Nano Today (2009) 4, 8195

available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanotoday

REVIEW

Shape-controlled synthesis of platinum nanocrystals

for catalytic and electrocatalytic applications
Jingyi Chen , Byungkwon Lim, Eric P. Lee, Younan Xia

Department of Biomedical Engineering, Washington University, St. Louis, MO 63130, USA

Received 11 September 2008; accepted 24 September 2008

KEYWORDS Summary Platinum has been widely used in many applications, especially for catalysis and
Platinum; fuel cell technology due to its ability to maneuver both oxidation and reduction reactions. In
Nanocrystal; addition to size, the shape or morphology of a Pt nanocrystal provides a sensitive knob for tuning
Catalyst; its catalytic and electrocatalytic properties. A number of chemical routes have been developed
Electrocatalyst to produce Pt nanocrystals with well-dened and controllable shapes to improve their perfor-
mance in terms of catalytic activity and selectivity. Conventional polyhedrons (e.g., cubes,
octahedrons, and tetrahedrons) and their overgrown structures (e.g., multipods) have all been
obtained in reasonably high yields, as well as some unconventional shapes (e.g., tetrahexa-
hedrons). Compared to commercially available Pt catalysts, these well-dened nanocrystals
exhibit greatly enhanced activity and selectivity for a range of reactions.
2008 Elsevier Ltd. All rights reserved.

Platinum plays an important role in a wide variety of appli-
cations. For examples, it serves as an excellent catalyst
for CO/NOx oxidation in catalytic converters, production
of nitric acid, rening of petroleum, and many organic
reactions such as hydrogenations [1]. It is also a critical com-
ponent of the fuel cell technology, where Pt acts as the most
effective electrocatalyst for the oxygen reduction reaction
(ORR) and fuel (including hydrogen, methanol, ethanol, and
formic acid) oxidation reaction [2]. As the demand for Pt
grows, the price of Pt has increased by more than four times
from $370 per oz in 1998 to $1600 per oz in 2008 over the last
decade [3]. It is predicted that the demand for Pt will grow
by another 10% in the next scal year [4]. Given the climb-
Corresponding authors.
E-mail addresses: chenj@seas.wustl.edu (J. Chen),
xia@biomed.wustl.edu (Y. Xia).
ing price of Pt, we must nd ways to reduce the amount of
Pt used in a specic application by increasing its catalytic
activity in order to lower the overall cost.
All of the applications mentioned above require the use
of Pt in a nely divided state. The catalytic and electrocat-
alytic activity depend on not only the ratio of surface area
to volume, but also the structure or arrangement of atoms
on the surface. Great effort has been made to increase
the ratio of surface area to volume by reducing the size
of Pt nanoparticles. Studies have also shown that by alter-
ing the surface structure of a bulk single crystal one can
manipulate the catalytic properties of a Pt-based catalyst
[5]. For instance, the hexagonal {1 1 1} surface of Pt was
found to be ve times more active that the square {1 0 0}
surface for the dehydrocyclization of n-heptane, while the
{1 0 0} surface was shown to be more active than the {1 1 1}
surface for the isomerization of isobutene [6]. It has also
been established that a rough surface containing terraced,

1748-0132/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.nantod.2008.09.002
82
Table 1 A summary of different shapes of Pt polyhedrons and their overgrown nanostructures that have been achieved in high
yields in various solvent systems.
Shapes Solvent system
Aqueous
Perfect/truncated cube Refs. [12,15,16,25]
Perfect/truncated octahedron Refs. [14,15,22]
Perfect/truncated tetrahedron Refs. [12,15,18,21]
Overgrowth Refs. [16,17]
Highly branched multipod
stepped, and kinked sites is generally more active than a
at, low-index surface [7]. By taking into account both size
and surface structure, one can tailor the catalytic activity
of a Pt-based catalyst at the nanoscale by controlling the
shape of Pt nanocrystals during their chemical syntheses. In
this review, we will focus on the syntheses of Pt nanocrystals
with well-dened and controllable shapes and their use in
catalytic and electrocatalytic applications.
Shape-controlled synthesis
Platinum has a face-centered cubic (fcc) crystal structure.
Unlike other fcc metals, such as Ag, Au, and Pd, the twinned
nanostructures are rarely formed in Pt probably due to the
high internal strain energies associated with these struc-
tures and the occurrence of oxidative etching (due to O2 )
during a typical synthesis [8,9]. As illustrated in Fig. 1,
the commonly observed Pt nanocrystals are all single crys-
talline in structure. During the past decade, a number of
these different shapes have been accomplished for single
crystalline Pt nanocrystals using chemical approaches. In
general, Pt nanocrystals are synthesized in the presence of
Figure 1 Schematic illustration of different shapes of Pt
nanocrystals derived from conventional single-crystal polyhe-
drons enclosed by the low-index planes {1 0 0} and {1 1 1}.
The rst column represents the perfect polyhedrons, while the
second column contains the truncated forms of the perfect
polyhedrons. The third and fourth columns compromise the
overgrown nanostructures and highly branched nanostructures
grown from the corners of the perfect polyhedrons, respec-
tively. The yellow and blue colors represent the {1 0 0} and
{1 1 1} facets, respectively.
J. Chen et al.
Polyol Non-polar
Ref. [22] Refs. [2830]
Ref. [22]
Ref. [32] Ref. [31]
Ref. [33] Refs. [38,39,41,60]
a capping agent via reduction of a Pt precursor, decom-
position of an organometallic complex, or a combination
of these two routes such as hydrogenated decomposition
of Pt(acac)2 . Table 1 summarizes the different shapes that
have been achieved in three solvent systems arranged
in the order from polar to non-polar: aqueous solution,
polyol, and organic medium. In this section, we mainly
focus on the formation of single-crystal polydrons enclosed
by the low-index facets{1 0 0} and {1 1 1}, as well as
their overgrown structures. We also discuss recent advance
in the synthetic approach based on an electrochemical
method to generate tetrahexahedrons bound by high-index
facets. We then demonstrate the formation of PdPt core-
shell bimetallic nanocrystals via a seeded epitaxial growth
method. Finally, we elaborate on a chemical route to single-
crystal Pt nanowires that is based upon FeIII -mediated polyol
reduction, as well as the use of this approach in the for-
mation of Pt nanowires on various supports for catalytic
applications.
Formation of Pt polyhedrons
Nanocrystals with a polyhedral shape are often enclosed
by a mix of {1 1 1} and {1 0 0} facets. For an fcc metal,
the crystal structure of commonly observed polyhedrons can
be divided into two categories: single crystalline structures
(e.g., cubes, octahedrons, and tetrahedrons) and twinned
structures (e.g., decahedrons and icosahedrons) [8]. In the
case of Pt, twinned structures are associated with high
internal strain energies and can easily be oxidized in a
synthesis. The Pt nanocrystals that have been synthesized
in high yields typically have a single crystal structure.
For an fcc single crystal, the surface energies associated
with the low-index crystallographic planes are in the order
of (1 1 1) < (1 0 0) < (1 1 0) [10]. From the viewpoint of Wulff
construction, the energetically favored shape would be a
truncated octahedron with the optimal truncation fullling
the condition of (1 0 0) /(1 1 1) = d(1 0 0) /d(1 1 1) , where d rep-
resents the distance from the facet to the center of the
particle and this parameter reects the ratio of growth rates
along 1 0 0 and 1 1 1 directions [11]. The ratio of these
two growth rates can be dened as R, which changes from
0.58 for a cube to 0.87 for a cuboctahedron and eventually
to 1.73 for an octahedron. One can alter the surface ener-
gies and thus growth rates by using various capping agents
in a shape-controlled synthesis. Together with manipulation
of the seed structures in the nucleation step by controlling
Shape-controlled synthesis of platinum nanocrystals 83

