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Cite this: DOI: 10.1039/c2cs35319a

www.rsc.org/csr REVIEW ARTICLE

Synthesis of colloidal metal and metal alloy nanoparticles for
electrochemical energy applications
Hongjun You,a Shengchun Yang,*a Bingjun Dinga and Hong Yang*b
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A

Received 7th August 2012

DOI: 10.1039/c2cs35319a

This Review is focused on the recent progresses in the synthetic approaches to the precise control
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of structure, size, shape, composition and multi-functionality of metal and metal alloy
nanoparticles. Many of these strategies have been developed based on colloidal methods, and to
limited extent, the galvanic and other methods. The shape, size and composition often govern
the chemical and catalytic properties that are important for electrochemical energy applications.
The structure–property relationship and the design in controllable structures and morphologies
for specific reactions such as oxygen reduction reaction (ORR) are emphasized.

1. Introduction control of the properties of materials. While the electronic

Since ‘‘nano’’, which is derived from the Greek word, ‘‘dwarf’’,
was introduced as a new concept in 1960s, the preparation of
nanomaterials through either bottom-up or top-down
approaches has been the focus of decades of scientific studies.
Understanding the nanoscale phenomena allows for better
a
Ministry of Education Key Laboratory for Non-Equilibrium
Synthesis and Modulation of Condensed Matter, State Key
Laboratory for Mechanical Behavior of Materials, School of
Science, Xi’an Jiaotong University, Xi’an, Shannxi 710049,
P. R. China. E-mail: ysch1209@mail.xjtu.edu.cn
b
Department of Chemical & Biomolecular Engineering, University of
Illinois at Urbana-Champaign, 114 Roger Adams Laboratory,
MC-712, 600 S. Mathews Ave., Urbana, Illinois, USA.
E-mail: hy66@illinois.edu; Fax: +1-217-333-052;
Tel: +1-217-244-6730
structures of metals and metal alloys do not typically show
quantum effects at the size comparable to semiconducting
quantum dots, their physical, chemical and catalysis properties
are no longer dependent exclusively on the composition either,
but also the size and shape when they are in low nanometer
(nm)-sized range. For instance, for gold, which has been
considered to be catalytically inactive for a long time,1 the
supported gold nanoparticle (NP) catalysts show an extra-
ordinary catalytic performance for low-temperature oxidation
of carbon monoxide2 and the hydrochlorination of ethyne to
vinyl chloride.3 The metal NPs of Au, Ag, Cu and Pd possess a
range of other properties, which can be controlled by varying
their size and morphology.4–9 In recent years, tremendous
progresses have been made on bimetallic nanocrystals because
of the newly developed capability in controlling the

Dr Hongjun You received his Dr Shengchun Yang received

MS and PhD degrees in
Materials Science and Engineer-
ing (with Professor Bingjun Ding
and Professor Hong Yang) from
Xi’an Jiaotong University in
2008 and 2011, respectively. He
spent two years (2008–
2010) as a visiting student in
the Department of Chemical
Engineering, University of
Rochester. In 2011 he joined the
School of Science and MOE Key
Laboratory for Non-Equilibrium
Hongjun You Synthesis and Modulation of
Condensed Matter in Xi’an
Jiaotong University. He has published over 20 papers in peer reviewed
journals. His research has involved growth mechanisms and the
application of colloidal noble metal and alloy nanomaterials.
his PhD degree in Physics
from Xi’an Jiaotong Univer-
sity (XJTU), China in 2008
under the supervision of Prof.
Ding Bingjun. Between 2007
and 2008, he worked in the
group of Professor Hong
Yang at the University of
Rochester as a research
scholar. He is currently an
Associate Professor in the
Department of Material
Physics at XJTU. His main
Shengchun Yang research interests are the
synthesis and assembly of
nanomaterials, and materials for energy applications such as
batteries, fuel cells and photocatalysis.

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.

composition and thus, physical and chemical properties.10,11
For instance, heterostructures of Pt–M (M = Au, Pd, Ru)
bimetallic NPs show much improved catalytic performance
toward oxygen reduction,12–18 formic acid oxidation,19,20 and
methanol oxygen,21–25 compared with Pt catalysts.
Generally, metallic NPs with specific morphologies are
prepared by controlling the anisotropic growth using surfactants,
or based on the intrinsic growth habits of crystals. The lattice
defects existing in crystal seeds are helpful for making symmetry-
reduced morphologies, such as one-dimensional (1-D) rod and
two-dimensional (2-D) plate. Surfactants typically play the roles
in tuning surface energy and particle dispersity through the
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A
interaction between the organic groups of surfactants and solvent
molecules. Through surfactant and metal surface interaction,
certain crystal plane of a given NP is often preferentially stabilized
by surfactants through strong binding in comparison with other
crystal planes.11 The growth based on crystal habits is
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mainly governed by surface energy. Nanocrystals form thermo-
dynamically stable cubes when {100} facets have the lowest
surface energy, while a tetrahedral shape forms when {111} facets
have the lowest surface energy.26–28
In the case of lattice defects, a stacking fault is a common
phenomenon for metal NPs. The final morphologies of nano-
crystals are often affected by the number of twin defects, such
as, single twin, cyclic penta-twin, and multiple planar
twins.10,29,30 Every single one of the above factors can play
the dominant role in the growth behavior of nanocrystals, and
controlling the shape of NPs often requires a synergy among
the various factors. Therefore, although the equilibrium shape
of an face-centered cubic (FCC) metal nanocrystal typically
has a truncated octahedral shape in an inert gas or vacuum,24
nanocrystals that are bounded by high-index facets with
high surface energy still form in solution phase.31–36 The
stabilization can arise from the change of surface energy due
to the interactions between different particle surfaces and
capping agents, additives, and solvents. Thus, crystal growth
habits in a colloidal system can greatly deviate from those with
Prof. Bingjun Ding received
his PhD degrees in Materials
Science and Engineering from
Xi’an Jiaotong University in
1990. In 1993 he worked at
University of Minnesota as a
Senior Visiting Scholar.
Dr Ding was the Editor-in-
Chief of the book entitled
‘‘Nanostructured Materials’’
published in 2004. He was a
National Science and Technol-
ogy Progress Award (second
prize, 2008) recipient. Now he
Bingjun Ding is a Professor for Advanced
Materials in the State
Key Laboratory for Mechanical Behavior of Materials,
Xi’an Jiaotong University. His research interests include
electrical contact materials, vacuum arcs and their applications,
plasma coatings and nanostructured materials.
Chem. Soc. Rev.
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pristine faces. In addition, by introducing the twin defects
during the nucleation and growth stages, the total free energy
can be reduced to a level lower than that of the Wulff
polyhedron.8 Decahedron and icosahedron are two kinds of
such morphologies.
The colloidal metal and metal alloy NPs, especially platinum
and platinum-based alloys have been the choice of catalysts
in many important chemical and electrochemical reactions
including oxygen reduction reaction (ORR) and direct methanol
oxidation reaction (MOR). It is well known that catalytic
reactions are sensitive to the electronic structure and surface
atomic arrangement or coordination, which can be controlled by
tuning the composition and shape of NP catalysts.18,25,37 Thus,
engineering the structures of colloidal alloy NPs is a rational
approach to improve the properties or to obtain desirable
functions.38,39
In this Review, we will discuss the general growth mechanisms
and strategies developed in recent years in the synthesis of
colloidal metal and metal alloy nanocrystals with controlled
morphologies. Some catalytic applications of Pt-based colloidal
NPs will be discussed as well.
2. General mechanisms for the synthesis of
colloidal metal and metal alloy nanocrystals
2.1 Surface energy and surfactant-governed growth
For pristine single crystal metal particles, surface energy plays
the most important role on the growth of crystals. It controls
the crystal formation through two main mechanisms. One is
based on the thermodynamic equilibrium, and the metal
crystal shape is predicted by lowest total surface energy. The
other is based on the growth kinetics, the atom diffusion on
different surfaces is a limiting factor. Most noble metals
crystallize in an FCC lattice, in which the surfaces possessing
the lowest surface energy are usually the low-index {111},
{110}, and {100} facets.40,41 Typically, the thermodynamic
Prof. Hong Yang received his
PhD degree from University of
Toronto in 1998. After working
at Harvard University as an
NSERC postdoctoral fellow, he
started his independent research
at University of Rochester before
joining the faculty of University
of Illinois at Urbana-Champaign
as a Professor of Chemical and
Biomolecular Engineering in
January 2012. Dr Yang is an
NSERC Canada Doctoral Prize
winner and an NSF CAREER
Hong Yang Award recipient. He is a Section
Editor on Nanotechnology for
Current Opinion in Chemical Engineering, and serves on the editorial
boards of Nano Today and other journals. His research interests
include the shape control of nanocrystals, surface modification,
electrocatalysts, and nanomaterials for energy and biological
applications.
This journal is c The Royal Society of Chemistry 2012

