and hence,
the growth on {100} should be faster than that on {111}
theoretically. This is not consistent with our results. This
difference could be caused by the selective adsorption of I− on
Pd(100). Once Pd is deposited on the {100} of Au decahedra,
Pd(100) is relatively densely covered by I− due to the strong
affinity between Pd atoms on (100) and I−. Therefore, the
surface free energy of {100} reduced. As a result, {111} was
more active than {100}, and consequently, the growth on
{111} was favored. When no KI was added, although CTAB
has affinity with Pd atoms, it was not strong enough to reduce
the surface free energy of {100}. Therefore, the surface free
energy of {100} was close to that of {111} and all surface atoms
of Au decahedra served as nucleation sites, causing the
formation of Au@Pd NPs. When the KI concentration was
low, I− was not enough to cover all {100}, so growth along
⟨100⟩ also occurred, resulting in the formation of Au@Pd NPs
partly.
Mechanistic Study. In our system, CTAB and I− were
introduced as growth-directing agents. CTAB and I− have been
demonstrated to have affinity with noble metals or ions (Ag,
Au, Pd).68 That is why they are often used as growth-directing
agents.68−72 It is widely believed that I− has stronger affinity
with noble substances than CTAB. Theoretically, Almora-
Barrios and co-workers also demonstrated that I− had much
stronger affinity with noble metals than Br− and Cl− by
performing density functional theory simulations.73 Korgel and
co-workers investigated how I− affected the growth of Au NRs
in aqueous CTAB solution.69 They found that I− still had a
significant effect on the growth of Au NRs; even a trace amount Figure 6. UV−vis spectra and optical photographs of (A1−A2)
of I− was present in high concentration of CTAB. We found H2PdCl4, (B1−B2) H2PdCl4 + KI, (C1−C2) H2PdCl4 + CTAB, (D1−
that the product prepared in two cases (KI/H2PdCl4 = 0.05 and D2) H2PdCl4 + CTAB + KI. The concentrations of the above agents
were equal to that in the standard procedure of Pd−Au−Pd NRs.
without KI) had no distinct difference (Figure S13 and Figure
5A). Thereby, compared with Korgel’s system, the significance
After analyzing the above results, it could be known that, in
of I− is not that much due to metal difference in our system.
the solution (CTAB + H2PdCl4 + KI), both I− and CTAB were
Here, two competitions are believed to govern the growth of
involved in complexing with H2PdCl4 simultaneously. If only I−
Pd−Au−Pd NRs. (I) CTAB competes with I− in complexing
complexed with H2PdCl4, its color and UV−vis spectrum
with H2PdCl4. (II) CTAB competes with I− in adsorbing on Au
should be close to that of the solution (KI + H2PdCl4).
decahedra. In order to demonstrate the competitive complex- Provided that only CTAB was involved in complexing with
ing, a UV−vis spectrometer was used to record the absorption H2PdCl4, two solutions (CTAB + H2PdCl4 + KI, CTAB +
change of four solutions. For the pale yellow H2PdCl4 solution H2PdCl4) should have similar UV−vis absorption and color.
(Figure 6A2), it has a strong absorption peak at 235 nm (Figure However, the UV−vis absorption and color of solution (CTAB
6A1). After KI was added into the above H2PdCl4, the + H2PdCl4 + KI) were different from these of other solutions.
absorption at short wavelength decreased and the peak shifted This supports the conclusion that both CTAB and I− were
to 223 nm. A clear absorption at 362 nm was also observed involved in the complexing with H2PdCl4 simultaneously.
(Figure 6B1). Meanwhile, the solution color changed from pale When the concentrations of CTAB and H2PdCl4 were kept
yellow to dark brown (Figure 6B2). This indicated that unchanged, the solution color and UV−vis spectra changed
complexing between I− and H2PdCl4 occurred. If CTAB rather with KI because the complexing between H2PdCl4 and I−
than KI was added to the H2PdCl4 solution, the absorption at increased (Figure S14). Similarly, when KI and H2PdCl4 was
short wavelength increased significantly and the peak moved to constant, the concentration of CTAB also affected the
250 nm (Figure 6C1). Besides, a relatively weak absorption absorption and color (Figure S15). This confirms the presence
peak appeared at 340 nm. The resulting solution was sandy of the competitive complexing.
