Article

pubs.acs.org/Langmuir

Direct Synthesis of Palladium Nanocrystals in Aqueous Solution with

Systematic Shape Evolution
Shu-Ya Liu, Yuan-Ting Shen, Chun-Ya Chiu, Sourav Rej, Po-Heng Lin, Yu-Chi Tsao,
and Michael H. Huang*
Department of Chemistry and Frontier Research Center on Fundamental and Applied Science of Matter, National Tsing Hua
University, Hsinchu 30013, Taiwan
*
S Supporting Information

ABSTRACT: Palladium octahedra, truncated octahedra, cubocta-

hedra, truncated cubes, and nanocubes with sizes of tens of
nanometers have been synthesized in an aqueous mixture of
H2PdCl4 solution, cetyltrimethylammonium chloride (CTAC)
surfactant, KBr solution, dilute KI solution, and ascorbic acid
solution at 35 °C for 30 min. By tuning the amount of dilute KBr
solution introduced, particle shape control can be achieved. Adjusting the volumes of the Pd precursor and KBr solutions added,
smaller and larger Pd nanocrystals were obtained with excellent shape control. Extensive structural and optical characterization of
these nanocrystals has been performed. Two absorption bands in the ultraviolet region can be discerned for these Pd
nanocrystals. Concave Pd cubes can also be prepared. Pd cubes were found to grow at a faster rate than that for the formation of
octahedra. The concentrations of KBr and KI in the solution are so low that spectral shifts were not detected upon their addition
to the solution. The Pd nanocrystals can readily be used for various applications after simple removal of surfactant.

■ INTRODUCTION
Palladium nanostructures are highly useful nanomaterials
because they have been shown to efficiently catalyze organic
coupling reactions such as Suzuki and Sonogashira reactions.1,2
They also catalyze hydrogenation and formic acid oxidation
reactions.3−11 A wide variety of Pd nanocrystal morphologies
has been prepared including rods, plates, and polyhedra.12 With
regard to the examination of facet-dependent catalytic proper-
ties of Pd nanocrystals, it is still necessary to synthesize Pd
nanoparticles exposing specific surface facets such as cubes and
octahedra.13−16 With respect to the synthesis of polyhedral Pd
nanocrystals, an important direction of research is to grow Pd
nanocrystals with systematic shape evolution. This is because
factors controlling the particle shape can be easily identified and
the synthesized nanocrystals are most suitable for facet-
dependent property studies.17,18 Although Au−Pd core−shell
nanocrystals with systematic shape evolution from cubic to
octahedral structures have been achieved, it is still desirable to
grow pure Pd nanocrystals with this series of shape
evolution.1,19 Preparation of Pd cuboctahedra, truncated
octahedra, and octahedra from the oxidative etching of pre-
formed Pd cubes and redeposition of the dissolved Pd ions
have been demonstrated, but this approach is more
complicated.20 Use of poly(vinylpyrrolidone) (PVP) as a
stabilizer in a polyol system may require an additional PVP
removal process.20,21 Further growth of cubic Pd seeds is
successful in producing Pd cubes, octahedra, and rhombic
dodecahedra, but more experimental steps are needed.22−26
More recently, direct synthesis of Pd cubes, octahedra, and
rhombic dodecahedra has been reported, yet the reagents used
and their amounts are less systematic to clearly identify the
factors affecting the particle shape.27,28 Thus, it is still important
to develop a simple and direct method to make Pd nanocrystals
in aqueous solution with tunable shape and size.
In this study, a simple method has been developed for the
direct formation of Pd nanocrystals in aqueous solution with
systematic shape evolution from octahedral to cubic structures
through fine control of the amount of KBr introduced. Particles
with tunable size can be achieved. Concave Pd nanocubes were
also prepared using this method. Formation of different particle
shapes has been shown to be related to their different growth
rates. The importance of addition of tiny amounts of KBr and
KI during particle synthesis has been verified.
■ EXPERIMENTAL SECTION
Chemicals. Palladium(II) chloride powder (PdCl2, 99%, Aldrich),
cetyltrimethylammonium chloride (CTAC, 95%, TCI), L(+)-ascorbic
acid (AA, 99.7%, Aldrich), potassium bromide (KBr, Merck),
potassium iodide (KI, Showa), and hydrochloric acid (HCl, 37%,
Sigma-Aldrich) were used as received. A 10 mM H2PdCl4 solution was
prepared by completely dissolving 0.0178 g of PdCl2 powder in 10 mL
of 20 mM HCl solution.
Synthesis of Palladium Nanocrystals. For the growth of Pd
octahedra, truncated octahedra, cuboctahedra, truncated cubes, and
cubes, 9.175, 9.150, 9.145, 9.135, and 9.125 mL of deionized water
were respectively introduced into sample vials. Subsequently, 0.048 g
of CTAC and 0.7 mL of 10 mM H2PdCl4 solution were added to each
of the sample vials. The vials were kept in a water bath set at 35 °C
throughout the particle synthesis. Then 0, 25, 30, 40, and 50 μL of 1.0
Received: April 14, 2015
Revised: May 31, 2015

