Platinum nanomaterials

DOI: 10.1002/smll.200600015
Pt Nanoparticles Surfactant-Directed
Assembled into Colloidal Spheres and used
as Substrates in Forming Pt Nanorods and
Nanowires**
Jingyi Chen, Yujie Xiong, Yadong Yin, and
Younan Xia*
One-dimensional (1D) nanostructures have been extensively
studied in recent years because of their extraordinary prop-
erties arising from reduction in both dimensionality and
size, as well as their potential applications in fabricating
nanoscale devices.
[1]
In spite of many successful demonstra-
tions, it remains a grand challenge to produce large quanti-
ties of 1D nanostructures from various noble metals, togeth-
er with well-controlled dimensions and morphologies. Here,
we demonstrate that Pt nanoparticles formed via polyol re-
duction could be assembled into spherical aggregates under
the direction of sodium dodecyl sulfate (SDS) and then
serve as substrates to generate Pt nanorods and nanowires.
Platinum has found widespread use in a range of appli-
cations due to its unique physical and chemical properties.
[2]
For instance, it prevails as a major catalyst in many industri-
al processes such as the synthesis of nitric acid, reduction of
pollutant gases emitted from automobiles, oil cracking, and
proton-membrane-exchange (PME) fuel cells.
[3]
A great
deal of effort has been devoted to the preparation of Pt
nanostructures via chemical protocols.
[4]
However, most of
these previous studies have been limited to nanoparticles;
only polycrystalline nanorods and nanotubes have recently
been prepared by templating against channels within porous
materials,
[5]
Ag or Se nanowires,
[6]
and assemblies of organic
surfactants.
[7]
Although template-directed syntheses have
proven straightforward and versatile, they are restricted by
a number of drawbacks that may include, for example, the
requirement of template removal in order to generate pure
product, the limited scope of morphological variation, and
the polycrystallinity usually associated with the product.
In a recent study,
[8]
we discovered that the addition of a
small amount of an iron species (Fe
2+
or Fe
3+
) to the polyol
process could significantly alter the reduction kinetics of a
Pt precursor and thus induce the formation of Pt nanorods
characterized by uniform diameters and relatively high
aspect ratios. We demonstrate here that the synthesis could
be further modified to program the growth of such nanorods
into nanowires with lengths >500 nm. Based on our previ-
ous scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) studies of the reaction mecha-
nism, Pt nanoparticles tended to aggregate into large colloi-
dal spheres before the concentration of Pt atoms was re-
duced to a certain level to facilitate highly anisotropic
growth. When SDS was added as the directing agent, the
spherical aggregates could be synthesized with much smaller
sizes. These spherical aggregates were sufficiently stable in
solvents such as acetone, alcohol, and water, even under the
application of sonication for up to 30 min. As a result, these
spherical aggregates could serve as substrates to grow Pt
nanorods and nanowires through polyol reduction in the
presence of a trace amount of iron species. As a major ad-
vantage over previous protocols, one might be able to use
materials less precious than Pt to form the substrates for
growing Pt nanowires with controllable lengths.
[8d]
Figure 1 illustrates the two-step protocol that was de-
signed to achieve a tight control over the formation of Pt
nanorods and nanowires. In the first step, Pt nanoparticles
were formed and then assembled into spherical aggregates
when H
2
PtCl
6
was reduced by ethylene glycol (EG) at
1108C in the presence of SDS. Depending on the molar
ratio of H
2
PtCl
6
to SDS, the Pt nanoparticles were found to
exist in different forms. When the molar ratio of H
2
PtCl
6
to
SDS was lower than 1:1, the Pt nanoparticles were well-dis-
persed as individual entities (product A in Figure 1). As the
molar ratio was increased to 1:5, the Pt nanoparticles were
directed by SDS to further assemble into submicrometer-
sized spheres (product B in Figure 1). These spherical aggre-
gates could be separated from the reaction solution and
washed several times with ethanol and water. In the next
step, these spherical aggregates were added to 4 mL of EG
with a trace amount of iron species. After heating at 1108C
in air for one hour to activate the surface layer of the aggre-
gates, certain amounts of H
2
PtCl
6
/EG and PVP/EG (PVP:
poly(vinyl pyrrolidone)) were then added dropwise to the
reaction. Similar to our previous observations,
[8a]
the Pt
IV
species were reduced at an extremely slow rate, and the re-
sultant Pt atoms started to nucleate and grow into uniform
1D nanostructures on the surface of each aggregate (pro-
duct C in Figure 1).
Figure 2 shows TEM and SEM images of Pt nanostruc-
tures corresponding to the products illustrated in Figure 1.
