Article

Cite This: J. Phys. Chem. C XXXX, XXX, XXX−XXX pubs.acs.org/JPCC

Systematic Shape Evolution of Gold Nanocrystals Achieved through

Adjustment in the Amount of HAuCl4 Solution Used
Bing-Hong Kuo, Chi-Fu Hsia, Tzu-Ning Chen, and Michael H. Huang*
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua
University, Hsinchu 30013, Taiwan
*
S Supporting Information

ABSTRACT: Past work on the synthesis of gold nanocrystals has

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revealed that changing the reaction cell potential enables particle shape
evolution. Although various parameters in the Nernst equation has been
used to achieve this, adjusting the metal precursor concentration has not
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been demonstrated before. Using the reported synthetic conditions with

cetyltrimethylammonium chloride (CTAC) surfactants to grow gold
nanocubes, rhombic dodecahedra, and octahedra as the starting points,
fixing the ascorbic acid volume, and tuning the volume of HAuCl4
solution introduced allow the formation of the same series of crystal
shape evolution from rhombic dodecahedral to trisoctahedral and cubic
structures in the presence of a tiny amount of NaBr. In another series, by
gradually increasing the HAuCl4 solution volume but fixing potassium
iodide and ascorbic acid volumes, gold nanocrystals with tunable
morphologies from octahedra to corner-truncated octahedra, edge- and
corner-truncated octahedra, and rhombic dodecahedra can be synthesized. These results demonstrate that adjustment of the
metal precursor concentration is also effective in metal particle shape control. Using spectral analysis, the formation of CTA−
AuCl4 and CTA−AuCl2 complexes has been confirmed, so CTAC acts as a coordinating species to the metal source and
provides halide ions to influence the overall cell potential. Thus, all species in the reaction mixture are noninnocent and are
involved in redox chemistry. The strategy has been applied to the synthesis of small Cu nanocubes with tunable sizes and
nanowires.

■ INTRODUCTION
Synthesis of polyhedral metal nanocrystals with tunable shapes
and controlled sizes enables investigation of their facet-
dependent catalytic properties in diverse organic reactions.1−5
They are also useful as surface-enhanced Raman substrates6−8
and are excellent building blocks for the fabrication of
supercrystals.9−13 To grow Au, Pd, and other noble metal
nanocrystals with shape evolution, different approaches have
been adopted, including the variation in the amount of the
reducing agent added,14−17 metal precursor selection,18
introduction of tunable amounts of bromide or iodide
ions,17,19−21 surfactant choice such as cetyltrimethylammo-
nium bromide (CTAB) or cetyltrimethylammonium chloride
(CTAC) and its amount,7,22 adjustment in the reaction
temperature,20 and HCl oxidative etching.23 All these strategies
are actually related, if we understand that Au and Pd particle
shapes can be tuned by changing the redox potential of the
reaction involved. These parameters directly or indirectly tune
the overall reaction potential either by changing the reduction
potential of the metal precursor through ligand exchange with
different halide ions or by tuning the reaction quotient Q
through adjustment in the amount of the reducing agent
introduced. Thus, CTAC and CTAB surfactants are not
innocent acting only as capping agents because of the halides
they carry. Basically, these parameters tune one or more
variables in the Nernst equation to change the reaction
potential and thus the free energy of reaction (ΔG = −nFE).
Hence, varying the reaction temperature can also be effective,
but this is more difficult to control precisely. Tuning ΔG
means tuning the driving force for the reaction, and this in turn
gives different rates of solution color changes or tunable
reduction rates in the formation of various particle
morphologies. For Ag and Cu nanocrystals, systematic shape
evolution in aqueous solution is much more difficult to
achieve, possibly because of the low reduction potentials of
AgCl and AgBr which are hard to avoid and the favorable
formation of CuCl and CuBr through the reduction of CuCl2/
CuBr2 or in the presence of CTAB/CTAC surfactants, so
cubes are generally obtained.24,25 Although these known
strategies are successful in tuning particle shapes, examination
of the Nernst equation suggests that varying the metal
precursor concentration should also be effective because
both the reducing agent and the metal precursor concen-
trations appear in the reaction quotient Q. However, such a
Received: August 30, 2018
Revised: October 12, 2018
Published: October 15, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcc.8b08479