© XXXX American Chemical Society A DOI: 10.1021/acs.langmuir.5b01337

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Figure 1. SEM images of (a1−a3) Pd octahedra with average particle sizes of 56, 64, and 69 nm, (b1−b3) truncated octahedra with average sizes of
49, 58, and 61 nm, (c1−c3) cuboctahedra with average sizes of 52, 55, and 60 nm, (d1−d3) truncated cubes with average sizes of 47, 54, and 57, and
(e1−e3) nanocubes with average sizes of 45, 48, and 61 nm. All scale bars are equal to 100 nm.

× 10−3 M KBr solution were introduced to make Pd octahedra,
truncated octahedra, cuboctahedra, truncated cubes, and cubes,
respectively. The vials were left undisturbed in the water bath for 15
min for halide ligand replacement reaction to complete.1 Next, 5 μL of
1.0 × 10−3 M KI solution was introduced, and the solution was left
undisturbed for another 15 min. Finally, 120 μL of 0.05 M AA was
added with thorough mixing, and the mixture was kept in the water
bath for another 30 min to form Pd nanocrystals. The solution color
turned light brown quickly within 30 s of introduction of AA and
became dark brown in 30 min. Finally, the particles were collected by
centrifugation at 4000 rpm for 10 min. The precipitate was centrifuged
one more time with 10 mL deionized water at 4000 rpm for 10 min to
remove the surfactant. Experimental conditions for the formation of
Pd nanocrystals with smaller and larger sizes are given in the
Supporting Information.
Synthesis of Pd Concave Cubes. First, 0.048 g of CTAC, 8.795
mL of deionized water, and 0.7 mL of 10 mM H2PdCl4 solution were
mixed in a sample vial. The vial was kept in a water bath set at 60 °C.
Then 50 μL of 1.0 × 10−3 M KBr solution was introduced, and the vial
was left undisturbed for 15 min. Next, 5 μL of 1.0 × 10−3 M KI
solution was introduced, and the solution was left undisturbed for
another 15 min. After 450 μL of 0.05 M AA was added, the solution
was thoroughly mixed. The mixture was kept in the water bath set at
60 °C for 30 min to form the concave cubes. The particles were
collected by centrifugation at 4000 rpm for 10 min. The precipitate
was centrifuged again with 10 mL of deionized water at 4000 rpm for
10 min.
Instrumentation. Transmission electron microscopy (TEM)
characterization was performed on a JEOL JEM-2100 electron
microscope with an operating voltage of 200 kV. Scanning electron
microscopy (SEM) images of samples were obtained using a JEOL
JSM-7000F electron microscope. Powder X-ray diffraction (XRD)
patterns were recorded on a Shimadzu XRD-6000 diffractometer with
Cu Kα radiation. UV−vis spectra were collected using a JASCO V-670