Consistent with the schematic drawing, uniform spherical
aggregates of Pt nanoparticles could be synthesized under
the direction of SDS and further used as substrates to form
Pt nanorods and nanowires. Figure 2A shows a TEM image
of the Pt nanoparticles when the reduction of the Pt
IV
pre-
[*] J. Chen, Dr. Y. Xiong, Prof. Y. Xia
Department of Chemistry, University of Washington
Seattle, WA 98195-1700 (USA)
Fax: (+1) 206-685-8665
E-mail : xia@chem.washington.edu
Dr. Y. Yin
The Molecular Foundry
Lawrence Berkeley National Laboratory
Berkeley, CA 94720 (USA)
[**] This work was supported in part by the NSF (DMR-0451788) and
a fellowship from the David and Lucile Packard Foundation. Y.X.
is a Camille Dreyfus Teacher Scholar. This work used the Nano-
tech User Facility (NTUF) at the University of Washington, a
member of the National Nanotechnology Infrastructure Network
(NNIN) funded by the NSF. We also thank the Molecular Foundry
at the Lawrence Berkeley National Laboratory for the HRTEM
analysis.
Supporting information for this article is available on the WWW
under http://www.small-journal.com or from the author.
1340 2006 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim small 2006, 2, No. 11, 13401343
communications
S
P
E
C
I
A
L
S
E
C
T
I
O
N
cursor was performed at a molar ratio of 1:1 for H
2
PtCl
6
to
SDS. The inset gives a magnified TEM image of the nano-
particles, which were roughly spherical in shape with a
mean diameter of %5 nm.
Figure 2B shows an
SEM image of the product
when the molar ratio of
H
2
PtCl
6
to SDS was in-
creased to 1:5. The upper-
right inset shows a TEM
image of a single spherical
aggregate of %200 nm in
diameter, while the lower-
left inset gives a magnified
SEM image of the surface
layer of this aggregate,
confirming the presence of
a dense array of Pt nano-
particles %5 nm in size.
The X-ray diffraction
(XRD) pattern shown in
Figure S1 (see Supporting
Information) indicates that
the Pt in the spherical ag-
gregates was crystallized in
a face-centered cubic (fcc)
structure similar to bulk
Pt. Note that similar spher-
ical aggregates of Pt nano-
particles were also ob-
tained by increasing the
molar ratio of H
2
PtCl
6
to
SDS up to 1:35. These
spherical aggregates could
be prepared as stable sus-
pensions in water or EG
for a month.
Figure 2C shows an
SEM image of the Pt struc-
tures when the iron-medi-
ated reduction was carried
out in air with the spheri-
cal aggregates serving as
substrates. The final prod-
uct contained submicrome-
ter-sized objects of Pt
nanoparticles whose sur-
faces had been covered by
a dense array of uniform
nanorods. Compared with
our previous studies, the
overall size of these aggre-
gates had been reduced by
more than five times. By
taking advantage of the
nucleation site on the sub-
strate surface, it should be
possible to use much less
H
2
PtCl
6
to form the same
quantity of Pt nanorods and nanowires. Since the nanowires
were loosely attached to the surface of substrate, they could
be released via brief sonication without breaking the spheri-
cal aggregates. Once free, the wires could be harvested by
Figure 1. A schematic illustration of the two-step method used to form Pt nanorods/nanowires on the sur-
face of a spherical aggregate of Pt nanoparticles. In the initial step, the spherical aggregate of Pt nanoparti-
cles was synthesized by reducing [PtCl
6
]
2
ions in the presence of a high concentration of sodium dodecyl
sulfate (SDS). In the second step, this aggregate was used as a substrate to direct the formation of Pt nano-
rods/nanowires.
Figure 2. A) TEM image of well-dispersed Pt nanoparticles, and B) SEM image of spherical aggregates of Pt
nanoparticles; both samples were prepared via polyol reduction at two different molar ratios between
H
2
PtCl
6
and SDS: A) 1:1; B) 1:5. The inset in (A) shows a magnified image of the Pt nanoparticles whose
mean diameter was approximately 5 nm. The insets in (B) show SEM (lower-left) and TEM (upper-right)
images of a spherical aggregate of Pt nanoparticles, revealing the presence of a dense array of Pt nanoparti-
cles on the surface. C) SEM image of Pt nanorods grown on the surfaces of spherical aggregates. D) TEM
image of Pt nanorods after they had been released from the surface by brief sonication. The inset in (D)
gives a typical selective-area electron diffraction (SAED) pattern of the Pt nanorods, with the four rings
indexed to the {111}, {200}, {220}, and {311} planes. Note that several nanorods could grow from the same
seed of the Pt nanoparticle, resulting in a branched morphology.
small 2006, 2, No. 11, 13401343 2006 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.small-journal.com 1341
S
P
E
C
I
A
L
S
E
C
T
I
O
N
centrifugation and then redispersed in ethanol or water
without introducing additional surfactants. Figure 2D shows
a typical TEM image of some Pt nanorods ( %5 nm in diam-
eter) obtained using this procedure. The inset shows a se-
lected-area electron diffraction (SAED) pattern. The four
rings could be indexed to the {111}, {200}, {220}, and {311}
planes of fcc Pt, respectively. It is clear that the Pt nanorods
synthesized using this method were crystallized with an fcc
structure similar to the bulk solid.