J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
simple and obvious way to adjust the overall reaction potential
has never been demonstrated before, although adjustment of
both the reducing agent and precursor amounts was successful
in making bimetallic core−shell nanocrystals with systematic
shape evolution and tunable sizes.26,27 Yet, there was no good
understanding of why such an approach was effective. It is
understandable why no one has tried to mainly adjust the
metal source amount to tune the particle shape because
intuitively doing so should only change the particle size and/or
yield. Thus, the idea that the particle shape is linked to the
metal source concentration sounds strange to most people.
This work explores the growth of gold nanocrystals with
systematic shape evolution using the previously developed
synthetic conditions as the starting point and varies the volume
of HAuCl4 solution over a wide range to achieve similar shape
tunability.15,19 The same shape transformation from rhombic
dodecahedral to cubic structures in the presence of NaBr and
from octahedral to rhombic dodecahedral structures in another
series with potassium iodide (KI) has been achieved. To
completely understand the roles of all species added in the
growth of these nanocrystals, the possibility of CTA+ acting as
a coordinating ligand to form CTA−AuCl4 and CTA−AuCl2
complexes was examined spectroscopically. The complex
formation has been confirmed. Thus, all species added to the
reaction mixture actually take part in the redox reaction,
including halide ions and CTAC surfactants. Using this
synthetic approach, the amount of copper acetate was varied
to achieve the formation of small Cu nanocubes with tunable
sizes and nanowires.
■ EXPERIMENTAL METHODS
Chemicals. Hydrogen tetrachloroaurate trihydrate
(HAuCl4·3H2O, Aldrich, 99.9%), CTAC (TCI, 95%), sodium
borohydride (NaBH4, Sigma-Aldrich, 98%), ascorbic acid (AA,
Riedel-de Haën, 99.7%), sodium bromide (NaBr, UCW), KI
(J. T. Baker), cupric acetate monohydrate (Cu(CH3COO)2·
H2O, 98%, J. T. Baker), and L(+)-sodium ascorbate (SA, 98%,
Sigma-Aldrich) were used without further purification. Ultra-
pure distilled and deionized water (18.3 MΩ) was used for all
preparations.
Preparation of Gold Seed Solution. A volume of 10 mL
aqueous solution containing 0.10 M CTAC and 2.5 × 10−4 M
HAuCl4 was prepared. Concurrently, 10 mL of 0.02 M NaBH4
was made in ice-cold solution. To the HAuCl4 solution was
added 0.45 mL of the NaBH4 solution with stirring. The
resulting solution immediately turned brown, indicating the
formation of gold particles. The seed solution was aged for 1 h
at 30 °C to decompose excess borohydride by water.
Synthesis of Gold Nanocrystals with Shape Evolution
from Rhombic Dodecahedral to Cubic Structures. The
procedure is based on our reported method.15 In the first set of
reaction conditions, a growth solution was prepared in two
vials. First, 0.32 g of the CTAC surfactant was added. The
concentration of CTAC in the final solution is 0.1 M.
Depending on the gold particle shape to be synthesized,
slightly different volumes of deionized water were added to
each vial (9.625, 9.655, and 9.715 mL for cubes, trisoctahedra,
and rhombic dodecahedra, respectively) to reach 10 mL for the
total solution volume. The vials were placed in a water bath set
at 25 °C. Next, 160, 220, and 250 μL of 0.01 M HAuCl4
solution were added for the syntheses of rhombic dodecahedra,
trisoctahedra, and cubes, respectively, and 10 μL of 0.01 M
NaBr was introduced. Finally, 90 μL of 0.04 M AA was added
B DOI: 10.1021/acs.jpcc.8b08479
Article
to form the growth solution. The solution color turned
colorless after the addition of AA, indicating the reduction of