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Fig. 1 Shape evolution during the surface growth for a metal single
crystal (adapted with permission from ref. 8. Copyright 2009 Wiley-VCH).
(a) Growth rate of y surface is more rapid than x surface that results in the
elongation of the x surface and the eventual disappearance of the y
surface, and (b) vice versa. The length of an arrow is directly proportional
to the growth rate. Surfactant-tuned Ag NP growth. TEM images of (c)
spherical, single crystal Ag seeds, (d) Ag octahedral NPs capped with
sodium citrate (Na3CA), (e) Ag cubic NPs capped with PVP. (Adapted
with permission from ref. 44. Copyright 2010 American Chemical
Society.) Ag polyhedrons grown from 40-nm cubic seeds in the presence
of 0.1 mM PVP with times of (f) 5 min, (g) 10 min, (h) 20 min and 1.0 mM
PVP with times of (i) 5 min, (j) 10 min, (k) 20 min. (Adapted with
permission from ref. 46. Copyright 2012 American Chemical Society.)
equilibrium shape of single-crystalline particle is a truncated
octahedron (Wulff polyhedrons).26 This morphology is mainly
bound by {111} and {100} facets, with the {110} facets
bridging the two. When kinetic factors are taken into con-
sideration, the final crystal has the shape determined through
the crystal growth from primary nuclei. In general, atoms
firstly deposit on a surface to form adsorbed atoms, then move
on the surface to positions with the lowest energy to form
crystals. During this process, the diffusion of atoms is confined
more strongly on high energy surfaces than that on low energy
surfaces, resulting in a rapid growth on high-energy surfaces.
As illustrated in Fig. 1a–b, the continuous growth results in
the expansion of slow growing facets at the expense of the fast
growing ones, producing a polyhedron, bound largely by slow
growing facets. Such kinetically controlled growth results in
the enlargement of one set of crystallographic facets at the
expense of others, and leads to the formation of new shapes.8
For Ag nanocrystals, the shape evolves from a cube to a
cuboctahedron and finally to an octahedron, with an increas-
ing ratio of surface areas between {111} and {100} facets.27,28
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In practice, capping agents are almost always used to tune
the surface energy and thus to change the growth habit of
different facets of colloid metal and metal alloy nanocrystals.
Most surfactants, the commonly used capping agents, are
adsorbed on the surfaces of nanocrystals through chemical
or physical adsorption, in which the electrons on the
surfactants and surface atoms form strong interaction.42 The
surfaces of nanocrystals are greatly stabilized by surfactant
molecules, as the surface energy decreases. The electronic
structures of different facets are different, therefore the
adsorption energies of a surfactant on different facets are
different. For instance, when oleylamine and oleic acid are
used as surface capping agents, the adsorption energy of Pt
crystal facets follows the order of {110} 4 {100} 4 {111}.42
Without surfactant, the {100} surface energies of FCC metals
are close to that of the {111} surface. Thus two distinct shapes,
namely, octahedra enclosed by {111} facets and nanocubes/
nanobars enclosed by {100} facets, can be produced by adding
different surfactants. A good example is the shape control of
Ag nanocrystals by using different capping agents. Octahedra
with {111} facets form when citrate is used in the synthesis,
because citrate binds more strongly to Ag {111} than {100}
facets.43,44 On the another hand, with Br ions and the
surfactant of poly(vinyl pyrrolidone) (PVP), which have been
shown to bind more strongly to Ag {100} than {111} facets,
Ag nanocubes/nanobars bound by {100} facets are produced
(Fig. 1c–d).44,45 In the absence of PVP, the free energy of
various low-index facets of Ag polyhedron increases in the
order of {111} o {100} o {110}, so only with the increase of
PVP concentration can Ag NPs be transformed from octahedra
to cubes (Fig. 1f–k).46
Besides altering the surface energy, surfactant molecules can
sometimes prevent the metal atoms depositing on the surface
of metal NPs. Thus, both shape and size can be controlled by
surfactant molecules. In some cases, tiny colloids of metal NPs
are obtained by using surfactants that bind strongly with metal
surfaces. For instance, thiol-based surfactant molecules bind
with gold atoms, thus the size of gold NPs can be controlled
by using relatively large amounts of surfactants.47 Those
surfactant molecules that show selected adsorption on metal
atoms and facets are used to create the anisotropic growth,
because the growth of facets covered by surfactant molecules is
limited. Under this condition, NPs with anisotropic shapes are
obtained, such as nanowires,48 nanorods,49 and nanoplates.7
Some surfactants, such as cetyltrimethylammonium bromide
(CTAB), prefer adsorption on the surfaces, altering the growth
of the NP to form facets with high curvature.50 Others prefer
adsorption on the apexes and edges of NPs, thus preventing
these regions from being etched.51 Under certain conditions,
the interactions between surfactants and metal NPs change
not only the growth habits, but the seed structures, such as
twin-planes. An example is the synthesis of Pt multipods from
platinum acetylacetonate [Pt(acac)2] in the presence of
adamantanecarboxylic acid (ACA), hexadecylamine (HDA),
and 1,2-alkanediol. The alkyl length of the diol and the
competitive binding of HDA, ACA and 1,2-alkanediol on
the surface of crystals were found to be the critical point in
the shape control. Fig. 2 shows the effect of molar ratios
between dodecanediol (DDD) and HDA on the final morphologies
Chem. Soc. Rev.