Figure 2 Transmission electron micrographs of single-crystal Pt nanocrystals in the polyhedral shapes: (a) tetrahedrons synthesized
with H2 as a reducing agent in the presence of sodium polyacrylate (modied with permission from [12], copyright 1996 American
Association for the Advancement of Science); (b) octahedrons synthesized by modifying polyol process with the addition of Ag+
(modied with permission from [22], copyright 2005 American Chemical Society); (c) cuboctahedrons prepared in the presence of
tetradecyltrimethylammonium bromide (TTAB) with a high concentration of NaBH4 as a reducing agent (modied with permission
from [24], copyright 2007 American Chemical Society); and (d) cubes prepared in the presence of TTAB and a low concentration of
NaBH4 (modied with permission from [24], copyright 2007 American Chemical Society).

the reaction kinetics, different morphologies for the single
crystal polyhedrons can be achieved.
Cubes, octahedrons, and tetrahedrons are the three
polyhedrons that have been selectively produced in the
shape-controlled synthesis of Pt nanocrystals by altering the
capping agents. El-Sayed and coworkers were the rst to
demonstrate the synthesis of Pt nanocrystals in the shape of
cube, tetrahedron, and truncated octahedron through the
reduction of K2 PtCl4 by H2 gas in aqueous solutions by vary-
ing the concentration of sodium polyacrylate (the capping
agent) [12,13]. They found that the Pt tetrahedrons were
stabilized at high concentrations of sodium polyacrylate
(Fig. 2a). At low concentrations of sodium polyacrylate, the
Pt tetrahedrons could be transformed to truncated octahe-
drons, eventually resulting in the formation of cubes due to
the deposition of Pt atoms on the {1 1 1} facets [14]. Switch-
ing the capping agent to poly(vinyl pyrrolidone) (PVP), a
same trend was also observed by Miyake and coworkers [15]
that tetrahedrons dominated at high concentrations of PVP
whereas cubes were formed at low concentrations of PVP.
Since then, a number of research groups have investigated
this synthesis [1621]. In a recent study, Yang and cowork-
ers found that the addition of Ag+ to a polyol synthesis could
enhance the growth along 1 0 0 axis and/or suppresses
the growth along 1 1 1 axis [22]. As the concentration
of Ag+ increased in the reaction mixture, the majority of
the Pt nanocrystals were found to change from cubes to
cuboctahedrons, and eventually to octahedrons (Fig. 2b).
By varying the capping agent (e.g., type and concentration),
Pt nanocrystals could be synthesized in the form of tetrahe-
dron, octahedron, or cube, as well as their truncated forms.
These results suggest that both the selectivity of a capping
agent for a specic facet and its concentration play impor-
tant roles in the formation of well-dened polyhedrons.
Pt nanocrystals of different morphologies can also be
obtained through the control of reaction kinetics by vary-
ing reduction conditions. When the reduction is relatively
fast, the nanocrystallite seeds tend to grow and form the
thermodynamically favored shape (i.e., truncated octahe-
dron) in an effort to minimize the surface energy. When
the reduction is slowed down, the shape of a Pt nanocrys-
tal becomes more sensitive to the capping agent. Yang
84 J. Chen et al.

Figure 3 Transmission electron micrographs of Pt nanocrystals with a branched morphology: (a) overgrowth from eight corners
of cubes prepared by decomposition of Pt(acac)2 at a high precursor concentration under H2 atmosphere (modied with permission
from [31], copyright 2007 Wiley-VCH); (b) overgrowth from corners of octahedrons (indicated by a blue arrow) and tetrahedrons
(indicated by a red arrow) prepared using the polyol process with the addition of NaNO3 as an oxidative etchant (modied with
permission from [32], copyright 2004 American Chemical Society); (c) highly branched multipods prepared using the polyol process
in the presence of a trace amount of FeIII species under the protection of N2 after initial exposure to air for 11.5 h (modied with
permission from [33], copyright 2005 Wiley-VCH); and (d) star-like Pt nanoparticles prepared with the addition of Pt tetrahedrons
as seeds (modied with permission from [34], copyright 2008 American Chemical Society).