B DOI: 10.1021/acs.langmuir.5b01337
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spectrophotometer. X-ray photoelectron spectroscopy (XPS) charac-
terization was carried out on a ULVAC-PHI Quantera SXM high-
resolution XPS spectrometer. Data were recorded with a mono-
chromatized Al anode as the excitation source. The C 1s peak was
chosen as the reference peak.
■ RESULTS AND DISCUSSION
In this study, we have developed a method to directly grow Pd
nanocrystals with shape control by mixing an aqueous solution
of H2PdCl4, CTAC surfactant, KBr, KI, and ascorbic acid at 35
°C for 30 min. By simply tuning the volume of 10−3 M KBr
solution from 0 to 50 μL, Pd nanocrystals with systematic shape
evolution from octahedral to cubic structures were obtained.
Figure 1 shows SEM images of the synthesized Pd octahedra,
truncated octahedra, cuboctahedra, truncated cubes, and cubes
(panels a2−e2) with sizes of 64 ± 5, 58 ± 6, 55 ± 5, 54 ± 4,
and 48 ± 2 nm, respectively. Pd particles with high size and
shape control have been produced, such that they readily
formed ordered assembly structures. Figure S1 in the
Supporting Information gives the size distribution histograms
of these nanocrystals. It is also important to be able to tune the
particle dimensions. To make smaller Pd nanocrystals, the
amounts of H2PdCl4, KBr, and KI solutions used have been
reduced. Similarly, the volumes of these same reagents were
increased to enlarge the particle sizes while still maintaining the
particle shapes. Figure 1 also presents SEM images of the
smaller Pd octahedra (average size of 56 nm), truncated
octahedra (49 nm), cuboctahedra (52 nm), truncated cubes (47
nm), and cubes (45 nm) (see panels a1−e1). SEM images for
the larger Pd octahedra (69 nm), truncated octahedra (61 nm),
cuboctahedra (60 nm), truncated cubes (57 nm), and cubes
(61 nm) are also shown in Figure 1 (panels c3−e3). Again,
particles in all these samples are highly uniform in size and
shape. The tiny amount of KI introduced (5 μL of 10−3 M KI)
was found to be critical to the formation of uniform octahedral
Pd nanocrystals and possibly other particle shapes. In the
absence of KI, large platelike structures were produced (see
Figure S2). Iodide, acting as a strong binding ligand, is believed
to bind to the Pd precursor by replacing some of its chloride
ligands, thus affecting the reduction potential and kinetics of
the starting Pd precursor. Interestingly, using the same
condition to make medium-sized Pd cubes, but raising the
volume of ascorbic acid added to 340 and 450 μL and the
reaction temperature to 60 °C, Pd cubes with slight concave
faces were obtained (see Figure S3). Use of a larger amount of
ascorbic acid led to the formation of smaller concave cubes. Pd
concave cubes possess high-index facets and can show an
enhanced catalytic activity.1,29−31 Pd concave cubes with
sharply raised edges and corners have also been reported.32
Further structural characterization of the Pd nanocrystals has
been performed through XRD and TEM analysis. Figure 2
displays the XRD patterns of the medium-sized Pd nanocrystals
with different shapes. An exceptionally strong (200) reflection
peak has been recorded for Pd cubes and truncated cubes due
to their preferential orientation of deposition on the substrate
with their {100} faces parallel to the substrate surface.
Cuboctahedra yield approximately equal intensity for the
(111) and (200) peaks because of their significant {100} and
{111} faces. As expected, octahedra and truncated octahedra
show a strong (111) peak compared to that of the (200) peak
because of their predominant {111} surfaces. TEM character-
ization of the Pd nanocrystals is presented in Figure 3. The
labeled zone axes indicate the viewing directions of the
C DOI: 10.1021/acs.langmuir.5b01337
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Figure 2. XRD patterns of the synthesized Pd nanocrystals with
medium particle sizes. A standard XRD pattern of Pd is also provided.
particles. The selected-area electron diffraction (SAED)
patterns reveal the single-crystalline nature of these nanocryst-
als. Corner truncations of the cuboctahedra and truncated
cubes are clearly identifiable. The concave cubes show slightly
depressed faces. Particles with some size distribution are
observed in the TEM images because a dilute droplet of Pd
nanocrystals was added to a TEM grid. When a drop of
concentrated polyhedral particles is added to a substrate, they
are more likely to assemble with some particle size sorting, as
seen in the SEM images. High-resolution TEM images showing
the lattice fringes of Pd nanocrystals and their d-spacing values
are available in Figure S4, confirming that a Pd octahedron is
bound by (111) lattice planes and a cube is bound by the (200)
planes.
The synthesis of Pd nanocrystals with systematic shape
evolution and tunable size allows a more complete analysis of
their optical properties. Figure 4 presents UV−vis extinction
spectra of the Pd nanocrystal samples. Two absorption bands
can be discerned for these Pd nanostructures. The first band
has a fixed position at 250 nm. With increasing particle sizes,
the second absorption band becomes more red-shifted from
290 nm to beyond 350 nm. For cubic particles with an average
particle size similar to that of octahedral particles, they generally
show a more red-shifted band position, possibly because cubic
particles have a greater volume than octahedral particles.
It is nice to know that simple adjustment of a small volume
of KBr solution introduced is effective at tuning the Pd
nanocrystal morphology. Figure 5 shows photographs of the
solutions as a function of reaction time in the growth of Pd
nanocubes and octahedra. The solution color turns dark more
quickly in the formation of Pd nanocubes than for the growth
of octahedra, showing cubes are produced at a faster rate. Again
formation of nanocrystals of different shapes is related to their
relative growth rates.1,17 Particle growth appears to be
essentially complete within 10 min of reaction, as no further
color change was observed. Figure 6 displays the corresponding
UV−vis spectra of the solutions. The 226 and 286 nm peaks
from the formation of [CTA+]2[PdCl42−] complex decrease
progressively, while the band at around 350 nm from the
formation of Pd particles emerges. The absorbance vs time
plots clearly show that the descending rates of 226 and 286 nm
peaks are appreciably faster in the formation of Pd cubes. The
effectiveness of KBr to tune the Pd particle morphology should
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Figure 3. TEM images of single Pd nanocrystals, their corresponding SAED patterns, and TEM images of the particles over larger areas: (a1−a3) Pd
octahedra, (b1−b3) truncated octahedra, (c1−c3) cuboctahedra, (d1−d3) truncated cubes, (e1−e3) cubes, and (f1−f3) concave cubes.