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Fig. 2 TEM images showing the effect of molar ratios between HDA
and DDD on the formation of Pt multipods: (a) 2.5 : 1, (b) 1.6 : 1,
(c) 1.1 : 1, (d) 0.83 : 1, (e) 0.55 : 1 and (f) 0.27 : 1, respectively.
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of Pt nanostructures. The multipod growth formed with high
aspect ratios when the HDA/DDD ratio was around unity.
The length of alkyl chain of the capping agents also showed a
significant effect on the anisotropic growth of Pt nano-
structures. As shown in Fig. 3, under the given set of testing
conditions, only polyhedral shapes were obtained when the
diols had 14 or more carbon atoms in the alkyl groups.
2.2 Diffusion-limited growth
In a typical metal and metal alloy crystal growth, atoms are
the building units which deposit on crystal surfaces. They
diffuse subsequently to the lattice points to decrease the system
free energy. Under thermodynamically controlled conditions,
atoms diffuse to the position with lowest free energy to form
the stable form of the crystal.
In practice, however, there are many kinetic conditions
which limit the atomic diffusion and thus have important
effects on the final crystal morphology. As shown in Fig. 4a,
kinetic effects not only prevent the atoms from diffusing to the
Fig. 3 TEM images showing the effect of alkyl length of the diol on
the formation of Pt multipods. The diols used were (a) decanediol,
(b) dodecanediol, (c) tetradecanediol, and (d) hexadecanediol, respectively.
The reaction time was kept at 160 min.
Chem. Soc. Rev.
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Fig. 4 Atomic diffusion-induced shape transformation. (a) Illustra-
tion of diffusion paths for atoms with different energy barriers and at
different positions on a metal surface (reprinted with permission from
ref. 55. Copyright 2006 by the American Physical Society). (b) A
diffusion-limited aggregate consisting of 3600 particles on a square
lattice obtained through a computer simulation (reprinted with permission
from ref. 56. Copyright 1981 by the American Physical Society). (c) Pt
island growth on Pt (111) surface with temperature increasing from 200 K,
to 400 K, to 455 K, to 640 K, and to 710 K, (and 425K with additional
annealing at 710 K for 1 min), respectively, from left to right images
(reprinted with permission from ref. 63. Copyright 1993 by the American
Physical Society). (d, e) Morphology obtained by Monte Carlo simula-
tions as a function of atomic diffusion barrier at edge (Eedge): (d) 0.85 eV,
0.58 eV, 0.50 eV, 0.40 eV, and 0.25 eV, respectively, from left to right
images; and (e) 0.80 eV, 0.60 eV, 0.53 eV, 0.48 eV, and 0.35 eV,
respectively, from left to right images, under two different sets of
conditions (reprinted with permission from ref. 55. Copyright 2006 by
the American Physical Society).
lowest energy positions, but also constrain the routes for the
diffusion on surfaces.52–54 Depended on the initial position,
the atom may diffuse on terraces, along edges, or at corners of
the surface. The diffusion rate can be described as the
following:55
Vt = V0exp(Et/kT) (1)
where, V0 is the attempt frequency, Et is the energy barrier for
diffusion, k is the Boltzmann constant, and T is temperature.
Usually the energy barriers for diffusion follow the order of
edge 4 corner 4 terrace.
Monte Carlo simulation is used to study this diffusion-
limited growth (Fig. 4b). This method was firstly developed
to study the diffusion-limited aggregation (DLA) of particles.56
It has subsequently been used widely to study the atom/
ion-mediated diffusion-limited growth.57 For wet-chemistry
synthesis, many factors may effect the diffusion-limited growth,
such as convection,58 concentration,59 additive,60 temperature,61
and thickness of diffusion layer.57,62 Often those factors govern
This journal is c The Royal Society of Chemistry 2012

the kinetics, such as atomic diffusion, leading to anisotropic
growth. For example, when temperature decreases, atomic
diffusion becomes weak and the growth of Pt crystals becomes
anisotropic and the morphology transforms from fractal to
dendrite and eventually trigonal or hexagonal shape
(Fig. 4c).63 This process can be simulated by DLA method, as
shown in Fig. 4d and e.55 With the decrease of the diffusion
energy barrier, the atomic diffusion becomes easy accordingly,
thus the morphology changes from fractal to dendrite and
eventually the predicted polyhedral shapes, matching very well
with experimental data. In the synthesis of colloid metal nano-
crystals, most of the precursors are metal ions in solution, so the
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A
concentration gradient,64 reduction rate65 and diffusion57 all
have important effects on the growth.
2.3 Particle-mediated growth
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Besides the atom-mediated growth, recently a new growth
model, i.e. the non-classical particle-mediated crystallization
pathway has been developed based on biomineralization
processes.66,67 In the classical crystal growth model, the basic
growth units are atoms/ions, however, in the particle-mediated
growth, the building units are NPs, as illustrated in Fig. 5. The
particle-mediated growth was observed in metal oxides,68,69
and colloidal metal nanocrystals, such as Au,50 Ag,41,70 Pt,71,72
and PtRu.73 In the particle-mediated growth process, the
particles as building units do not simply aggregate with each
other. It often involves a mechanism, known as the oriented
attachment (OA),74 in which the nanocrystals align along a
common crystallographic direction in order to minimize the
interface energy. This particle-by-particle growth process often
leads to the formation of so-called mesocrystals (Fig. 5b).
They are ordered superstructures composed of many individual
nanocrystals that share common crystallographic planes,
exhibiting scattering properties similar to those of single
crystals.75
Recently, in situ transmission electron microscopy (TEM)
technique was used to study the growth of colloidal Pt
nanocrystals in solution (Fig. 6a and b).76,77 Particle-mediated
growth was found to be a common process for the formation
of nanocrystals in solution. A new type of liquid cell based on
the entrapment of liquid between layers of graphene was
further developed for the in situ TEM technique.78 This
improved design not only allows for further confirmation of
Fig. 5 Illustration of two growth models: (a) the classical atom-
mediated growth and (b) the non-classical particle-mediated growth.
This journal is c The Royal Society of Chemistry 2012
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the particle-mediated growth, but also shows that besides the
OA growth, an Ostwald ripening (OR)/coarsening process is
occurring simultaneously (Fig. 6c and d). In the OR process,
atoms diffuse on the surface to decrease the surface area and
thus the overall surface energy. When the sizes of NPs are
similar, the atoms diffuse toward each other to fill the pit area
between the two NPs. If the size is very different, the atoms in
the small NP diffuse to the large one, as shown in Fig. 6d. This
result matches very well with molecular dynamics (MD)
simulations for Ag–Pt alloy NP-mediated growth.42
Many factors can have important effects on the particle-
mediated growth process. By controlling these factors, various
mesocrystals with new structures and morphologies are
obtainable by using NPs as the building blocks. Uniform
apple-shaped and spherical core–shell ZnO mesocrystals
were made from nanoplates, driven by the intrinsic dipole
interaction.79,80 Similarly, sea urchin-, flower- and meatball-like
Au mesocrystals were also synthesized.50
Shape and structure of NP building units are usually critical
for the formation of mesocrystals with controllable shapes,
because NPs prefer to attach to one other through the facets
with the highest surface energy or surface area in order to
decrease the total free energy. For example, in a truncated
octahedral metal or metal alloy NP, {111} facets have a larger
area than {100} facets and selected surfactant molecules can
have stronger adsorption on {100} facets than {111} facets. In
such cases, the truncated octahedral NPs attach to each other
through {111} facets and form dendritic,73 multioctahedral,71
porous cubic,72 and sea urchin-like mesocrystals,50 as shown in
Fig. 7.
The intrinsic structures of NP building units are important
for the particle-mediated growth. As shown in Fig. 8, two
kinds of NP-mediated growth were observed in a wet-chemistry
synthesis of Ag NPs.41 With the size of the Ag NPs decreased,
the crystallinity of the structures went down. The large Ag NPs,
which are made of truncated octahedral crystals, grew along the
h111i directions through {111} facets, resulting in the formation
of dendritic mesocrystals. The small Ag NPs, which had low
crystallinity and pseudo-spherical shape, however, aggregated
one by one without preferred directions, resulting in a fractal
shape. The OA mechanism cannot be used to explain the later
nanocluster-mediated growth to form polycrystalline structures.
Besides the shape and structure of NPs, synthesis conditions
greatly affect the particle-mediated growth as well, because
they may change the atomic diffusion, adsorption energy of
surfactant, and interaction between NPs. As illustrated in
Fig. 9a and b, colloidal NPs move in the liquid phase due to
Brownian motion, and collide with each other at a frequency
that can be described as:81
f = kTr2/3/3pZR (2)
where r is the density of NPs with a radius of R in a solution
with a viscosity of Z. Upon collision, surfactant may prevent
the capped NPs from attaching to each other. At the same
time, van der Waals interaction, polarization force, and
other interparticle interactions favor the attachment of NPs.
Diffusion of atoms on the surface at interparticle regions
results in the fusion of NP building blocks (Fig. 9a and b).
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Fig. 6 (a) Illustration of the window for the cell used for in situ TEM study of nanocrystal growth in solution. (b) A series of video frames
captured at 12.1, 12.1, 24.2, and 77.0 s in the liquid cell for (A, B, and C) a particle growing by coalescence with a smaller particle and (D, E, and F)
a particle growing through steady accretion of atoms. (Adapted with permission from ref. 77. Copyright 2009 American Association for the
Advancement of Science.) (c) Illustration of encapsulated solution between graphene sheets and (d) in situ TEM images showing the two types of
growth modes. (Adapted with permission from ref. 78. Copyright 20012 American Association for the Advancement of Science.)