and coworkers have prepared Pt cuboctahedrons and cubes
by reducing K2 PtCl4 with H2 generated in situ from the
hydrolysis of NaBH4 in the presence of tetradecyltrimethy-
lammonium bromide (TTAB) as a surfactant [23,24]. In this
case, the amount of H2 production, ultimately the reduction
rate, can be controlled by adjusting the pH with NaOH for
the hydrolysis of NaBH4 . At low pH, large amount of H2 was
produced and cuboctahedrons were formed at fast reduc-
tion rate by taking the thermodynamically favored shape
(Fig. 2c). At high pH, small amount of H2 was generated
and selective growth along 1 1 1 directions of cubocta-
hedrons led to the formation of cubes at slow reduction
rate (Fig. 2d). Switching to EO13 PO30 EO13 triblock copoly-
mers as a stabilizer, the size of Pt nanocrystals can be
precisely controlled in the range of 3.56.6 nm via seeded
growth by subsequently adding the precursor to the reaction
[25]. Replacing NaBH4 with a milder reducing agent (e.g.,
ascorbic acid), Pt nanodendrites were obtained as the nal
products [23,26]. Cubic Pt nanocrystals were also synthe-
sized by several other groups. Chen and coworkers prepared
Pt nanocubes by reducing K2 PtCl6 with NaBH4 in an aque-
ous medium, and then transferred them into an organic
medium through dodecanethiol modication under the inu-
ence of HCl, a phase-transfer inducer [27]. Using an organic
medium, Tilley and coworkers have demonstrated the syn-
thesis of Pt nanocubes by decomposing Pt(acac)2 under H2
atmosphere [28]. Recently, Sun and coworkers have obtained
Pt nanocubes of different sizes via thermal decomposition
of Pt(acac)2 with a trace amount of Fe(CO)5 at different
temperatures [29,30].
Overgrowth of polyhedrons into branched
structures
Overgrowth is often observed in the shape-controlled syn-
thesis of Pt nanocrystals. In most cases, overgrowth is
initiated from the corners of a polyhedral seed and further
Shape-controlled synthesis of platinum nanocrystals 85

Figure 4 Electron micrographs of Pt multiple-octahedral nanocrystals: (a and b) TEM and (c) HRTEM images of a sample prepared
by using PVP as a reducing agent in the presence of Fe(III) species. The atomic steps on the Pt {1 1 1} surfaces are indicated by red
arrows. (d) TEM and SEM (inset) images of another sample prepared under the same conditions as in (a) except that the concentration
of FeCl3 was increased by 2.5 times.

developed into a highly branched nanostructure, such as
tetrapod, octapod, and multipod (also known as a porous
structure). The following two criteria have to be met in
order to induce overgrowth in a reaction system: a low
concentration of seeds and a high concentration of free Pt
atoms. Two approaches have been demonstrated to achieve
overgrowth on Pt polyhedral seeds. One approach is based
on the decomposition of an organometallic precursor such
as Pt(acac)2 at low temperatures under H2 atmosphere [31].
The reaction occurred at a relatively slow rate to maintain
a low concentration for the initially formed seeds. When
a high concentration of Pt precursor was used, the excess
Pt atoms accumulated in the reaction induced overgrowth
on the {1 1 1} facets or the eight corners of a truncated
cube or cuboctahedron (Fig. 3a). The second approach is
to introduce an oxidative etchant (e.g., NaNO3 ) into the
polyol process [32]. The overgrowth was found to initiate
from the four corners of a tetrahedron or the six corners
of an octahedron (Fig. 3b). Highly branched nanocrystals
could also be obtained when FeIII species was employed as
an oxidative etchant and coupled with O2 existing in the
polyol process [33]. The key to the formation of branched
nanostructures is to abruptly block oxidative etching by
removing O2 through a continuous N2 ow through the reac-
tion system. In this case, the initial concentration of Pt
seeds was kept at an extremely low level. By blocking
oxidative etching, the concentration of Pt atoms dramat-
ically increased to a high level, leading to overgrowth of
the seeds into highly branched nanostructures (Fig. 3c).
More recently, El-Sayed and coworkers demonstrated the
formation of multiple-armed single-crystal Pt nanostruc-
tures (Fig. 3d) from tetrahedral seeds through an overgrowth
mechanism [34].
In a related study, our group have also demonstrated
that highly faceted Pt nanocrystals with a large number of
interconnected arms in a quasi-octahedral shape (Fig. 4a)
could be prepared simply by reducing H2 PtCl6 precursor with
PVP as a reducing agent in an aqueous solution contain-
ing a trace amount of FeIII species [35]. The formation of
these multiple-octahedral nanostructures can be attributed
to the overgrowth of truncated octahedral Pt seeds along
the 1 0 0 directions in the presence of FeIII species. In this
case, FeIII species could oxidize both Pt atoms and nuclei
back to PtII species and thus signicantly slow down the over-
all reduction rate. Once some Pt seeds had been formed in
the solution, further reduction of the PtII species could be
accelerated via an autocatalytic process, and thereby a high
concentration of Pt atoms could be generated. Since the
86 J. Chen et al.

Figure 5 Schematic illustration and the corresponding TEM images of a proposed 5-step growth process for forming a planar
tripod: (1) growth on three troughs of seed crystal resulting in its enclosure; (2) selective growth around the tip regenerating the
trough; (3) enclosure of trough and growth around the tip; (4) repetition of step 2 and 3 along the three directions resulting in a
tripod; and (5) ripening causing the edges to smoothen. Scale bars are 10 nm for TEM images (ae), and 100 nm for TEM image (f)
(modied with permission from [38], copyright 2007 American Chemical Society).