Au3+ to Au+ species. Then, 25 μL of the seed solution was
added to one growth solution with shaking until the solution
color turned light pink (∼5 s). Next, 25 μL of this solution was
added to the second growth solution with thorough mixing for
5−10 s. The solution was aged for 15 min and centrifuged at
3000 rpm for 10 min to collect the particles using a Hermle
Z323 centrifuge. After removing the top solution, 40 mL of
deionized water was added to the precipitate, and the solution
was centrifuged again using the same condition.
In another set of experiments, the reaction conditions are
the same as described above with the exception of the volumes
of HAuCl4 and AA solution used. Here, the volumes of
HAuCl4 solution added are 250, 300, and 420 μL for the
formation of Au rhombic dodecahedra, trisoctahedra, and
cubes, respectively, and 150 μL of AA was introduced.
Synthesis of Gold Nanocrystals with Shape Evolution
from Octahedral to Rhombic Dodecahedral Structures.
The procedure is based on our reported method.19 In the first
set of reaction conditions, a growth solution was prepared in
two vials. First, 0.32 g of the CTAC surfactant was added, and
then 9.635, 9.595, 9.565, 9.525, and 9.485 mL of deionized
water were added to each vial for the growth of Au octahedra,
corner-truncated octahedra, edge- and corner-truncated
octahedra (type I and type II), and rhombic dodecahedra,
respectively. The vials were kept in a water bath set at 20−25
°C. To the first growth solution were added 100, 140, 170,
210, and 250 μL of 0.01 M HAuCl4 solution to make Au
octahedra, corner-truncated octahedra, edge- and corner-
truncated octahedra (I), edge- and corner-truncated octahedra
(II), and rhombic dodecahedra, respectively. Finally, 20 μL of
0.001 M KI and 220 μL of 0.04 M AA were introduced to the
growth solution. Again, the solution color turned colorless after
the addition of AA, signifying the formation of Au+ species.
Next, 25 μL of the seed solution was added to the first growth
solution with shaking until the solution color turned light pink
(∼5 s). Then, 25 μL of this solution was transferred to the
second growth solution with thorough mixing for 5−10 s. The
solution was aged for 15 min and centrifuged at 2500 rpm for
10 min to collect the particles. After removal of the top
solution, 40 mL of deionized water was added to the
precipitate, and the solution was centrifuged again using the
same condition.
In another set of experiments, the synthesis conditions are
the same as described above with the exception of the volumes
of HAuCl4 and KI solutions used. Here, 250, 300, 380, 460,
and 520 μL of HAuCl4 solution were added to make Au
octahedra, corner-truncated octahedra, edge- and corner-
truncated octahedra (I), edge- and corner-truncated octahedra
(II), and rhombic dodecahedra, respectively. In addition, 50
μL of 0.001 M KI solution was introduced.
Synthesis of Copper Nanocubes with Tunable Sizes
and Nanowires. The procedure was adopted from our
reported method.25 To make copper nanocrystals from cubes
to wires, 0.048 g of CTAC and different volumes of deionized
water were added to each vial (see Table S1 in the Supporting
Information for detail). Then, 50, 250, 270, and 300 μL of 0.1
M copper acetate solution were added and mixed thoroughly.
Next, 100 μL of 0.5 M SA solution was introduced and mixed
well. The vials were placed in an oven and heated to 100 °C for
40 min. After cooling the vials to room temperature, the
solutions were centrifuged at 6500 rpm for 5 min. The
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Scheme 1. Scheme Illustration of the Synthetic Conditions Used for Growing Gold Nanocrystals with Systematic Shape
Evolution