Theoretical calculation and experimental observation both conditions. It has been used as a powerful approach to the
show that these factors have important effects on the particle- crystal engineering of complicated nanostructures.92 Yang and
mediated AgPt nanowire growth, as shown in Fig. 9c.42 coworkers developed a simple etchant system for silver NPs.93
By carefully tuning the amount and composition of etchant,
2.4 Defects in seed-induced anisotropic growth they successively controlled the transformation of octahedral
silver NPs into truncated structures with etched edges and then
Control of shape can also be achieved through the seed-
back to cubic structures with slightly rough features.28 In
mediated growth. Since metals and metal alloys are often
addition, at a high concentration of NH4OH/H2O2 the selective
cubic phase, defects, especially twinning, need to be created
etching of {100} surfaces becomes pronounced, resulting in
in the initial seed crystals in order to generate symmetry-
concave features that eventually form octapods, which have
reduced morphology in a colloidal synthesis. In other words,
the same symmetry as that for the starting silver octahedral
the stacking faults break the symmetry in face-centered cubic
nanocrystals (Fig. 11a). Tilley et al. has found that the high-
metals and metal alloys, and enable the formation of anisotropic
concentration acetylacetonate species from the reaction
nanocrystals with 1-D, 2-D and 3-D morphologies. The final
precursor may also act as the etchant.94 It is preferred to etch
shapes depend on both the type and number of defects. The
and dissolve the platinum from the {100} facets rather than
functions of defects in seeds have been recently
{111} facets due to the high surface energy bound by {100}
reviewed.8,9,30,82–87 Therefore, only several examples are selected
facets. This process led to a morphological transformation of Pt
and discussed here. Fig. 10 shows that the shapes of Pt
NPs from initially formed nanocubes to octapod-like nano-
nanocrystals formed depending on the type and number of twin
crystals (Fig. 11b). Yang et al. reported that the core–shell
planes in seed crystals. The seeds with cuboctahedral structure
Au@Ag nanorods can be etched by FeCl3 to produce a number
lead to the formation of anisotropic needles of multipods, while
of dumbbell-like Ag-tipped Au nanorods.92 The selective
the single- and penta-twined seeds lead to the formation
etching from the side of the core–shell nanorods was attributed
of tripod-,29 pentapod- and rod-like49 structures. Seeds with
to the increased reactivity of these facets due to the low level of
two or more parallel twin planes or stacking faults form
surface passivation by surfactants (CTAB). Oxygen molecules
triangular or hexagonal nanoplates/prisms.49,88–90 The single
can selectively shorten the single-crystalline Au nanorods95 and
twinned seeds also grow to right bipyramid NPs by controlling
generate hollow structures from Pd nanocubes by mild oxidative
the growth environments.91
etching.96 Xiong97 and Xia98 demonstrated that the etching
process triggered by citric acid led to the transformation of
2.5 Chemical etching on colloidal NPs
Ag NPs from nanocubes to nanospheres, respectively. Jin and
Chemical etching of as-made NPs can be used to generate coworkers found that H2O2 can be used as a mild etchant to
complex architectures by using different etchants and reaction controllably dissolve Ag atoms from the Ag/Au bimetallic

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Fig. 9 Illustration of formation of metal nanowires through the particle-

mediated process: (a) two NPs attached with each other during the initial
steps, (b) attachment of NPs or nanorods to form nanowires. (c) Simulation
and experimental data showing the effects of diffusion of atoms using mean
square displacement (MSD), and adsorption energy of capping agents on
the formation of AgPt nanowires (adapted with permission from ref. 42.
Copyright 2010 American Chemical Society).

Fig. 7 (a–d) TEM images of metal and metal alloy nanostructures

formed according to the particle-mediated growth model: (a) PtRu
nanodendrites (adapted with permission from ref. 73. Copyright 2007
American Chemical Society), (b) Pt multioctahedra (adapted with
permission from ref. 72. Copyright 2008 American Chemical Society),
(c) Pt porous nanocubes (adapted with permission from ref. 71.
Copyright 2010 American Chemical Society), and (d) Au sea urchin-
like NPs (adapted with permission from ref. 50. Copyright 2012 the
Royal Society of Chemistry). Selected area electron diffraction
(SAED) image (inset) shows broadened diffraction spots. (e) Illustration
of the three-dimensional (3D) nanostructures formed through
the particle-mediated growth (adapted with permission from ref. 50.
Copyright 2012 the Royal Society of Chemistry).

Fig. 10 (a–c) Possible formation mechanisms of branched nano-

Fig. 8 Different Ag NPs served as building units for particle-
mediated growth: (a) amorphous spheres and (b) crystal truncated
octahedra (adapted with permission from ref. 41. Copyright 2011
American Chemical Society).
structures from seed crystals with or without defects (adapted with permis-
sion from ref. 85. Copyright 2010 Wiley-VCH): (a) the penta-twinned
decahedral crystals evolving into (d) pentapods and (e) nanorods (adapted
with permission from ref. 49. Copyright 2005 Wiley-VCH) through the
growth along h112i and h110i directions, respectively; (b) the octahedron
nanocrystals evolving into (f) isotropic needles or (g) anisotropic nano-
structures from the tips of the seeds; (c) a truncated bicrystal bound by
{111} planes to form planar tripod growing from the stacking fault in the
bicrystals involving three re-entant troughs with edges directed inwards
(concave). The crystals eventually grow into (h) tripod structures.