concentration of Pt seeds is kept low in the presence of FeIII
species, overgrowth of Pt seeds dominated the growth step.
This simple approach enabled us to produce highly faceted
Pt nanocrystals with a large number of edge, corner, and
surface step atoms (Fig. 4b and c) in high yields, without
the need of organic solvents, additional seeds, and sub-
strates. It was also found that the overall dimension of the
multiple-octahedral Pt nanocrystals could be readily con-
trolled by varying the concentration of FeIII species added
to the reaction (Fig. 4d).
As pointed out previously, twinned nanocrystals of Pt are
hard to obtain because of their high internal strain energies
and easiness to be dissolved by oxidative etching. Occasion-
ally, single-twinned particles were observed in the reduction
of H2 PtCl6 with NaBH4 using mercaptosuccinic acid as the
stabilizer [36]. In the kinetically controlled process that
involves a very weak reducing agent such as PVP, small tri-
angular nanoplates were found to only represent 10% of the
nal product, a yield much lower than those achieved for
other fcc metals (e.g., Ag and Pd) using the same strategy
[37]. Although the plate-like nanostructures of Pt are dif-
cult to produce using a kinetically controlled strategy, planar
tripod nanostructures were often observed. These planar tri-
pod nanostructures (Fig. 5) are believed to derive from Pt
seeds containing a single twin along the {1 1 1} plane [38]. In
this case, the planar tripods were produced via the decom-
position of Pt(acac)2 in the presence of a reducing agent
such as 1,2-alkanediols with adamantanecarboxylic acid and
hexadecylamine as stabilizing agents [3941]. Other than
tripods, shapes like mono-, and bi-, pods were also observed
during the same synthesis, and they were proposed to grow
from the decahedrally and icosahedrally twinned seeds,
respectively [38]. Using a similar method, multipods or
porous nanostructures have been obtained by altering the
concentration of Pt precursor. Nanocrystals in the planar
tripod shape were also observed at a low yield in the hydro-
genated decomposition of an organometallic precursor [31].
They were probably formed through the same mechanism
that involved overgrowth from the corners of singly twinned
triangular plates.
Electrochemical synthesis of unconventional
shapes
Many unconventional polyhedrons for example, the tetra-
hexahedron bound by {hk0}, the trapezohedron by {hkk},
the trisoctahedron by {hhl}, and the hexoctahedron by {hkl}
with h > k > l are usually found in minerals of noble met-
als [42]. Generally, these unconventional shapes are hard
to produce using an ordinary chemical method as their sur-
face energies are too high. Nevertheless, Pt nanocrystals
in the tetrahexahedral shape (Fig. 6a and b) have recently
been achieved by Sun, Wang and their coworkers by elec-
trochemically treating spherical particles of Pt deposited on
glassy carbon with a square-wave potential in the presence
of ascorbic acid and sulfuric acid [43]. For a tetrahexahe-
dron (THH), the nanocrystal exhibits Oh symmetry and is
enclosed by 24 high-index facets, which can be viewed as
a cube with each face capped by a square-based pyramid
(Fig. 6cf). In the electrochemical treatment, the square-
wave potential was believed by these authors to mediate
the adsorption behavior of oxygen on various facets of
Pt particles, leading to the formation of such an uncon-
ventional shape. The oxygen atoms could preferentially
adsorb onto the high-index facets and preserve these sur-
faces. In contrast, it was difcult for the oxygen atoms
to absorb onto the low-index facets. Instead, they sim-
ply displaced the Pt atoms on these surfaces, resulting
in disappearance of these facets. The existence of these
high-index facets such as {7 3 0}, {2 1 0}, and/or {5 2 0}
that contain a large number of atomic steps and dangling
bonds makes this shape incredibly active for electrocatalytic
applications.
Shape-controlled synthesis of platinum nanocrystals 87

Seeded epitaxial growth shell, demonstrating the layer-by-layer epitaxial growth of

Heterogeneous epitaxy has been used in gas-phase depo-
sition to prepare heterostructures or junctions [44,45].
Recently, various core-shell bimetallic nanostructures have
also been prepared via heterogeneous epitaxial growth in
the solution phase, in which preformed nanocrystals with
well-dened shapes served as primary sites, i.e. seeds, for
heterogeneous nucleation of a secondary metal with a dif-
ferent chemical identity [46]. It has been shown that a close
lattice match between the seed and the deposited atoms
plays the most critical role in achieving conformal epitaxial
growth for the secondary metal. Since a lattice mismatch
between Pd and Pt is very small (only 0.77%), Pd is expected
to be well suited for achieving conformal epitaxial growth
of Pt. In this regard, we have recently demonstrated that Pt
nanoplates with large lateral dimensions (e.g., edge lengths
>50 nm) could be obtained by using Pd nanoplates as seeds
for heteroepitaxial deposition of Pt (Fig. 7a) [47]. In this
approach, the Pd nanoplates were synthesized by reduc-
ing a Na2 PdCl4 precursor with PVP as a reducing agent and
then served as seeds for the nucleation of Pt atoms formed
by reducing H2 PtCl6 with citric acid. The resulting prod-
uct consists of the core being a hexagonal or triangular Pd
nanoplate and the shell being made of a thin, uniform Pt
Pt on Pd surface (Fig. 7be). The successful preparation of
PdPt core-shell nanoplates through the epitaxial growth
of Pt on Pd suggests that this methodology could be further
extended to generate various PdPt binary nanostructures
by taking advantage of the wide range of shapes that have
already been achieved for Pd nanocrystals.
Growth of nanorods and nanowires
One-dimensional (1D) nanostructures such as rods, wires,
belts, and tubes are characterized by high aspect ratios. 1D
nanostructures of Pt can be fabricated by templating against
channels in porous membranes, sacricial structures (e.g.,
Ag or Se nanowires), as well as self-assembled structures
of surfactants [4851]. Despite the versatility of template-
based syntheses, they are restricted by several drawbacks,
including the requirement of template removal to obtain a
pure product, the limited scope of morphological variation,
and the polycrystallinity often associated with the prod-
uct. Here we only focus on the formation of Pt nanorods
or nanowires via a template-free chemical route. The rst
attempt to generate single-crystal Pt nanorods or nanowires
was accomplished by Xia and coworkers [52]. The 1D nanos-
tructures can be obtained under conditions similar to the

Figure 6 (a) Schematic illustration of the electrochemical preparation of Pt tetrahexahedrons (THHs) from the Pt spheres (agglom-
erates of Pt nanoparticles) under the square-wave potential, which inuenced the dissolution of the spherical particles and the
formation of the Pt THHs; (b) low-magnication SEM image of the Pt THH product; (c and d) high-magnication SEM images of
a Pt THH along different orientations, illustrating the shape of the THH; (e) geometrical model drawing of an ideal THH; and (f)
high-magnication SEM image of a Pt THH, showing the imperfect vertices as a result of unequally sized neighboring facets (modied
with permission from [43], copyright 2007 American Association for the Advancement of Science).
88 J. Chen et al.

aforementioned polyol synthesis for Pt branched nanostruc-
tures. In this case, however, the reaction was allowed to
proceed in air for the entire process, without introduc-
ing N2 . Hence, the rate of precursor reduction was kept
extremely slow, resulting in the formation of hierarchi-
cally agglomerated structures with Pt nanorods grown on
the surface (Fig. 8a and b). The nanorods could be easily
released into the solution by sonication and re-dispersed in
another solvent (Fig. 8c). High-resolution TEM imaging of
these Pt nanorods revealed that they grow along the 1 1 1
axis (Fig. 8d), different from the single-crystal nanorods or
nanowires of Au and Pd which typically grow along the 1 0 0