In another demonstration, we combined the two steps
into one and performed the synthesis without separating the
aggregates of Pt nanoparticles from the solution. More in-
terestingly, we were able to control the length of the Pt
nanorods and obtain long nanowires by controlling the
amount of H
2
PtCl
6
sequentially added to the reaction. Fig-
ure 3A shows an SEM image of the product when an ex-
tremely small amount of H
2
PtCl
6
precursor (1 mm in final
concentration) was added and reduced by EG under air in
the presence of a trace amount of iron species. Similar to
the product B shown in Figure 1, the surface of each aggre-
gate was mainly covered by small Pt nanoparticles due to a
very low concentration of the Pt precursor. Additional
H
2
PtCl
6
was then introduced at two different concentrations
to the reaction (1 mm and 10 mm in final concentration) to
obtain the products depicted in Figure 3B and C, respective-
ly. Again, the concentra-
tion of Pt atoms would be
greatly reduced because
Pt
0
could be oxidized back
to Pt
II
by Fe
3+
. The addi-
tion of Pt atoms was
switched to a highly aniso-
tropic mode to form 1D
nanostructures on the sur-
face of each aggregate. Fig-
ure 3B shows an SEM
image of the Pt aggregates
whose surfaces were parti-
ally covered by Pt nano-
rods. Due to the relatively
low concentration of
H
2
PtCl
6
, only a portion of
these aggregates was cov-
ered with dense arrays of
Pt nanorods. Figure 3C
shows an SEM image of
the Pt aggregates where all
of their surfaces were cov-
ered with Pt nanowires.
Because the H
2
PtCl
6
pre-
cursor existed in the solu-
tion at a low concentration
for a long period of time,
the Pt atoms could grow
into nanowires more than
500 nm in length, as shown
in Figure 3D. After synthe-
sis, the Pt nanowires could
also be separated from the
substrates via a combination of brief sonication and centri-
fugation.
Figure 4A shows a TEM image of some long Pt nano-
wires that were released from the sample shown in Fig-
ure 3C. As mentioned above, the Pt nanowires were loosely
attached to the surface of the substrate (i.e. , the spherical
aggregate of Pt nanoparticles) and could be sonicated off
and then collected by centrifugation and redispersed in
water or ethanol. Due to the small diameters of these nano-
wires, it is highly possible to break the nanowires during the
sonication process. The inset shows a typical SAED pattern.
Figure 4B shows a high-resolution (HR) TEM image re-
corded from the end of a single Pt nanowire, indicating that
the nanowire grew along the <111> direction. The lattice
spacing between the {111} planes, 0.23 nm, is in agreement
with the value of the bulk crystal. Figure 4C shows a
HRTEM image recorded from the bending part of a Pt
nanowire, showing that the nanowire was still a single crys-
tal. Both arms of the bending nanowire grew along the
<111> direction, with an angle of 1348 between the two
arms. Figure 4D shows a TEM image of an individual Pt
nanowire that was more than 500 nm in length.
In summary, we have synthesized Pt nanowires with con-
trollable lengths by using spherical aggregates of Pt nano-
particles as substrates and by adding different amounts of Pt
Figure 3. A) SEM image of spherical aggregates of Pt nanoparticles that were obtained when an extremely
small amount of H
2
PtCl
6
precursor (1 mm) was added and reduced by EG in air in the presence of a trace
amount of iron species. B, C) SEM images of Pt nanostructures that were obtained by consecutively adding
1 mL of two different concentrations of Pt precursor to the reaction mixture without removing the product:
B) 1 mm and C) 10 mm H
2
PtCl
6
, respectively. D) SEM image showing a magnified view of the long Pt nano-
wires grown on the surface, as boxed in (C).
1342 www.small-journal.com 2006 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim small 2006, 2, No. 11, 13401343
communications
S
P
E
C
I
A
L
S
E
C
T
I
O
N
precursor to the reaction mixture. The spherical aggregates
(200 nm in diameter) were, in turn, prepared under the di-
rection of an organic surfactant such as SDS. As an immedi-
ate advantage over our previously demonstrated systems,
the spherical aggregates were more uniform in size and
shape, and could be more than five times smaller in dimen-
sion. As a result, these aggregates would provide a larger
surface area for the nucleation and growth of Pt nanorods
and nanowires. After synthesis, the Pt nanorods and nano-
wires could also be separated from the substrates through a
combination of brief sonication and centrifugation. If neces-
sary, the spherical aggregates could be reused as substrates
for additional rounds of nanowire growth. We note that Pt
has recently been synthesized as branched nanocrystals by a
number of research groups.