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
 View Online

of {730}, {210}, and {520} surfaces, respectively.105 In their

approach, spherical Pt NPs were transformed into the THH
shape by applying a square-wave potential with an upper
potential of 1.2 V and a low potential between 0.1 V and
0.2 V at 10 Hz in a solution of 0.1 M H2SO4 and 30 mM
ascorbic acid for a time period from 10 to 60 min. Palladium
THH NPs bound by {730} facets106 and concave THH Pt NPs
enclosed by {910} and other high-index facets107 were
obtained using similar electrochemical methods.
Interactions between oxygen and hydroxyl species and
metal NP surface may cause the formation of nanoparticles
with these high-index planes. The electropotential cycles de-
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stroy the low-index facets and promote the formation of high-

index facets. However, metal NPs enclosed by low-index facets
were also obtained with the electrochemical method, such as
Pt nanocubes,108 and rhombic, dodecahedral, tetragonal bi-
pyramidal and cubic NPs.109 Thus, the mechanism of this
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electrochemical treatment in controlling the shape of colloidal

metal NPs needs further exploration.
Recently, Yang group obtained Pt cubic nanoboxes using a
electrochemical method (Fig. 12).110 In this method, Pt-on-Ag
heteronanostructures were firstly synthesized and the Pt hol-
low nanostructures were obtained by dissolving Ag atoms
electrochemically. Further treatment by applying 3000 linear
Fig. 11 Metal and metal alloy NPs prepared through chemical
etching. (a) SEM images showing the morphological changes of the
silver octahedral NPs during the etching progress (adapted with
permission from ref. 93. Copyright 2010 American Chemical Society).
(b) TEM images of platinum nanostructures obtained from reactions
of 75, 120, 240, and 500 min, respectively, from left to right (adapted
with permission from ref. 94. Copyright 2009 American Chemical
Society). The structures made from (c) spherical, (d) cubic, and
(e) cylindrical shapes through sequential galvanic exchange and
Kirkendall growth at room temperature (each TEM image is accompanied
with a drawing illustrating the morphology of the nanostructure). (Adapted
with permission from ref. 101. Copyright 2011 American Association for
the Advancement of Science.)

hollow nanoshells to produce porous hollow nanostructures.99

Xia et al. presented an etching-induced growth, in which the
oxidative etching on the corners combined with overgrowth on
the three adjacent faces lead to the shape transformation of
silver nanocubes to truncated octahedra.100 Recently, Puntes
and coworkers101 developed a synthetic route for carving silver
nanocrystals by simultaneous or sequential galvanic replacement
(Fig. 11c–e).102,103 Kirkendall effect104 also played an important
role in producing hollow NPs with diverse morphology and
composition.

2.6 Others
Besides the above colloidal approaches, there are a few other
methods that have been developed. Electrochemical synthesis
and gas reducing agent using carbon monoxide (CO) are two
of the more powerful methods for controlling the shape of
nanoparticles.
2.6.1 Electrochemical methods. Sun and Wang’s group
used an electrochemical method to obtain Pt tetrahexahedral
(THH) nanocrystals that are bounded by 24 high-index facets
Fig. 12 (a) TEM and (b–c) HRTEM images of Pt hollow nanocubes
prepared by the electrochemical methods. Inset of (a) shows the
corresponding potential cycling profile. Individual hollow cubes
imaged under various tilting angles with respect to the direction of
the imaging beam are shown in (c). (Reprinted with permission from
ref. 110. Copyright 2010 American Chemical Society.)

Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
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sweeps in a potential range between 0.6 and 1.0 V and at a scan

rate of 100 mV s1 resulted in the generation of ultrafine Pt
cubic nanoboxes. These Pt cubic nanoboxes had an average
edge length of 6 nm and wall thickness of only 1.5 nm, which is
about 4 unit cells.

2.6.2 Gas reducing agents based on carbon monoxide. While

most of the syntheses of NPs are performed using soluble solid
or miscible liquid reducing agents, carbon monoxide (CO) has
recently been introduced in the system of colloidal metal and
metal alloy nanostructures. In these new systems, CO plays
critical roles for the control of morphology. The CO-contain-
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ing organometallic also works in the shape control of NPs.

Metal carbonyl compounds, such as Fe(CO)5, W(CO)6,
Co2(CO)8 and Mn2(CO)10 are essential in the synthesis of
cubic Pt and Pt3M (M = Co, Fe, Ni, Mn) NPs.111–115 In the
original work, the zero-valent metals were considered as the
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key for the formation of nanocubes. However, no Pt nano-

cubes were formed when Co2(CO)8 was replaced by other Co
sources.113 It thus appeared that CO decomposed from the
carbonyls during the reaction possibly was the key chemical
ingredient for the formation of nanocubes.5,116,117 By using
CO gas alone, both Pt and Pt–M (M = Co, Fe, Ni, Pd) cubic
NPs were obtained. This CO-based approach was later developed
into an effective method, which is called GRAILS (gas reducing
agent in liquid solution) and used to synthesize octahedral NPs of
Pt alloys (Pt–M, M = Co, Fe, Ni, Pd).116
Fourier transform infrared spectroscopy (FT-IR) measure-
ments demonstrate the CO adsorption preferably on {100}
surfaces of Pt NPs, and DFT (density functional theory)
calculations indicate that the (100) surface becomes more
stable than the (111) surface after the adsorption of CO and
alkanyl amines (RNH2). Though the selective interaction
between CO and various surfaces of noble metals is important,
the roles of CO in the shape control of metal and metal alloy
NPs are still not fully understood. The cubic nanocrystals
bounded by {100} facets should be the main products if CO
binding to this surface dominates the reaction pathway.5,118,119
However, octahedrons,116 nanowires,117 and nanoplates7 are
also readily obtained by using CO gas in conjunction with
different capping agents or additives. Surface segregation is
often considered to be a key role of CO gas on the formation
of nanocrystals of metal and alloy,118,120–123 while its ability to
tune the surface energy has not been studied with care. The Fig. 13 SEM images of (a) slightly truncated silver nanocubes and
kinetic effects of CO gas on different facets, such as the the products after they reacted with (b) 0.3 mL and (c) 1.5 mL of
different reducing rates of CO on various facets, require better aqueous HAuCl4 solution (1 mM), respectively (adapted with permis-
understanding. The effect of CO gas on the nuclei and seed sion from ref. 103. Copyright 2002 American Association for the
formation is also important. Advancement of Science). SEM and TEM images of (d, e) octahedral,
(f) cubic and (g) star-shaped hollow PtCu alloy mesoparticles, using
Cu2O as the sacrificial template (adapted with permission from
3. Template-directed growth ref. 142. Copyright 2011 American Chemical Society). (h) Schematic
illustration of the formation of (i) Pt nanotubes and (j) Pd nanowires
3.1 Morphology control through the sacrificial template based on Te nanowire templates (adapted with permission from
Hollow or porous structures are often synthesized using ref. 139. Copyright 2009 Wiley-VCH).
templates of a variety of shaped NPs. In this context, silver
NPs are often used as the sacrificial template for the preparation NPs. Even nonmetallic materials, such as cuprous oxide,141,142 are
of metallic nanostructures with a range of morphologies able to act as templates for the synthesis of hollow noble metal
via galvanic reaction.102,103,124–131 Besides silver, nickel,132 NPs. Fig. 13a–c show a few examples of hollow structures
cobalt,133–135 selenium,136 and tellurium137–140 were also used as prepared with different kinds of sacrificial templates. When the
sacrificial templates to prepare hollow and porous noble metal silver nanocrystals were used as templates (Fig. 13a), the initial