precipitate was centrifuged one more time with 5 mL of AuCl4 − + AA(C6H8O6 )

deionized water at 6500 rpm for 5 min. Finally, the synthesized
copper nanocrystals were dispersed in deionized water. → AuCl 2− + DAA(C6H6O6 ) + 2Cl− + 2H+ (1)
Instrumentation. Transmission electron microscopy
2AuCl 2− + AA(C6H8O6 )
(TEM) characterization was performed on a JEOL JEM-
2100 microscope with an operating voltage of 200 kV. → 2Au + DAA(C6H6O6 ) + 4Cl− + 2H+ (2)
Scanning electron microscopy (SEM) images of the samples The Nernst equation gives the cell potential under
were obtained using a JEOL JSM-7000F electron microscope. nonstandard states with reagent concentrations differing from
Powder X-ray diffraction (XRD) patterns were recorded on a 1 M.
Shimadzu XRD-6000 diffractometer with Cu Kα radiation. RT
UV−vis absorption spectra were acquired with the use of a E = E°− ln Q
nF
JASCO V-570 spectrophotometer.

■
RESULTS AND DISCUSSION
To make gold nanocrystals, HAuCl4 is typically reduced by AA
through the following two reactions. AA is oxidized to
dehydroascorbic acid (DAA). AuCl2− species is formed as an
intermediate species because the gold solution initially turns
colorless before being further reduced to metallic gold.
C DOI: 10.1021/acs.jpcc.8b08479
Combining eqs 1 and 2, we can write the reaction quotient
as
[DAA]3 [Cl−]8 [H+]6
Q=
[AuCl4 −]2 [AA]3
Previously, we have synthesized Au nanocubes, trisoctahe-
dra, and rhombic dodecahedra by only varying the volume of
AA added in an aqueous mixture of CTAC surfactant, HAuCl4,
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Figure 1. SEM images of the synthesized Au (a,d) rhombic dodecahedra, (b,e) trisoctahedra, and (c,f) cubes by adding (a−c) 90 μL and (d−f) 150
μL of AA and increasing the volumes of HAuCl4 solution added.

NaBr, and AA.15 According to the reaction quotient, it should

be possible to tune the cell potential by changing the HAuCl4
concentration. To test whether varying the volume of HAuCl4
can also give the same crystal shape evolution, the same
reaction conditions used to synthesize Au cubes (adding 90 μL
of AA) and rhombic dodecahedra (150 μL of AA) were
adopted as the starting points. This strategy makes perfect
sense because there is no need to search for new reaction
conditions. For the complete reagent amounts and exper-
imental procedure used, see Scheme 1. SEM images in Figure
1a−c show that maintaining the volume of 0.04 M AA added
at 90 μL, but decreasing the volume of 0.01 M HAuCl4
solution from 250 μL originally used to grow gold nanocubes
to 220 and 160 μL, trisoctahedra and rhombic dodecahedra
were respectively synthesized. By using the condition of 150
μL of AA and 250 μL of HAuCl4 solution for making rhombic
dodecahedra, but increasing the HAuCl4 volume to 300 and
420 μL, trisoctahedra and cubes can be respectively
synthesized (Figure 1d−f). Figure S1 summarizes the
HAuCl4 volumes used and the resulting nanocrystal structures.
The particles are highly uniform in size and shape that the
cubes and rhombic dodecahedra spontaneously self-assemble
into ordered packing arrangements. The results clearly
demonstrate that simply tuning the amount of the metal
source is also effective in crystal shape evolution. Figure S2
Figure 2. XRD patterns of the synthesized Au nanocrystals with
gives the size measurements of these particles. Average sizes for tunable shapes.
the synthesized Au rhombic dodecahedra, trisoctahedra, and
cubes are 82, 96, and 87 nm, respectively, using 90 μL of AA,
and 90, 104, and 94 nm using 150 μL of AA. Figure S3 On the basis of this successful demonstration, we have tested
provides their size distribution histograms. The particles another series to grow gold nanocrystals with systematic shape
synthesized with 150 μL of AA are generally larger than evolution from rhombic dodecahedral to octahedral structures
by maintaining the amount of 0.04 M AA constant at 220 μL,
those obtained in the previous report.15 This is understandable
but increasing the volume of 0.001 M KI from 20 to 50 μL.
because more gold precursors have been added to achieve
Despite the tiny difference in the amount of KI introduced,
shape evolution. shape evolution has been achieved because of partial chloride
XRD patterns of the synthesized gold cubes, trisoctahedra, ligand replacement of AuCl4− by iodide to tune the reduction
and rhombic dodecahedra are given in Figure 2, matching with potential of the metal precursor.19 Beginning with the addition
the standard XRD pattern of gold. Cubes show only the (200) of 20 μL of KI solution and 250 μL of HAuCl4 solution
peak, and rhombic dodecahedra display strong (111) and originally used to make rhombic dodecahedra, continuously
(220) peaks because of their oriented assembly on the decreasing the volume of HAuCl4 solution added to 100 μL
substrate. Figure S4 presents TEM characterization of the Au yielded edge- and corner-truncated octahedra (type II, 210 μL
cubes, trisoctahedra, and rhombic dodecahedra. The perfect of HAuCl4; type I, 170 μL of HAuCl4), corner-truncated
trisoctahedra should expose high-index {221} surfaces.28 octahedra, and octahedra. Figure 3a−e shows SEM images of
Selected-area electron diffraction patterns taken on individual the synthesized gold nanocrystals. Again, the particle size and
crystals show that they are all single-crystalline. shape are highly uniform that they readily self-assemble into
D DOI: 10.1021/acs.jpcc.8b08479
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Figure 3. SEM images of Au (a,f) octahedra, (b,g) corner-truncated octahedra, (c,h) edge- and corner-truncated octahedra (I), (d,i) edge- and
corner-truncated octahedra (II), and (e,j) rhombic dodecahedra synthesized by increasing the volume of HAuCl4 solution introduced and adding
(a−e) 20 μL and (f−j) 50 μL of 0.001 M KI solution.