be due to the partial replacement of chloride with bromide for
the Pd precursor to form [PdBrxCl4−x2−].1,33 Iodide ions should
also replace the chloride ligands, but the volume of KI solution
used is fixed. The reduction potentials of PdBr42− (0.49 V vs
SHE) and PdI42− (0.2279 V) to Pd are lower than that of
PdCl42− (0.59 V).34 The Pd precursors used for the formation
of Pd octahedra contain some iodide ligands, while the Pd
precursors used for the growth of cubes have more bromide
D DOI: 10.1021/acs.langmuir.5b01337
ligands attached. This may explain the relatively faster
reduction rate observed in the growth of Pd nanocubes.
However, the tiny amounts of KI and KBr introduced, and their
simultaneous presence in the solution makes the prediction of
relative particle growth rates difficult.
With the tiny difference in the volume of 10−3 M KBr
solution added to control the particle shape, it is interesting to
see if any spectral shift can be detected. Figure 4f presents UV−
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Figure 4. UV−vis extinction spectra of the synthesized Pd (a) octahedra, (b) truncated octahedra, (c) cuboctahedra, (d) truncated cubes, and (e)
cubes with different sizes. The arrows indicate the measured particle sizes. (f) UV−vis spectra taken at various stages of reagent addition in the
preparation of the Pd nanocrystal solution. No spectral change can be detected upon the addition of KI and KBr solutions.

Figure 5. Photographs of the solutions taken during the synthesis of (a) Pd octahedra and (b) nanocubes.