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
 View Online

galvanic reaction induce the formation of pinholes appearing on

the six faces of each cube (Fig. 13b), after their reactions with
HAuCl4 solution. These reactions are initiated locally at a high-
energy site (e.g., surface step, point defect, or hole in capping
layer)143 rather than over the entire cube surface. The further
dissolution of Ag and deposition of Au facilitate the conversion of
the nanocube into a nanobox (Fig. 13b and c).144
Cuprous oxide was a good sacrificial template for the
synthesis of non-spherical hollow metal cages of Ag, Au, Pt,
Pd and PtPd alloy (Fig. 13).140,141 After removing the Cu2O
core, the morphologies of the template can be preserved in the
final products. This method offers a facile approach to the
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synthesis of hollow meso-/nano-cages. Uniform Pt and Pd

nanowires/nanotubes with a diameter of only several nano-
meters (nm) and an aspect ratio of B10 000 were made using
ultrathin tellurium nanowires as both reducing agent and
sacrificial template.145,146 Valence states of metal precursors
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were found to play a key role for the formation of tubes or

solid wires (Fig. 13).139,140 Besides noble nanowires/tubes,
platinum nanosponges, nanonetworks, nanodendrites and
Au–Te hybrid nanomaterials were made using tellurium nanowires
as the sacrificial template.137,138
3.2 Templated growth by self-assembled molecules
The assembly of organic molecules, such as OA and oleic acid,
leads to the formation of well-organized nanostructures. Such
low-dimensional structures are able to act as soft-templates to
confine the growth of nanowires due to the strong interactions
between amine or other functional groups and metal ion
species. The size of Au and Pt based alloy nanowires obtained
through this way is typically quite small with diameter around
3 nm or less. As illustrated in Fig. 14, Au(III) in AuCl4 ions
was reduced to Au(I) and form the Au+-oleylamine complex
when it was dissolved in oleylamine.145 The as-formed
complex would further assemble into rod-like micelle-type
structures, which confined the anisotropic growth of Au
nanowires.145–148 Besides the organic phase, ultrathin Pt and
Pt based alloy nanowire networks have been synthesized by
co-reducing the metallic precursors in a soft template formed
by CTAB in a two-phase water-chloroform system.48,149
3.3 Hollow structures formed using gas bubbles as template
Gas bubbles formed in situ in a liquid solution can be used to
create hollow particles.154,155 The approach is thought to
involve both gas bubbles and fine NPs, with a coalescence of
fine NPs at the gas/liquid interface to form closed shells
around the bubbles.150,151 Most of the early work on using
gas bubbles as templates has been focused on metal oxides,
sulfides and carbonate, which has been reviewed by Lou and
coworkers.152
In recent years, gas bubbles have been developed to synthe-
size noble metal hollow structures. Huang et al.153 prepared
hollow Au NPs with a complete nanocrystalline shell and a
50 nm hollow core via electroless deposition using electro-
chemically generated hydrogen bubbles as both the template
and reducing agent.154 Three steps were involved during the
process: (1) creation of hydrogen bubbles electrochemically;
(2) reduction of an Au+ complex around these bubbles
Fig. 14 (a) Schematic illustration of the growth process for ultrathin
Au nanowires (adapted with permission from ref. 145. Copyright 2008
American Chemical Society). The cooperative interaction between the
Au precursor and oleylamine leads to the formation of a mesostructure,
followed by in situ slow reduction. (b) Low and (c) high magnification
TEM images of Au nanowires (adapted with permission from ref. 146.
Copyright 2008 American Chemical Society). (d) TEM image of PtRu
nanowires (adapted with permission from ref. 48. Copyright 2010
American Chemical Society).
to form Au clusters; and (3) further electroless deposition of Au
on the formed clusters through an autocatalytic disproportionation
reaction. By controlling the shell thickness, particle size can be
varied from 100 to 150 nm.153
Chrisey et al. prepared hollow ZnOx and Fe–Ni alloy NPs
using pulsed laser ablation of bulk Zn and permalloy in
ethanol–water binary mixtures.155 They found that the
formation of hollow NPs were due to the trapping of laser-
produced nanoclusters at the interfaces of cavitation bubbles
and the bonding of the nanoclusters by capillary attraction
nanoclusters. Sacher et al. prepared a porous Pt NP film with a
porosity 495% presumably using the CO2 bubbles produced
when formic acid was used in the reduction of H2PtCl6 at 80 1C.156
The generation of gas bubbles from the decomposition
of organometallic compounds may also be facilitated using
molten salts. The bubbles formed in molten salts have been
used as templates for the synthesis of noble metal hollow
spheres157 and concave shapes158 by depositing the metal
atoms at the gas–liquid interface. The typical mode of
formation is depicted in Fig. 15. The Pt(acac)2 powder was
firstly dispersed into the NaOH–KOH molten salt through
stirring. Pt(acac)2 powder sublimed at 180 1C (Step I in
Fig. 15a).
When the temperature increased to 200 1C, the decomposition
of Pt(acac)2 started to accelerate (Step II in Fig. 15a). The
concentration of Pt atoms thus should increase at the interface.
These Pt species coalesced and formed small nuclei which grew
into nanocrystals at the interface. These Pt clusters at the
interface could further act as the nucleation centers which induce
the epitaxial growth of metallic shell. As the reaction proceeded,

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Fig. 15 Schematic illustration for the formation of Pt hollow spheres
and nanosheets via in situ chemical vapor deposition in NaOH–KOH
molten salts (reprinted with permission from ref. 157. Copyright 2012
the Royal Society of Chemistry).
a Pt shell formed around the bubbles (Step III in Fig. 15a). The
shells may fracture to form nanosheets with various sizes and
shapes when the bubbles reach to the air-liquid interface and the
pressure inside builds up (Fig. 15b).
4. Inorganic species-mediated formation
4.1 Cation-mediated formation of metal nanostructures
Under potential deposition (UPD) occurs during the for-
mation of a metal adlayer onto a different metallic substrate.
In this process, the less noble metal is deposited onto the
substrate to form a thin layer.159 The UPD process on the
noble metal NP surface may greatly affect the surface energy,
leading to the anisotropic growth.160 Several metal ions, such
as Ag(I), Cu(II) and Pd(IV) were showed to change the colloidal
growth of noble metal nanocrystals (Table 1). Ag(I) ions were
used to slow down the growth of Au NPs selectively. The
underpotential deposition of Ag(I) prefers the less covered
crystal facets, such as high-indexed plane and steps to form an
Ag(0) monolayer or submonolayer coverage. The modified
surfaces or regions grow more slowly and became dominant in
the final structures.161 Thus some of noble metal NPs with
high surface energy such as tetrahexahedra (convex cubes/
rods),162 concave cubes,36 and bipyramid161 are synthesized
using this approach. Mirkin and coworkers confirmed, using
X-ray photoelectron spectroscopy and inductively coupled
plasma atomic emission spectroscopy, that Ag underpotential
deposition stabilizes the various surface facets including high-
indexed crystal planes, such as {110}, {310} and {720}
(Fig. 16).163 Lu and coworkers report the synergistic effect of
Pd(II) and Ag(I) on the shape-selective growth of polyhedral
Au nanocrystals.164 By varying the concentrations of Ag(I)
and Pd(II) in solution, truncated tetrahexahedra (THHs)
bound by {310} and {111} facets, truncated ditetragonal
prisms (DTPs) enclosed by {310} facets, and multiple-twinned
This journal is c The Royal Society of Chemistry 2012
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bipyramids of gold nanocrystals were made. Mirkin and
coworkers also reported a bottom-up approach to the syn-
thesis of Au octahedra with tailored hollow features using
Ag(I) assisted UPD, in which a high concentration of Ag+ was
thought to stabilize the {111} facets of the octahedral, while
the rate of Au+ reduction controlled the dimensions of the
hollow features.165 In addition, Cu(II)166 and Pd(II)164 ions can
also induce the UPD-assisted anisotropic growth of NPs, as
summarized in Table 1.
4.2 Nanocrystal- or atom-induced anisotropic growth
Besides the aforementioned methods, certain foreign nano-
crystals or atoms formed in situ formed or added are able to
improve the anisotropic growth of noble metal NPs. Xia et al.
reported the synthesis of ultrathin Au nanowires by Fe and Ag
NP-assisted aging of the AuCl–oleylamine complex in various
organic solvents.146,167 In those studies, the ultrathin Au
nanorods/wires were evolved from the unstable Au NPs
initially derived from the reaction between the Fe and Ag
NPs and the [AuCl(OLA)] complex. The change of reaction
kinetics altered the rate for the formation of Au(0) toward the
growth of Au nanorods or wires.168 In situ produced
W,112,114,169,170 Cr171 and Co113,172 atoms in synthesis of Pt,
Pt3Co, Pt3Fe, Pt3Ni and PtCo polyhedron NPs were thought
to be the foreign atoms which change the reaction kinetics in
both reduction and growth stages for the anisotropic growth
of nanocrystals. The detailed roles of metallic nanocrystals or
atoms in promoting the anisotropic growth of noble metal
NPs still remains unclear, however.
4.3 Anion and other non-metal-based additives
Besides cation ions or clusters and metal atoms, inorganic
anions (including Cl, Br, I, and NO3) may affect the
synthesis of noble metal NPs (Table 2). One known influence
of these inorganic nonmetallic ions on the growth of noble
metal NPs is their use in preferred oxidative etching and in
removing the defects formed in the seeds or in decreasing the
reduction reaction kinetics of metal precursors. Effects of such
ions sometimes are hard to confirm, as these ionic species are
often the counter ions for the cation surfactant capping agents.
The best examples are the shape controlled syntheses of Ag
and Pd NPs using the polyol approach. It was found that the
twinned particles formed in the early stage could be removed
by selective etching and dissolution by chloride and oxygen,
leaving only the single crystalline ones to grow into nanoscale
cubes and tetrahedrons.174–176 Similarly, sodium sulfide
(Na2S) and sodium hydrosulfide (NaHS) were also found to
be effective for the preparation of single crystal Ag nanocubes
by etching and removing the twinned crystals.177 The etching
process could be partially reduced by introducing Fe(II) or
Fe(III) species to remove the oxygen adsorbed on the crystal
surface, leading to the formation of single twinned NPs.178
The etching triggered by inorganic ions also changed the
kinetics for the reduction of precursors, the growth rates
associated with different crystallographic directions, and thus
the morphology of final products. Sodium nitrate179 and Fe(III)180
were able to slow down the reduction of Pt precursors in ethylene
glycol (EG). The change in reaction kinetics for making Pt
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Table 1 Colloidal metal and metal alloy NPs synthesized in the presence of foreign metallic additives