beige and different from the H2PdCl4 solution (Figure It is known that I− has stronger complexing capacity than
6A2,C2). Therefore, it is easy to know that CTAB complexed CTAB.73 The complexing of CTAB with H2PdCl4 might be
with H2PdCl4 in this solution. Once simultaneously introducing attributed to its high concentration, which strengthened its
KI and CTAB to H2PdCl4 solution, the absorption peak at competitiveness (in the standard preparation, CTAB was 0.05
short wavelength shifted to 260 nm and the intensity reduced M and I− was only 0.004 M). This competitive complexing also
clearly (Figure 6D1). An intensive absorption at 330 nm was could be demonstrated by the CTAB-concentration-dependent
observed, and moreover, the solution became brownish (Figure reduction rate. As discussed above, noble metal ions and halide
6D2). ions can form stable complexes, for example, AgCl. After
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H2PdCl4 complexes with CTAB or I−, the reduction potential
of Pd/[CTAB-H2PdCl4] or Pd/[I−-H2PdCl4] is low, compared
with Pd/H2PdCl4. As a result, it is difficult to reduce them to
atoms, compared with free metal ones. As is well-known, the
complexing capacity of CTAB is weaker than that of I−;69,71−74
it is reasonable that the reduction potential of Pd/I−-H2PdCl4 is
lower than that of Pd/CTAB-H2PdCl4.68,69 That is to say, it is
easy to reduce Pd(II) in CTAB-H2PdCl4 to atom, compared
with that in I−-H2PdCl4. That is why no Pd growth was
observed when a high concentration of KI was present (Figure
S12). Therefore, the competitive complexing should allow
adjusting the reduction rate of Pd(II) to Pd(0) through
changing the concentration of CTAB.
In order to evaluate the reduction rate of Pd(II) to Pd(0), a
UV−vis spectrophotometer was used to record time-dependent
absorption. As shown in Figure 6D, for the solution containing
KI, CTAB, and H2PdCl4, the most distinctive absorption was
observed at about 330 nm. Therefore, it could be used to
evaluate the concentration change of H2PdCl4, that is,
reduction rate. In the case of 0.025 M CTAB, the absorption
peak disappeared after 40 min (Figure 7A1), indicating that the
Figure 7. TEM images of products prepared using different
concentrations of CTAB and corresponding time-dependent UV−vis
spectra (H2PdCl4/Au = 10, AA/H2PdCl4 = 2; KI/H2PdCl4 = 4): (A1−
A3) 0.025 M; (B1−B3) 0.05 M; (C1−C3) 0.1 M.
complete consummation of H2PdCl4 needed 40 min. With
CTAB concentration increasing to 0.05 M, 20 min was needed
to consume all H2PdCl4 (Figure 7B1). When 0.1 M CTAB was
added, the reduction rate further increased and no H2PdCl4 was
detected after 15 min (Figure 7C1). Clearly, a high
concentration of CTAB facilitated the reduction of Pd(II) to
Pd(0) because the CTAB-H2PdCl4 complex increased and
reduction was accelerated. In case of low concentration of
CTAB, I−-H2PdCl4 complex dominated and reduction rate
decreased. This result further confirms the competitive
complexing.
Interestingly, the CTAB concentration also had important
impacts on product shape and structure. When the CTAB
concentration was 0.025 M, most of the products were Pd
nanocubes with single-crystalline feature and others were PFT
Pd−Au−Pd NRs (Figure 7A2,A3). This suggests that self-
nucleation of Pd dominated and the selective growth of Pd on
Au decahedra was not favored. Because Pd atoms grew into
nanocubes, the Pd atoms depositing on the Au decahedra
F DOI: 10.1021/acs.chemmater.6b02871
Article
surface relatively decreased. As a result, the Pd−Au−Pd NRs
are very short. Once increasing CTAB to 0.05 M, self-
nucleation was not observed and long Pd−Au−Pd NRs formed,
clearly indicating that high concentration of CTAB facilitated
the preferential growth of Pd on Au decahedra (Figure
7B2,B3). Further increasing the CTAB concentration had no
significant effect on product quality (Figure 7C2,C3).
The above results clearly suggest that high concentration of
CTAB preferred the selective growth of Pd on the Au
decahedra surface and low concentration of CTAB facilitated
self-nucleation. As is well-known, both CTAB and I− can
adsorb on the Au atom,68−72 so it is believed that CTAB
competes with I− in adsorbing on Au decahedra here. Varying
the CTAB concentration can affect the competition. Compared
with CTAB, I− has very strong affinity with Au decahedra and
can greatly reduce their activity of surface atoms.68 The
inactivation does not facilitate the selective growth of Pd on Au
decahedra (Scheme 1). When CTAB molecules were added,
some of them adsorbed on Au decahedra through competing
with I−. As a result, the adsorption of I− on Au decahedra
reduced and this increased the surface activity of Au decahedra.