Figure 7 (a) Schematic illustration of the formation of PdPt core-shell nanoplates through epitaxial growth of Pt shells on
Pd nanoplates with a hexagonal or triangular cross-section; (b) STEM image and (c) cross-sectional compositional line prole of a
PdPt core-shell nanoplate with a hexagonal shape; (d) STEM image and (e) cross-sectional compositional line proles of a PdPt
core-shell nanoplate with a triangular shape (modied with permission from [47], copyright 2008 American Chemical Society). In
the composition line proles, blue and red represent Pd and Pt, respectively.
Shape-controlled synthesis of platinum nanocrystals 89

Figure 8 Electron micrographs of Pt nanowires synthesized via polyol reduction with the addition of FeIII species: (a) SEM image
of the hierarchically structured Pt agglomerates; (b) SEM image of the Pt nanowires covered on the surface of the Pt agglomerates;
(c) TEM image of Pt nanowires sonicated off the Pt agglomerates; and (d) HRTEM characterization of an individual Pt nanowire from
the same sample, showing that the Pt nanowire grows along 1 1 1 direction (modied with permission from [52], copyright 2004
American Chemical Society). (e) SEM image of the Pt hierarchical structures synthesized using the same strategy with the addition
of Pt nanoparticle agglomerates assembled by sodium dodecyl sulfate; and (d) amplied SEM image of Pt long nanowires from the
box indicated in (e) (modied with permission from [57], copyright 2008 American Chemical Society).

axis. The mechanism responsible for Pt nanorod growth slowed down to keep the concentration of Pt atoms at a level
along the 1 1 1 axis remains unclear, although overgrowth below the critical concentration for nucleation. Another
on one of the eight {1 1 1} facets of a cuboctahedral seed mechanism involves the formation of long chain PtII or PtIV
might be involved. In this case, the reduction had to be complexes such as [PtCl4 ]2 or its water-substituted form
90 J. Chen et al.

Figure 9 Electron micrographs of Pt nanorods grown on various substrates via polyol reduction with the addition of FeIII species:
(a) a polymeric sphere coated with Pd nanoparticles (modied with permission form [65], copyright 2006 Wiley-VCH); (b) TiO2
nanobers coated with Pt nanoparticles (modied with permission form [66], copyright 2008 American Chemical Society); (c) a Si
substrate with pyramidal cavities etched on the surface (modied with permission from [68], copyright 2008 Springer); and (d) a Pt
metal gauze (modied with permission from [69], copyright 2007 American Chemical Society).