Additive Shape Composition Capping agents and Solventa Facet Ref.

Pd(II) Au PDDA in glycol {111} + {100} 164

{111} + {110},
Au PDDA in glycol 164
{111}

Au CTAB in H2O {037} 162

Ag(I)
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Au CTAB + CTAC, CTAB + DDAB in H2O {720}, {520} 35, 36

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Au TEG in H2O {611} + {111} 33

Oleylamine in hexane oleylamine in

Au {111} 146, 167
Ag NPs, Fe NPs chloroform

Low ratio of Ag(I)/ Au PDDA in glycol {111} + {310} 164

Pd(II)

High ratio of Ag(I)/ Au PDDA in glycol {310} 164

Pd(II)

Au/Pd alloy OTAC in glycol {431} 166

Ag PVP in H2O {221} 32

Cu(II)

Pd CTAB in H2O {111} + {110} 173

Pt, Pt3Co, Pt3Fe, 112, 114,

Oleic acid and oleylamine {100}, {111}
W(CO)6 Cr(CO)6 Pt3Ni 169–171

Oleylamine, 1,2-dichlorobenzene and 1,2- {100}, {111} +

Pt, PtCo 113, 172
Co NCs Co2(CO)8 hexadecanediol {110}

a
PPDA = poly(diallyldimethylammonium chloride), CTAC = cetyltrimethylammonium chloride, DDAB = didodecyldimethylammonium
bromide, TEG = tetra(ethylene glycol), OTAC = octadecyl trimethyl ammonium chloride.

nanocrystals ultimately led to the formation of different morphol-
ogies. Recently, Zheng et al. found that Fe(III) ions etched the Pd
seeds at the early stage of the reaction to induce the formation of
branched mesocrystalline Pd nanocorolla.181
CTAB and CTAC are the common used surfactants for the
synthesis of noble metal NPs. In recent years, various kinds of
noble metal NPs with high-indexed surfaces have been pre-
pared using CTAB and CTAC as capping agents. However, it
is interesting that CTAB and CTAC always show an opposite
effect configuration as capping agents for the preparation of
NPs, although these two capping agents contain the same
cation surfactant group. CTAC was found to facilitate the
formation of concave cubes, while CTAB led to the formation
of tetrahexahedra (convex cubes) when all the other conditions
were kept the same.35,36,162 When NaCl were used as addi-
tional additives, trisoctahedral Au NPs with a single twin
plane and high-indexed facets were produced in the presence
of CTAC.182 Interestingly, Br was found to promote the
formation of concave nanocubes rather than a convex form of
Pt or Pt alloys from their initial cubic morphology. Although
the mechanism for Cl and Br mediated growth is still largely
unclear, a generally acceptable explanation is that both
Br and Cl are able to slow down the reduction of
precursors,183,184 which is a prerequisite for the formation of
noble metal concave or convex nanocubes by combining with
other additives, such as Ag+,33 Na2H2P2O7,185 and Cu2+.166