Therefore, the selective growth of Pd on Au decahedra was
facilitated (Scheme 1). When CTAB was low, it could not
compete with I− and the adsorption of I− on Au decahedra was
dominant (Figure 7A2 and Scheme 1). In this case, Au
decahedra were coated by I− densely and their activity
decreased. For this reason, the growth of Pd on Au decahedra
was not favored, so self-nucleation occurred and led to the
formation of pure Pd nanocubes. When CTAB was increased, a
large number of CTAB molecules increased their competitive-
ness, so the absorption of CTAB increased and the adsorption
of I− on Au decahedra relatively reduced. More active sites were
exposed (Figure 7 B2,C2 and Scheme 1). Therefore, the
growth of Pd on Au decahedra was promoted.
For confirming the competitive adsorption on Au decahedra,
a set of experiments similar to these (Figure 7A,B) were carried
out except for that no AA was added. After heating for 10 min
at 90 °C, Au decahedra were collected via centrifugation and
then purified using water for three times to remove excess
CTAB and I−. The I and Br elements adsorbing on Au
decahedra were analyzed with XPS. Although XPS is unable to
provide surface composition precisely, the relative intensity
change of I and Br signals recorded from the one same sample
could be used to roughly evaluate the evolution of the
elemental ratio on Au decahedra. In two cases, both I and Br
elements were detected on the surface of Au decahedra (Figure
8A1,A2,B1,B2). In the case of 0.05 M CTAB, the intensity of
I3d was about 10 times stronger than Br3d (Figure 8A1,A2).
When CTAB was decreased to 0.025 M, the intensity of I
element increased drastically and almost 80 times higher than
Br element (Figure 8B1,B2). This demonstrates that low
concentration of CTAB facilitated the adsorption of I− on Au
decahedra. Meanwhile, the Au4f signal also changed with CTAB
due to the strong affinity between I− and Au. In the case of
0.025 M CTAB, I− strongly adsorbed on the surface of Au
decahedra and formed a dense layer. As a result, no signal of Au
element could be detected because of the small depth of
penetration of XPS technology (Figure 8B3). When CTAB was
increased to 0.05 M, the I− adsorbing on Au decahedra greatly
reduced, and therefore, a clear Au4f signal was detected (Figure
8A3). This also confirms that the adsorption of I− on Au
decahedra decreases with CTAB increasing.
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials Article

Scheme 1. Influence from the Competitive Adsorption of I− and CTAB on Au Decahedron

Figure 8. (A1) I3d (inset is the enlarged pattern of area marked by the dashed box), (B1) Br3d, (B3) Au4f XPS spectra recoded from Au decahedra
treated with 0.05 M CTAB solution. (B1) I3d, (B2) Br3d, (B3) Au4f XPS spectra recoded from Au decahedra treated with 0.025 M CTAB solution.

Hexadecyltrimethylammonium chloride (CTAC) is another
capping agent widely used in the preparation of noble
nanostructures.24 Compared with CTAB and I−, CTAC has
weak affinity with noble substances.67 Here, CTAC was used to
replace CTAB for further investigating the competitive
adsorption. The results show that short Pd−Au−Pd NRs
formed only when CTAC was 2 M (Figure S16A1−A3). In the
cases of 1 and 0.5 M, the selective growth of Pd on Au
decahedra was blocked and lots of Pd nanocubes formed,
indicating that the self-nucleation of Pd was dominant (Figure
S16B,C). This agrees with the above results (Figures 7 and 8).
Because CTAC has much weaker affinity with Au decahedra
than I−, they cannot compete with I− in adsorbing on Au
decahedra even at a high level. As a consequence, the
adsorption of I− on Au decahedra dominated and caused self-
nucleation. When CTAC was increased to 2 M, a large number
G DOI: 10.1021/acs.chemmater.6b02871
of them enhanced their competitiveness and increased their
adsorption on Au decahedra, so the adsorption of I− reduced
relatively. For this reason, Au decahedra were activated and the
preferential growth of Pd on their surfaces was promoted.