[PtCl2 (H2 O)2 ] prior to their reduction to Pt atoms [5356].
Upon reduction, these long chain complexes could directly
evolve into nanorods. This mechanism could explain why the
growth direction of the Pt nanorods was different from those
observed for other fcc noble metals.
Long nanowires of Pt (Fig. 8ef) could be generated when
the synthesis was performed with the addition of Pt nanopar-
ticle agglomerates assembled in the presence of sodium
dodecyl sulphate [57]. In addition to this polyol-based route,
Pt nanorods and nanowires have been synthesized using a
-irradiation method [58], formic acid reduction at low tem-
perature [59], and a soft template method (e.g. long alkyl
chain amine) [60,61]. In related work, interconnected Pt
nanowires have been synthesized using a water-chloroform
two-phase system that contained cetyltrimethyl-ammonium
bromide (CTAB) [62]. It was proposed that the worm-like
micellar network formed within the droplets of chloroform
led to the conned reduction of Pt precursor and nanocrystal
growth into this unique morphology. The two-phase system
(e.g., water-organic solvent) was also investigated by sev-
eral other groups and networks of thin Pt nanowires were
produced [63,64].
Inspired by the growth mechanism of the hierarchi-
cal structures, we also demonstrated the growth of Pt
nanorods/nanowires on several different substrates for
catalytic applications by using the FeIII -mediated polyol pro-
cess. Fig. 9a shows that the Pt nanorods could be grown
on the silica or polymer beads, when the surfaces of these
beads were decorated with thin layers of Pd nanoparti-
cles [65]. As ceramic materials often serve as supports
for catalysts, we have further demonstrated the growth of
Pt nanowires on TiO2 nanobers (Fig. 9b) [66,67]. These
TiO2 nanobers coated with Pt nanowires could be readily
processed as membranes for industrial applications. Fur-
thermore, Pt nanorods were prepared on other supports such
as silicon wafers and metal gauzes for fuel cell applications,
as shown in Fig. 9c and d, respectively [68,69]. In all these
cases, the growth of Pt nanorods/nanowires seemed to fol-
low the same mechanism as the aforementioned one since
the growth direction was along 1 1 1 axis.
Catalytic and electrocatalytic applications
As mentioned at the beginning of this review article, Pt
serves as a key catalyst for many reactions and industrial
applications. The catalytic properties of a catalyst can be
evaluated in terms of reactivity, selectivity, and stability.
Shape-controlled synthesis of platinum nanocrystals
In general, Pt nanocrystals of ner sizes provide higher sur-
face/volume ratios, thereby increasing the catalytic activity
compared to larger crystals of the same mass. Moreover, Pt
nanocrystals with specically tailored surface structures (or
facets) are also expected to improve the activity and selec-
tivity of a catalyst. In this section, we take some recent
examples to highlight the impacts of shape-controlled Pt
nanocrystals on both catalytic and electrocatalytic applica-
tions.
Catalytic activity and selectivity
Pt can catalyze many organic reactions, especially those
involving hydrogen in the so-called hydrogenation processes
[70,71]. As established with single crystals, the activity and
selectivity of these reactions is sensitive to the crystallo-
graphic planes and typically the catalytic activity can be
enhanced on high-index facets that are rich in stepped and
dangling atoms [5,7]. Through shape-controlled synthesis,
it is possible to maneuver the shape of a nanocrystal to
only expose a specic set of facets. For example, a tetra-
hedron is bounded by {1 1 1} facets and a cube is covered
by {1 0 0} facets, whereas a cuboctahedron is enclosed by
a mix of {1 0 0} and {1 1 1} facets. This class of novel nano-
materials holds promise for maximizing selectivity and/or
rate of catalytic reactions. In addition, they are excellent
model systems for basic mechanistic research in catalysis
[72] because (i) they have high enough surface areas for
accurate rate measurements at high pressures and even
transient kinetic or mechanistic studies at 1% of a monolayer
detection sensitivity, which is impossible with usual single
crystals of the type commonly studied by surface scientists;
(ii) they can provide FTIR spectra and other experimental
data for adsorbates that are far simpler to interpret (due
to the homogeneity in surface site); and (iii) the measured
results can be directly compared to calculations, which only
address single crystal surfaces. Here we only discuss how
these well-dened Pt nanocrystals alter the catalytic activ-
ity and how they are ranked relative to the bulk single
crystals.
El-Sayed and coworker investigated the effect of shape
on the catalytic activity and stability of Pt nanocrystals
[7377]. They conducted a comparative study with Pt
nanocrystals in different shapes, including tetrahedrons,
cubes, truncated octahedrons, and star-like nanoparticles
and focused on two types of reactions: the electron transfer
reaction between [Fe(CN)6 ]3 and S2 O3 2 , and the Suzuki
cross-coupling reaction between phenylboronic acid and
iodobenzene to yield biphenyl. They estimated from the
TEM analysis that the percentage of atoms located at either
corners or edges relative to the total surface atoms for
an individual tetrahedral, cubic, and truncated octahedral
nanocrystal of 5 nm in size and found the following num-
bers: 35%, 13%, and 6%, respectively [76,78]. When cubes enclosed by {1 0 0} facets and cuboctahedrons enclosed
these nanocrystals of different shapes were applied to
the electron transfer reaction, the average rate constant
of the reaction increased exponentially as the percent-
age of surface atoms at the corners and edges increased.
They also compared the catalytic performance of star-like
nanocrystals with the tetrahedrons on this electron trans-
fer reaction. The star-like nanocrystals contained high-index
91
facets such as (3 1 1) and were found to lower the acti-
vation energy of the reaction by 1.6 times compared to
the tetrahedral nanocrystals [34]. In the second case, how-
ever, little difference in the catalytic activity was found
for the Suzuki coupling reaction regarding to these differ-
ent shapes [77]. They examined the nanocrystals after the
reaction and found that the initially well-dened shapes of
the nanocrystals had disappeared. The change of shape for
the nanocrystals can be attributed to the interfacial free
energy that is strongly dependent on temperature variation
and molecule adsorption on the surface during the catalytic
reaction [79,80].
The study of catalytic activity of Pt nanocrystals for
hydrogenation reactions was conducted by Somorjai and
coworkers [24]. They compared the conversion percentage
of ethylene to ethane by using cubes, cuboctahedrons, and
porous nanoparticles. In this study, porous nanoparticles
were found to be the most active. The shape of the parti-
cles remained unchanged after the catalytic reaction. This
could be attributed to the larger size of the particles that
were used, relative to those used by El-Sayed and coworkers.
In the second case, Somorjai and coworkers examined the
catalytic selectivity of Pt cubes and cuboctahedrons in the
hydrogenation of benzene. Similar to bulk single crystals,
the cubic nanocrystals enclosed by {1 0 0} planes yield cyclo-
hexane as the product, whereas cuboctahedrons enclosed
by {1 1 1} planes in addition to {1 0 0} planes produce a
mixture of cyclohexane and cyclohexene as the nal prod-
uct (Fig. 10). Moreover, the apparent activation energy for
cyclohexane production catalyzed by the cubic nanocrystals
were found to be 10.9 0.4 kcal/mol, while the apparent
activation energy for cyclohexane and cyclohexene pro-
Figure 10 Turnover rates of cyclohexane (C6 H12 ) and cyclo-
hexene (C6 H10 ) formation for benzene hydrogenation on Pt
by both {1 0 0} and {1 1 1} facets (modied with permission from