Figure 4. UV−vis absorption spectra of the 94 nm Au nanocubes, 96 nm trisoctahedra, 82 nm rhombic dodecahedra, 90 nm edge- and corner-
truncated octahedra (II), 92 nm edge- and corner-truncated octahedra (I), 69 nm corner-truncated octahedra, and 80 nm octahedra.

E DOI: 10.1021/acs.jpcc.8b08479
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Figure 5. UV−vis absorption spectra of (a) 1 × 10−4 M HAuCl4 solution, (b) pure CTAC solution, (c,d) HAuCl4 and CTAC solution with molar
ratios of 1:1 and 1:4, (e,f) 1 × 10−4 M HAuCl4 solution and different volumes of 2 mM AA added.

ordered packing structures. Figure 4 shows the shape
difference between the two types of edge- and corner-truncated
octahedra (perfect triangular {111} faces for type II and
truncated triangular {111} faces or octagonal {100} faces for
type I). Alternatively, by adding 50 μL of KI solution and 250
μL of HAuCl4 solution to make octahedra, and gradually
increasing the volume of HAuCl4 solution added to 520 μL,
corner-truncated octahedra, edge- and corner-truncated
octahedra (type I and type II), and rhombic dodecahedra
can be synthesized. The particles are also highly monodisperse
in size and shape. Again, systematic shape evolution is
successful by simply adjusting the gold precursor amount.
Figures S2 and S3 give the size measurements of these particles
and their size distribution histograms. Average sizes of the
octahedra, corner-truncated octahedra, edge- and corner-
truncated octahedra (I), edge- and corner-truncated octahedra
(II), and rhombic dodecahedra are respectively 80, 69, 92, 90,
and 83 nm using 20 μL of KI, and 85, 71, 97, 93, and 94 nm
using 50 μL of KI.
XRD patterns of this series of particle shapes are also
available in Figure 2. Because {111} and {110} faces are often
observed to orient parallel to the substrate surface for corner-
truncated octahedra and edge- and corner-truncated octahedra,
their XRD patterns show strong (111) and (220) reflection
F DOI: 10.1021/acs.jpcc.8b08479
peaks. For octahedra, the appearance of strong (111) and
(222) peaks is expected because their {111} faces are oriented
parallel to the substrate surface. UV−vis absorption spectra of
all these particle shapes are displayed in Figure 4. All samples
show only a single surface plasmon resonance (SPR)
absorption band, indicating their good size and shape
homogeneity. The narrow range of the recorded band
positions between 550 and 580 nm reflects their similar
sizes. The smallest 69 nm corner-truncated octahedra give an
SPR band at 550 nm.
The next goal of this work is to clarify the role of the CTAC
surfactant used in the synthesis of gold nanocrystals. This is
important because if CTA+ actually coordinates to the metal
center to tune its reduction potential, then the reaction
equations should be modified to reflect this fact. The notion of
CTA+X− (X− = Cl− or Br−) selectively adsorbing to some faces
of crystals promoting the growth of certain particle shapes is
questionable because gold crystals exposing {100}, {110}, and
{111} faces can all be synthesized as demonstrated here and
has been observed in another study,29 and supercrystal
formation from the assembly of cubes, octahedra, rhombic
dodecahedra, and other shapes is all possible using the same
surfactant molecules packing between adjacent nanocrystals.11
A series of spectral experiments has been conducted to check
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Figure 6. UV−vis absorption spectra of (a) HAuCl4 and CTAC solution with a molar ratio of 1:10 and (b−e) different volumes of 0.01 M AA
added to this solution. The 600 nm peak indicates the formation of Au particles.