E DOI: 10.1021/acs.langmuir.5b01337
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Figure 6. UV−vis extinction spectra of the final solutions taken as a function of the reaction time during the synthesis of (a) Pd octahedra and (b)
nanocubes. The 226 nm band absorbance initially decreases with time and eventually becomes steady. (c, d) Plots showing the changes in the
absorbance values of the (c) 226 nm band and the (d) 286 nm band as a function of the reaction time. The line at 6 min is drawn for comparison of
the relative consumption rates of the [CTA+]2[PdCl42−] complex.
vis spectra of the species added in the synthesis of medium-
sized Pd nanocubes. Upon mixing CTAC surfactant and
H2PdCl4 solution to form the [CTA+]2[PdCl42−] complex, no
further spectral shift was observed after the addition of KI and
KBr solutions, revealing that the ultrasmall amounts of KI and
KBr solutions used are insufficient in producing any spectral
shift. In the absence of CTAC surfactant, still no spectral shift
can be detected upon the introduction of the tiny amounts of
KBr and KI solutions (see Figure S5). It is remarkable that
addition of such a dilute KBr solution is effective at tuning the
particle growth rate and shape. The results imply that trace
halide impurity in the reagents can indeed lead to
irreproducible metal nanostructures.
In this study, the formation of Pd nanocrystals of different
shapes should not be attributed to adsorption of bromide ions
on selective faces because the tiny amounts of KBr solution
used here are far from sufficient for capping crystal surfaces (for
example, 600 mg of KBr added in the synthesis of 18 nm Pd
cubes).35,36 Moreover, Pd shell growth on polyhedral gold
cores has been found to proceed via incorporation of
surrounding irregularly shaped Pd structures before yielding a
well-defined shape.37 Molar ratios of H2PdCl4:KBr:KI are
1400:10:1 in the synthesis of Pd nanocubes. Pd nanocubes can
still be synthesized in the absence of bromide ions in the
solution.28 Au nanocrystals with various shapes have been
produced by adding the same amounts of NaBr.38 Bromide
ligand replacement tunes the reduction potential of the
precursor, which in turn adjusts the reduction rate and particle
growth rate. Previously no Br signals were detected in the XPS
spectrum of gold nanocubes synthesized using twice the
amount of NaBr than that used here to grow Pd nanocubes, so
bromide adsorption on the washed nanocube and cuboctahedra
surfaces is negligible.39 To prove this, XPS spectra of the
F DOI: 10.1021/acs.langmuir.5b01337
Article
unwashed solution after Pd nanocube synthesis and the
solution after one time washing were taken (see Figure S6).
The unwashed sample shows only noise-level amount of
bromide, while carbon, chloride, and nitrogen signals from the
surfactant are significant. Interestingly, the appearance of Pd
shoulders at ∼337 and 342 eV indicates the presence of a small
amount of Pd(II) species in the solution, which should
coordinate to chloride and some bromide ions.36 Iodide is
undetectable. After particle washing, bromide, nitrogen, and
chloride signals are undetectable. The carbon peak intensity has
reduced drastically. The Pd(II) shoulders also disappear. The
data show CTAC and residual Pd precursors have been cleanly
removed after one washing cycle. Again bromide concentration
on the particle surfaces is ultralow and undetectable in the
synthesis of Pd nanocubes.
■
CONCLUSIONS
Pd nanocrystals with systematic shape evolution from
octahedral to cuboctahedral and cubic morphologies have
been synthesized in aqueous solution by gradually increasing
the amount of KBr solution introduced. Only a trace amount of
KBr beyond optical and XPS detection was used. CTAC
surfactant and a tiny amount of KI solution were also added
into the reaction mixture. By adjusting the volumes of H2PdCl4
and KBr solutions added, particle sizes can be tuned, while still
maintaining their well-defined shapes. Extensive structural
characterization of the Pd nanocrystals has been performed.
Optical analysis reveals more red-shifted absorption bands for
Pd cubes than for octahedra of similar sizes. Visual and spectral
observation shows that Pd nanocubes are formed at a faster rate
than that for the growth of octahedra. The simple synthetic
procedure used here means that the Pd nanocrystals can be
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easily prepared for catalytic activity examination. They may also
be used as building blocks for the fabrication of supercrystals.
■
ASSOCIATED CONTENT
*
S Supporting Information
Exact reagent amounts used for growing Pd nanocrystals with
size control, particle size distribution histograms, additional
SEM and TEM images of the synthesized Pd nanocrystals,
UV−vis spectra, and XPS data. The Supporting Information is
available free of charge on the ACS Publications website at
DOI: 10.1021/acs.langmuir.5b01337.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: hyhuang@mx.nthu.edu.tw (M.H.H.).
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank the Ministry of Science and Technology of Taiwan
for support of this research (NSC 101-2113-M-007-018-MY3,
NSC 102-2811-M-007-003, and NSC 102-2633-M-007-002).
■
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H DOI: 10.1021/acs.langmuir.5b01337
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