[9]
All these new developments
will undoubtedly improve the performance of Pt nanostruc-
tures in many industrial applications.
Keywords:
nanoparticles
nanorods nanowires
platinum
polyol reduction
[1] Y. Xia, P. Yang, Y. Sun, Y.
Wu, B. Mayers, B. Gates, Y.
Yin, F. Kim, H. Yan, Adv.
Mater. 2003, 15, 353.
[2] See for example: F. A.
Cotton and G. Wilkinson,
Advanced Inorganic
Chemistry, 5th Ed. , Wiley,
New York, 1988, p. 868.
[3] a) A. Rouxoux, J. Schulz, H.
Patin, Chem. Rev. 2002,
102, 3757; b) K. R. Wil-
liams, G. T. Burstein, Catal.
Today 1997, 38, 401.
[4] a) T. S. Ahmadi, Z. L. Wang,
T. C. Green, A. Heglein,
M. A. El-Sayed, Science
1996, 272, 1924; b) T. Ter-
anishi, M. Hosoe, T.
Tanaka, M. Miyake, J. Phys.
Chem. B 1999, 103, 3818;
c) S. Chen, K. Kimra, J.
Phys. Chem. B 2001, 105,
5397; d) H. Wakayama, N.
Setoyama, Y. Fukushima,
Adv. Mater. 2003, 15, 742;
e) X. Teng, D. Black, N. J.
Watkins, Y. Gao, H. Yang,
Nano Lett. 2003, 3, 261.
[5] a) Y. Sakamoto, A. Fukuo-
ka, T. Higuchi, N. Shimo-
mura, S. Inagaki, M. Ichika-
wa, J. Phys. Chem. B 2004, 108, 853; b) A. Husain, J. Hone,
H. W. C. Postma, X. M. H. Huang, T. Drake, M. Barbic, Appl. Phys.
Lett. 2003, 83, 1240; c) X. Fu, Y. Wang, N. Wu, L. Gui, Y. Tang, J.
Mater. Chem. 2003, 13, 1192; d) H. J. Shin, R. Ryoo, Z. Liu, O.
Terasaki, J. Am. Chem. Soc. 2001, 123, 1246; e) Y. Han, J. Kim,
G. D. Stucky, Chem. Mater. 2000, 12, 2068.
[6] a) B. Mayers, X. Jiang, D. Sunderland, B. Cattle, Y. Xia, J. Am.
Chem. Soc. 2003, 125, 13364; b) Y. Sun, B. Wiley, Z.-Y. Li, Y. Xia,
J. Am. Chem. Soc. 2004, 126, 9399.
[7] a) T. Kijima, T. Yoshimura, M. Uota, T. Ikeda, D. Fujikawa, S.
Mouri, S. Uoyama, Angew. Chem. 2004, 116, 230; Angew. Chem.
Int. Ed. 2004, 43, 228.
[8] a) J. Chen, T. Herricks, M. Geissler, Y. Xia, J. Am. Chem. Soc.
2004, 126, 10854; b) J. Chen, T. Herricks, Y. Xia, Angew. Chem.
2005, 117, 2645; Angew. Chem. Int. Ed. 2005, 44, 2589; c) E.
Lee, J. Chen, Y. Yin, C. Campbell, Y. Xia, Adv. Mater. 2006, in
press.
[9] a) X. Teng, H. Yang, Nano. Lett. 2005, 5, 885; b) H. Song, F. Kim,
S. Connor, G. A. Somorjai, P. Yang, J. Phys. Chem. B 2005, 109,
188; c) X. Teng, X. Liang, S. Maksimuk, H. Yang, Small 2006, 2,
249.
Received: January 10, 2006
Published online on September 6, 2006
Figure 4. A) TEM image of some long Pt nanowires that had been removed from the surface of the sample
shown in Figure 3C. The inset shows a typical SAED pattern of these nanowires. B) HRTEM image of the tip
of an individual Pt nanowire, indicating that it was a single crystal, with its growth direction along the
<111> axis. C) HRTEM image of the bent part of an individual Pt nanowire, as boxed in (A), showing that
both segments of the bent nanowire grew along the <111> direction, and that the bending angle was
%1348. D) TEM image of an individual nanowire separated from the same sample. Note that this wire was
5 nm in diameter and more than 500 nm in length.
small 2006, 2, No. 11, 13401343 2006 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.small-journal.com 1343
S
P
E
C
I
A
L
S
E
C
T
I
O
N