Figure 7. (a) Cu nanowires and Cu nanocubes with average edge lengths of (b) 45, (c) 51, and (d) 72 nm by adjusting the volume of copper
acetate solution added.

the existence of CTA−HAuCl4 and CTA−HAuCl2 complex
formation. Figure S5 presents SEM images of the gold
nanocubes synthesized under normal 0.1 M CTAC concen-
tration and by replacing 0.1 M CTAC with 0.1 M NaCl
concentration. Nanocubes have completely disappeared in the
absence of CTAC, and only rice-shaped particles were
produced. Because this shape deterioration is not caused by
chloride ions, it is considered to be the CTA+ effect. Next,
UV−vis absorption spectra of HAuCl4, CTAC, and several
molar ratios of HAuCl4 to CTAC were taken (see Figures 5a−
d and 6a). CTAC has no absorption band, whereas the 1.0 ×
G DOI: 10.1021/acs.jpcc.8b08479
10−4 M HAuCl4 solution shows a sharp band at 217 nm and a
shoulder band at 290 nm. A solution with a 1:1 molar ratio of
HAuCl4 and CTAC shifts the HAuCl4 absorption bands to 238
and 334 nm with a long absorption tail into the visible light
region. This signifies the formation of the CTA−AuCl4
complex. Increasing the molar ratio of HAuCl4/CTAC to
1:10 barely shifts the absorption bands to 233 and 331 nm. If
0.5 mL of 2 mM AA solution is added to the 10−4 M HAuCl4
solution in the absence of CTAC, there is no change to the
absorption bands of HAuCl4. Increasing the AA volume to 1
mL gives a new band at 568 nm because of the formation of
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gold particles, yet the HAuCl4 bands remain unchanged. This
result indicates direct reduction of HAuCl4 to Au in the
absence of CTAC. Notice that the HAuCl4 peak absorbance
has decreased substantially because some gold source has been
converted to metallic gold.
If one starts with the solution having a 1:10 molar ratio of
HAuCl4/CTAC, adding 325 μL of 0.01 M AA generates a new
peak at 206 nm in addition to the original CTA−AuCl4 bands,
which are slightly shifted to 230 and 325 nm (Figure 6). With
400 μL of AA introduced, only two bands at 205 and 245 nm
are observed with significantly higher absorbance values than
the bands recorded adding just 325 μL of AA. This spectral
feature should result from the complete formation of the
CTA−AuCl2 complex because a reducing agent of sufficient
amount has been added to CTA−AuCl4. There is no visible
light absorption, further supporting the formation of colorless
CTA−AuCl2 species. After adding 500 μL of AA, the 245 nm
band has dropped significantly in absorbance, and the Au SPR
band at 600 nm has emerged (Figure 7).
The complex formation kinetics has been probed using the
reagent concentrations for making a growth solution for the
preparation of Au octahedra in the presence of 50 μL of 0.001
M KI solution. This growth solution condition was chosen
because the intermediate dendritic structures observed in the
synthesis of Au octahedra have been reported.19 Figure S6
reveals immediate formation of CTA−AuCl4 upon mixing
HAuCl4 and CTAC. Conversion of CTAC−AuCl4 to CTAC−
AuCl2 also happens instantly after the introduction of AA. If
the molar ratio of HAuCl4/CTAC is substantially reduced to
just 1:10, formation of CTA−AuCl4 is very slow, but its
conversion to CTA−AuCl2 also occurs instantly.
Because the spectral analysis suggests that CTA−AuCl4 and
CTA−AuCl2 complexes have been formed, eqs 1 and 2 should
be modified as shown below.
CTAAuCl4 + AA(C6H8O6 )
→ CTAAuCl 2 + DAA(C6H6O6 ) + 2H+ + 2Cl−
(3)
2CTAAuCl 2 + AA(C6H8O6 )
→ 2Au + DAA(C6H6O6 ) + 2H+ + 4Cl− + 2CTA+
(4)
A new reaction quotient can be obtained combining eqs 3
and 4. Again, Q is mainly determined by the metal precursor
and AA concentrations.
[DAA]3 [H+]6 [Cl−]8 [CTA+]2
Q=
[CTAAuCl4]2 [AA]3
For simplicity of calculation, Q has been replaced with Q′ by
removing the [DAA], [Cl−], and [CTA+] terms. The obtained
Q′ values for cubes and rhombic dodecahedra synthesized in