When 0.5 M halide-ion-free PVP was used, most of the
products were still decahedra and almost no significant growth
on Au decahedra surface was observed within 30 min (Figure
S17). Meanwhile, lots of small Pd NPs formed due to self-
nucleation. Because PVP has no halide ion, it is unable to
reduce the amount of I− on Au decahedra through competitive
adsorption. As a result, I− adsorbed on Au decahedra surface
densely, covered almost all active sites, and blocked the
selective growth of Pd. In this case, self-nucleation was
facilitated. This further demonstrates the competitive adsorp-
tion.
Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials
Figure 9. (A) Cyclic voltammograms of carbon-supported Pd−Au−Pd NRs, carbon-supported Pd nanocubes, and commercial Pd/C in a N2-
saturated 0.5 M HClO4 solution at 50 mV s−1. (B) Cyclic voltammograms of carbon-supported Pd−Au−Pd NRs, carbon-supported Pd nanocubes,
and commercial Pd/C in a N2-saturated 0.5 M H2SO4 and 0.5 M formic acid solution at 100 mV s−1.
Electrochemical Measurement. Pd-based nanomaterials
are potential anode catalysts in formic acid fuel cells.58 Noble
nanostructures with twinned planes have been demonstrated to
have better performance in catalysis because lots of crystal
faults are present.58 The prepared PFT NRs have 5 large
twinned planes, so they might be good anode catalysts in fuel
cells. Here, electrocatalytic oxidization of formic acid in alkaline
solution was chosen to investigate the activity of prepared NRs
(Figure S19A). In order to evaluate their performance,
commercial Pd/C and carbon-supported Pd nanocubes
catalysts were also tested (Figure S19B,C). Before electro-
chemical measurement, a CO-stripping procedure was used to
remove surface adsorbates (I− or others) and activate surface
atoms. After CO-stripping, clear hydrogen adsorption/
desorption peaks were recorded in the range from −0.3 to
0.1 V in three cases, indicating that material surfaces were
cleaned (Figure 9A). The oxidization peak current intensity of
Pd−Au−Pd NRs was 0.43 mA/cm2. For carbon-supported Pd
nanocubes, the oxidization peak current was about 0.10 mA/
cm2. In the case of commercial Pd/C, the oxidization peak
current intensity was close to 0.05 mA/cm2 (Figure 9B). It is
well-known that a nanocube is a typical nanostructure with a
single-crystalline feature. The HRTEM image of commercial
Pd/C shows that they are also 2−5 nm single-crystalline NPs.
The prepared Pd−Au−Pd NRs are PFT nanostructures.
Therefore, it is believed that the prepared NRs have high
activity due to the present twinned plane compared with the
other two catalysts. Besides, segmental noble NRs often have
unique plasmonic properties.1,43 The segmental Pd−Au−Pd
NRs might have such plasmonic properties and hold potential
applications in surface-enhanced Raman scattering.75
4. CONCLUSION
We have demonstrated that Pd−Au−Pd PFT NRs can be
synthesized through using Au decahedra as seeds. In the growth
of Pd−Au−Pd PFT NRs, Au decahedra determine the structure
of the product and the selective adsorption of I− on Pd(100)
facilitates the growth along ⟨110⟩. Besides, two competitions
(CTAB competes with I− in complexing with H2PdCl4 and in
adsorbing on Au decahedra) play important roles in the growth
of Pd−Au−Pd PFT NRs. The complexing between CTAB and
H2PdCl4 leads to fast growth of Pd NRs. However, the
complexing of KI and H2PdCl4 reduces the growth rate. The
H DOI: 10.1021/acs.chemmater.6b02871
Article
competitive adsorption of CTAB and I− on Au decahedra
determines the growth mode of Pd. High concentration of
CTAB reduces the adsorption of I− on Au decahedra, enhances
the activity of Au decahedra, and promotes the formation of
Pd−Au−Pd PFT NRs. Low CTAB concentration results in the
increasing of the adsorption of I− on the Au decahedra surface
and the reducing of their surface activity. Consequently, self-
nucleation is facilitated. For KI and CTAB are widely used
growth-directing agents in the synthesis of noble nanostruc-
tures, it is believed that our results could be helpful to the
controlled preparation of noble nanomaterials and the
modulation of nanomaterial properties.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.6b02871.
The preparation of Au decahedra, the syntheses of other
nanostructures, electrochemical tests, and the TEM and
HAADF images of products prepared using various
conditions (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: bachier@163.com (Y.Y.).
*E-mail: smhuang@wzu.edu.cn (S.H.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the NSFC (21471117, 21173159,
and 51420105002). The help from Dr. Guoyong Fang in
discussing the adsorption of halide ions on metal facets is
gratefully acknowledged.
■
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