[24], copyright 2007 American Chemical Society). Note that only
C6 H12 was formed on the Pt(1 0 0), while both C6 H12 and C6 H10
were produced on the Pt(1 1 1). The nanocrystals not only retain
the catalytic selectivity for the hydrogenation of benzene, but
increase the reactivity by three times compared to that of bulk
single crystals.
92
ductions catalyzed by the cuboctahedral nanocrystals were
8.3 0.2 and 12.2 0.4 kcal/mol, respectively. As compared
to the activation energy of the hydrogenation of benzene
on the bulk {1 0 0} and {1 1 1} planes, the value for Pt
nanocrystals was found to be three times lower. These dif-
ferences could be ascribed to the presence of more corner
and edge sites available on the nanocrystals for enhancing
catalytic activity or changes in electronic structure for the
Pt nanocrystals.
Xia and coworkers compared the catalytic activity of
Pt nanoparticles and Pt nanowires deposited on anatase
nanobers for the hydrogenation of methyl red [66]. The
highly porous nature of the brous membrane allowed
the methyl red solution to be passed through at a rate
as high as 0.5 mL/s (Fig. 11a). The catalytic activity of
the Pt nanostructures can be easily evaluated from the
UVvis spectra taken from solutions of methyl red after
Figure 11 (a) Schematic illustration of a continuous ow
cell used to convert the methyl red in an aqueous solution
into amines through a Pt-catalyzed hydrogenation reaction; and
(b) UVvis spectra recorded before and after the methyl red
solution passed through the ber membranes decorated with
Pt nanoparticles or nanowires (modied with permission from
[66], copyright 2008 American Chemical Society). Note that the
decrease in UVvis absorbance corresponded to azo bond cleav-
age of methyl red via hydrogenation after the 46 M methyl
red solution had passed through the anatase membranes whose
surfaces had been decorated for 3, 7, and 19 h with Pt nanopar-
ticles or with Pt nanowires (Pt NW).
J. Chen et al.
hydrogenation (Fig. 11b). The untreated methyl red solution
shows broad peaks from 500 to 575 nm. After the methyl red
solution had been saturated with H2 gas and passed through
the Pt-decorated ber membranes, a sharp reduction in
the absorbance was observed, indicating that the methyl
red solution had been catalytically hydrogenated. Fig. 11b
compares the performance of membranes coated with Pt
nanoparticles (at a deposition time of 3, 7, or 19 h) and Pt
nanowires. The catalytic activity correlated well with the
length of time for Pt nanoparticle deposition, with the 3 h
sample having the lowest activity and the 19 h sample having
the highest activity. This difference in catalytic activity was
mainly caused by the varying densities of Pt nanoparticles on
the membrane; as the density increased, there were more
active sites on the catalyst. The highest catalytic activity
occurred with the Pt-nanowire decorated membrane. This
could be attributed to the growth of Pt nanowires on the
ber that further enlarged the active surface area, resulting
in more efcient cleavage of the azo bond.
From these initial studies, we know that the well-dened
shapes of Pt nanocrystal not only retain the catalytic proper-
ties of the bulk metal, but also greatly enhance the catalytic
activity as more active sites (e.g., corner, edges, and steps)
are present in the nanostructures. It should also be pointed
out that the capping agents used in the shape-controlled syn-
thesis may alter the catalytic activity of the Pt nanocrystals.
For example, recent work by Yang and coworkers showed
that Pt nanocrystals capped with TTAB exhibit much higher
catalytic activity than PVP-capped Pt nanocrystals [23].
Therefore, it is of great importance to carefully examine
not only the effect of shape, but also the effect of cap-
ping agents and the stability of the nanocrystals during the
catalytic reaction.
Fuel cell applications
Electrocatalysts containing various metals are required to
enhance the rates of half reactions on the cathode and
anode of a fuel cell. One common type of fuel cell elec-
trocatalyst is based upon Pt nanoparticles supported on
carbon particles or Pt on carbon black (Pt/C). It is the most
widely used cathode catalyst system for the oxygen reduc-
tion reaction (ORR). Pt-based catalysts can also be used
for anode reactions to catalyze different oxidation reac-
tions depending on the type of fuels, for example, methanol
oxidation reaction (MOR) in the direct methanol fuel cell
or ethanol oxidation reaction (EOR) in the direct ethanol
fuel cell. The performance of the electrocatalyst is usu-
ally assessed by a set of parameters that include specic
activity current density based on electrochemical surface
area (ECSA) of the catalyst; mass activity current den-
sity based on mass of the catalyst; and durability the
loss of ECSA after a certain number of cyclic voltammetry
(CV) cycles. The shape of Pt nanocrystals plays an import
role in determining the performance of an electrocatalyst
because the adsorption behaviors of species involved in
the electrochemical reaction appears differently on vari-
ous facets of the nanocrystals. In ORR, the most commonly
used electrolytes are HClO4 and H2 SO4 . The catalytic activity
is strongly related to the surface structure. For exam-
ples, in the non-adsorbing electrolyte HClO4 , the activity
of ORR decreased in the order of (110) > (1 1 1) > (1 0 0) due
Shape-controlled synthesis of platinum nanocrystals
Figure 12 ORR polarization curves for 20-nm Pt multi-
octahedrons and Pt/C (E-TEK) catalyst recorded at room
temperature with a sweeping rate of 10 mV/s in O2 -saturated
HClO4 solution (0.1 M). The inset compares the specic activity
(left) and mass activity (right) for these two catalysts at 0.85 V.
The kinetic currents were calculated using mass-transport cor-
rection from ORR polarization curves. The loading of 20-nm Pt
multi-octahedrons and Pt/C (E-TEK) catalyst on the rotating disk
electrode was the same, 15 g(Pt)/cm2 .
to the decreased interaction strength between O2 and dif-
ferent surface structures and increased adsorption of the
OH species on these surfaces [81]. In comparison, for the
adsorbing H2 SO4 electrolyte, the activity of ORR decreased
in the order of (1 1 1) < (1 0 0) < (1 1 0), as determined by the
adsorption and inhibiting effect of bi-sulfate anion [81].
Xia and coworkers demonstrated that Pt multi-
octahedrons exhibited higher catalytic activity per unit
surface area than the commercial Pt/C (E-TEK) catalyst
due to the high ratio of {1 1 1} to {1 0 0} as exposed facets
and the presence of surface steps on their surfaces [35].
Fig. 12 shows the room temperature polarization curves
for the 20-nm Pt multi-octahedrons along with the Pt/C
(E-TEK) catalyst. The half-wave potentials for the 20-nm
Pt multi-octahedrons and Pt/C catalyst were 0.843 and
0.840 V, respectively. The inset of Fig. 12 compares their
specic activities (left) and mass activities (right) at 0.85 V.
Although similar mass activities were observed, the specic
activity of the 20-nm Pt multi-octahedrons was 2.7 times
higher than that of the Pt/C catalyst, presumably due to
the preferential exposure of {1 1 1} facets rich of surface
steps on their surfaces. In addition to activity, the durability
of 20-nm Pt multi-octahedron catalyst also increased as
compared with that of the Pt/C catalyst. The performance
degradation of Pt catalysts over time is mainly attributed
to the loss of ECSA. After 4000 cycles, the ECSA of 20-nm
Pt multi-octahedrons showed a slight loss of 5.7%, as
compared to 34% ECSA loss for Pt/C catalyst. The higher
durability of Pt multi-octahedrons can be attributed to
the unique morphology, i.e. a highly branched structure
consisting of interconnected octahedral arms. It is known
that Pt-nanoparticle coarsening and corrosion of carbon
support are the major contributions for ECSA loss of Pt/C
catalyst. It was found that 20-nm Pt multi-octahedrons