the presence of NaBr are available in the Supporting
Information, including the cell potential differences in the
formation of Au cubes and rhombic dodecahedra. In addition,
we have found that for gold cubes and rhombic dodecahedra
synthesized using two different HAuCl4 and AA amounts, their
AA/HAuCl4 mole ratio serves as a simple guideline for
predicting the particle shape (Table S2). For the AA/HAuCl4
mole ratio in the range of 2.25−2.4, rhombic dodecahedra are
synthesized. Lowering the AA/HAuCl4 mole ratio to 1.43−
H DOI: 10.1021/acs.jpcc.8b08479
Article
1.44, cubes are obtained. Such simple rules illustrate how gold
particle shape evolution is linked to metal precursor quantity.
As a test and an application of the synthetic strategy
discovered in this work, we have used our reported method for
growing Cu nanocubes and nanowires to achieve possible
shape evolution of polyhedral Cu nanocrystals.25 Previously,
Cu nanocubes with average edge lengths of 82, 95, and 108 nm
were synthesized by heating an aqueous mixture of CTAC,
copper acetate (Cu(OAc)2), and SA to 100 °C for 40 min. Cu
nanowires were also obtained the same way, but much more
SA was needed. CuCl42− should form in the presence of
CTAC, although initial CuCl2 formation is also possible. In the
new method, the amount of SA used was fixed, but the volume
of 0.1 M Cu(OAc)2 solution was varied from 50 to 250 and
270 μL to form Cu nanocubes with average edge lengths of 45,
51, and 72 nm. Further increasing the Cu(OAc)2 volume to
300 μL led to the production of nanowires, so similar crystal
shape change was observed. Figure S7 gives the size
distribution histograms of the synthesized Cu nanocubes.
These cubes are far smaller than those achievable using the
original conditions, making small Cu cubes below 50 nm easily
obtainable. The 45, 51, and 72 nm Cu cubes show an SPR
absorption band centered at 602, 605, and 620 nm,
respectively (Figure S8). These SPR band positions match
reasonably well with those of Au−Cu cubes of similar sizes.30
■ CONCLUSIONS
Recognizing that synthesis of gold particles with systematic
shape evolution is achieved by tuning the reaction cell
potential, a parameter in the Nernst equation never explored
to change particle shape is the metal precursor concentration.
Using our two reported series to make gold particles with
tunable shapes and starting with the conditions listed to grow
rhombic dodecahedra, cubes, and octahedra, increasing the
volume of HAuCl4 solution introduced also yields the same
series of crystal shape evolution from rhombic dodecahedra to
trisoctahedra and cubes, and from octahedra to corner-
truncated octahedra, edge-and corner-truncated octahedra,
and rhombic dodecahedra. Furthermore, spectral analysis has
confirmed the formation of CTA−AuCl4 and CTA−AuCl2
complexes, so CTAC (or CTAB) added to the reaction
mixture does not really act as a capping agent, but as a metal-
complexing agent and a source of halide. In addition, both
roles actively influence the overall reaction potential. This work
illustrates that practically everything added to the reaction
mixture in the synthesis of metal particles are involved in redox
chemistry. This fact should be recognized in the design of
reaction conditions and in explaining the synthesis results.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.8b08479.
Exact reagent amounts used for Au particle synthesis,
particle size measurements and size distribution histo-
grams, TEM characterization, and additional UV−vis
spectra (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: hyhuang@mx.nthu.edu.tw.
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
ORCID
Michael H. Huang: 0000-0002-5648-4345
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was funded by the Ministry of Science and
Technology of Taiwan (MOST 104-2119-M-007-013-MY3
and 105-2633-M-007-003).
■
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