after durability test retained their branched structure
without signicant particle coarsening, which also enables
93
their use as a catalyst without carbon support. Therefore,
carbon corrosion could be avoided in multi-octahedral Pt
nanocatalysts.
Recently, Sun and coworkers studied Pt nanocrystals,
such as cubes, truncated cubes, and polyhedrons, as cat-
alysts for ORR in H2 SO4 [29,30]. The specic activity of
the Pt nanocubes was found to be four times higher than
those of the polyhedrons or truncated cubes. Similar to
the bulk single crystals, this phenomenon was attributed to
the different adsorption abilities of bi-sulfates on Pt(1 0 0)
as compared to Pt(1 1 1) facets. This simple demonstra-
tion shows the potential of Pt nanocrystals with controlled
shapes for improving the fuel cell technology.
Similar to the shape effect on catalysis, the atoms at
the steps, edges, and kinks are catalytically more active;
therefore high-index facets are expected to exhibit higher
catalytic activity than the commonly formed low-index
facets. For instance, Pt THHs with high-index {730}, {210},
and/or {520} facets obtained through the electrochemical
treatment have been demonstrated for use as electro-
catalysts for ethanol and formic acid oxidation reactions,
respectively. In the this study, the Pt THHs were found to
be 2 times more efcient per unit surface area for the
electro-oxidation of ethanol and 4 times more efcient for
formic acid electro-oxidation as compared to Pt nanospheres
and the commercial 3.2 nm Pt/C catalysts [43]. The results
clearly show that the Pt THHs exhibit greatly enhanced cat-
alytic activity per unit surface area for the oxidation of small
organic molecules.
1D nanostructures of Pt also show increase in both cat-
alytic activity and stability for the fuel cell applications.
In a recent demonstration for MOR, Pt gauze covered with
Pt nanowires were found to enhance the catalytic activ-
ity by 1.6 times as compared to the plain Pt gauze [82].
This is because the ECSA of Pt nanowire decorated on the
metal surface increased by four times than that of the plain
metal surface. The stability of the Pt gauze covered with
Pt nanowires was also greatly enhanced. The results are in
agreement with a previous study [83], where Pt nanotubes
were examined by Yan and coworkers as electrocatalysts for
ORR and greatly increased stability was also observed for
these 1D nanostructures.
Conclusion
Platinum nanocrystals having well-dened shapes have been
achieved via various chemical routes in different solvent
systems. In general, the Pt nanocrystals are less diverse
in terms of shape variation as compared to Ag, Au, and
Pd because twinned structures are difcult to form in Pt
due to their high internal strain energies and susceptibil-
ity to oxidative etching. To date, only polyhedrons such
as cubes, octahedrons, tetrahedrons, and their overgrown
forms have been achieved for the shape-controlled synthe-
sis of Pt nanocrystals. Some unconventional shapes have
also been achieved for Pt nanocrystals by electrochemical
treatment. Through seeded epitaxial growth, we can obtain
Pt-containing bimetallic core/shell structures with different
shapes. All these advances in shape-controlled synthesis of
Pt nanocrystals provide an opportunity to engineer their cat-
alytic properties for various industrial applications. Initial
studies suggest that the shape of a Pt nanocrystal affects not
94
only the catalytic reactivity, but also the catalytic selectiv-
ity. Generally, Pt nanocrystals enclosed by high-index facets
exhibit much higher catalytic activity than those encased
by low-index facets. In the fuel cell technology, the cat-
alytic activity strongly depends on the interaction of the
species present in the solution and the surface structure
of the catalyst. The surface structures of Pt nanocrystals
could be engineered such to increase the activity and dura-
bility for both cathode and anode reactions. It is worthy
noting that the capping agents used in the production of Pt
nanocrystals may alter their catalytic activity. It remains to
be fully explored and understood how the sizes, shapes, sur-
face structures, and capping agents affect the catalytic and
electrocatalytic properties of Pt nanocrystals. Once these
relationships have been established, it will become possible
to design the next-generation catalysts and electrocatalysts
for a broad range of technologically important applications.
Acknowledgements
This work was supported in part by research grants from
NSF (DMR, 0804088 and 0451788), ACS (PRF-44353-AC10), a
DARPA-DURINT subcontract from Harvard University, and an
AFOSR-DURINT subcontract from SUNY Buffalo. Y.X. was a
Camille Dreyfus Teacher Scholar, an Alfred P. Sloan Research
Fellow, and a David and Lucile Packard Fellow in Science
and Engineering. B.L. was also partially supported by the
Postdoctoral Fellowship Program of the Korea Research
Foundation (KRF).
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Jingyi Chen received a B.S. from Sun Yat-
Sen University in China (1997), a M.A. in
chemistry with Professor Kimberly A. Bagley
from SUNY College at Buffalo (2002), and
a Ph.D. in chemistry and nanotechnology
with Professor Younan Xia from the Univer-
sity of Washington in Seattle (2006). She
then worked as a postdoctoral fellow at
Brookhaven National Laboratory. In May 2008,
she began as a Research Assistant Professor in
95
the Department of Biomedical Engineering at Washington University
in St. Louis. Her research interests include synthesis, characteriza-
tion, and surface functionalization of nanomaterials for applications
in catalysis and biomedical research.
Byungkwon Lim was born in Seoul, Korea,
in 1975. He received his B.S. (1998), M.S.
(2000), and Ph.D. (2004) degrees all from the
School of Chemical and Biological Engineer-
ing, Seoul National University, Korea. During
his graduate study, he worked on the synthesis
of polymeric and carboneous nanostructures
using vapor deposition polymerization. He
then worked as a senior researcher on the
synthesis and structural analysis of polymeric
materials for 3 years at LG Chem, Korea. He
has been working with Professor Younan Xia as a postdoctoral fellow
since March, 2007. His research interests include shape-controlled
synthesis of noble-metal nanocrystals, surface plasmonic proper-
ties, carboneous nanostructures, and catalysis.
Eric Lee received a B.S. degree in mathemat-
ics (2003) and a B.S.H. in chemistry (2004)
from Queens University in Kingston, Ontario.
In 2008, he received a Ph.D. degree with Pro-
fessor Younan Xia from the Department of
Biomedical Engineering at Washington Univer-
sity in St. Louis. He is now a postdoctoral
fellow with Professor Luke Lee at the Depart-
ment of Bioengineering at the University of
California, Berkeley. His research interests
include synthesis and utilization of metal
nanostructures for applications in elds such as catalysis, fuel cells,
and biomedical research.
Younan Xia received a B.S. degree in chemi-
cal physics from the University of Science and
Technology of China in 1987, a M.S. degree
in inorganic chemistry from the University
of Pennsylvania (with the late Professor Alan
G. MacDiarmid) in 1993, and a Ph.D. degree
in physical chemistry from Harvard Univer-
sity (with Professor George M. Whitesides) in
1996. He started as an Assistant Professor of
Chemistry at the University of Washington in
Seattle in 1997, and promoted to Associate
Professor and Professor in 2002 and 2004, respectively. In the fall
of 2007, he relocated to Washington University in St. Louis to take
the position of James M. McKelvey Professor for Advanced Materi-
als in Department of Biomedical Engineering. His research centers
on the design and synthesis of nanostructured materials with con-
trolled properties for applications in imaging, sensing, drug delivery,
cancer treatment, neural engineering, catalysis, energy conversion,
photonics, and electronics.