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Fig. 16 SEM images of (A) octahedra, (B) rhombic dodecahedra,
(C) truncated ditetragonal prisms, and (D) concave cubes synthesized
from solutions at Ag+/Au3+ molar ratios of 1 : 500, 1 : 50, 1 : 12.5, and
1 : 5, respectively (reprinted with permission from ref. 163. Copyright 2011
American Chemical Society). Scale bars: 200 nm.
Besides Br and Cl, introducing methylamine allows concave
Pt nanocrystals having {411} high-index facets to be prepared in
presence of PVP.186 Huang et al. have demonstrated a Mn3O4
NP-induced synthesis of polycrystalline twinned Pt NPs and
length-controlled Pt NRs with high index facets.187
5. Further understanding the formation of alloy
and bi-metallic nanocrystals
5.1 Alloying through atomic diffusion
Control of atomic diffusion in bimetallics is an effective way to
synthesize alloy NPs with designed sizes and compositions.
One such process involves mixing independently prepared
colloidal particles of pure metal A and B, and then heating
or sonicating in the presence of capping agents.198–202 As
shown in Fig. 17, after mixing the two colloidal suspensions,
NPs aggregate to form heterogeneous structures in order to
reduce the global Gibbs free energy.203 Coarsening of NPs
with small particles results in the formation of core–shell NPs.
Finally, the alloy NPs were formed because of the atomic
diffusion under favored reaction conditions (such as high
temperatures).199 Both the size and composition could be
fine-tuned based on the NP precursors.202 For example,
monodisperse AgAu alloy NPs were made through interfacial
diffusion of core/shell structured Ag/Au NPs using a
solvothermal synthesis method.198 In this case, Ag NPs were
first made by thermal reduction of AgNO3 in oleylamine.
These Ag NPs were used as seeds for the deposition of Au
NP through the reduction of HAuCl4 with oleylamine at 50 1C.
The AgAu alloy NPs formed after the core/shell structured
Ag/Au NPs were heated at 100 1C in oleylamine to facilitate
Ag and Au counter diffusion in the core/shell structure.
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Klabunde et al. reported that the mixture of either silver or
copper and gold NPs could be converted into monodisperse
alloy particles in presence of an alkanethiol under reflux.200
Bimetallic Ag/Au NPs with alloyed and core/shell structures
were also synthesized at the low temperature of 75 1C from the
preformed Ag and Au NPs in aqueous solution.201 At high
Ag/Au ratios, growth of an Ag shell on the surface of the
Ag/Au alloy core was possible; while at the low Ag/Au ratios
the formation of alloy particles was favored. Besides the
thermal process, ultrasound was used to make alloyed Ag–Au
NPs from a core/shell structure.199 The Schaak group devel-
oped low-temperature solution chemistry approaches to the
transformation of metal NPs into alloys and intermetallic
compounds.204 They prepared M–Zn (M = Au, Cu,
Pd),205,206 M–Pt (M = Sn, Pb, Sb, and Cu),207 M–Sn (M =
Co, Ni, Cu, Ag, Au, Pt, Ru)208 and M–Au (M = Fe, Co, Ni)209
alloy and intermetallic NPs with various morphologies from
preformed NPs with a second metal precursor in hot organic
solvents under reducing conditions.
5.2 Core–shell based bimetallic nanocrystals
In principle, the formation of multimetallic core–shell NPs or
core–shell like heterogeneous nanostructures including
dendrite, particle-on-particle, raspberry, or flower is usually
thermodynamically favored.30 A lower critical energy barrier
for the heterogeneous nucleation of second metal on the
preformed NP or core than that of homogenous nucleation
provides the driving force for the synthesis of core–shell
structured NPs. The formation process can be roughly divided
into three major types: layer-by-layer, island-on-wetting layer,
and island growth modes, depending on the overall excess
energy of the system, which is related to the surface and
interfacial energy terms, and the strain energy because of
lattice mismatch at the interface. In a colloidal synthesis
process, the heterogeneous deposition of a metal or metal
alloy on the core occurs through one of the above three growth
modes to form core–shell or core–shell like nanostructures in
the presence of capping ligands (Fig. 18a), while the metallic
cores can exist in either ordered or disordered form.210
Recently, electrochemical dealloying methods, chemical-
reaction-driven reconstruction approaches and UPD have
been developed for controlling bi- or multimetallic core–shell
like NPs, as shown in Fig. 18b and c.211–213 In a typical UPD
process for making Pt monolayer shell on selected metals, Cu
is used as the sacrificial layer (Fig. 18b).214,217 A Pt monolayer
can be deposited on different metallic NPs through the
galvanic reaction.211,214 The core–shell NPs prepared through
electrochemical dealloying can be due to the redox potential
difference between the two metal elements. The atom with the
low redox potential can be oxidized and dissolved into
solution by electrochemical treatment. For instance in AgPt
alloy NPs, after electrochemical removal of the more reactive
metal, such as Ag, core–shell like NPs surface rich in Pt could
be generated (Fig. 18c).212 Besides the electrochemical
approach, reacting gases, such as CO, NO, O2, and H2 can
selectively cause certain metal elements enriched on the outer
surface of alloy NPs (Fig. 18d).215 When Pd/Rh alloy NPs
were exposed to an oxidizing gas atmosphere of NO, the
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Table 2 Colloidal metal and metal alloy NPs synthesized in the presence of inorganic ion and neutral molecule additives

Additive Shape Composition Capping agent and solventa Facet Ref.

Ag PVP in EG {100} 188

Cl (HCl) Au CTAC/CTAB in H2O {720}/{410}/{310} 36

Au–Pd CTAB in H2O {111}/{100} 189

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Ag PVP in EG {111} + {100} 174

Cl (NaCl)

Au CTAC in H2O {331} 182

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Cl (KCl) Ag Trisodium citrate in H2O {111} 190

Cl (DDAC) Ag Oleylamine in octyl ether {100} 175

Cl/Br (CTAC/CTAB) Pd CTAC/CTAB in H2O {310} 184

Br (NaBr) Ag PVP in EG {111} 91

Br (KBr) Pd PVP in H2O {730} 191

Br (KBr), Na2H2P2O7 Pt PVP in H2O {720}/{510}/{830} 185

I (NaI) Pd PVP in H2O {111} + {100} 192

Pd, PdPt PVP in DMF {100} 193

Pd CTAB in H2O {111}, {110}, {100} 40

 Au CTAC in H2O 194
I (KI)

NO3 (NaNO3) Pt PVP in EG {111} 179

S2 (Na2S)/HS (NaHS) Ag PVP in EG {100} 177

Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
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Table 2 (continued )

Additive Shape Composition Capping agent and solventa Facet Ref.

{110} + {100} +
SCN (KSCN) Pd CTAB in H2O 195
{111}

O2 Pd PVP in EG {111} + {100} 176

HCHO Pd PVP in benzyl alcohol {111} + {110} 196

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Oleylamine and oleic acid in benzyl

CO Pt {100} 117
ether
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Au Oleylamine in chloroform {111}

Pt, PtFe, PtCo, PtNi, 116,

Oleylamine and oleic acid {100}, {111}
PtPd 197

CO + Br (CTAB/NaBr/ Pd PVP, CTAB/TBAB in DMF {111} 7

TBAB)

a
DMF = dimethylformamide, TBAB = NBu4Br.

However Ag–Pt alloys were obtained in nanocrystals with a

variety of compositions inside the above range.42,220
The Gibbs free energy of mixing (DGmix), which is typically
used to determine the relative stability of a bimetallic system,
is related to the enthalpy (DHmix) and entropy (DSmix) terms
by the following equation:

DGmix = GAB  XAGA  XBGB = DHmix  TDSmix

Fig. 17 Formation of intermetallic NPs through atomic diffusion
(digestive ripening): Step I, mixing the suspensions of colloids A and
B; Step II, heating or sonicating the samples to form core–shell NPs;
Step III, forming alloy NPs via atomic diffusion.
(3)
The subscripts AB, A and B denote the A–B bimetallic alloy
and constituent elements, respectively. When the surface
energy terms of metal NPs cannot be omitted, the Gibbs free
energy of bimetal alloy formation can be re-written as:225

core–shell NPs with Rh enriched surface were obtained. Rh
atoms were ‘‘pushed’’ back to the core, if the NP was exposed
to a reducing gas of CO.
5.3 Effects of particle size on alloy phase formation
With NP size decreases, the ratio of surface to total atoms
increases, and many size-related properties such as catalytic and
electronic properties change accordngly.216–219 At the same time,
the increasing ratio of surface energy to total free energy facilitates
the formation of alloy phases between two metals.30 Alloy phases
were readily detected with two immiscible metals in bulk, such as
Ag–Pt,220 Au–Pt,221 Au–Fe,222 Pt–Ru223 and Pb–Sn,224 when
they are made into crystals with diameters of a few nanometers.
For example, Ag–Pt binary alloys do not form stable alloy for
compositions between BAg2Pt98 and Ag95Pt5 at oB400 1C in
the bulk through high-temperature processing methods.
DGmix,NPs(r) = DGV,AB  (XADGV,A + XBDGV,B)
= DHmix  TDSmix–Dgmix(r) (4)
where XA and XB are the molar fractions of atom A and B
over the total atoms, respectively. This change results in the
increase of surface energy (Dgmix(r)). Qualitatively speaking,
when the NP size decreases, the corresponding surface energy
term increases and the mixture Gibbs free energy term
decreases. Thus, the bimetallic alloy phase may form more
easily in nanometer scale than in bulk. For immiscible
bimetallic materials, when the NP size decreases below a
certain value, stable alloy phases may form. As illustrated
in Fig. 19, NPs composed of metal A and B (which
are immiscible in bulk) are able to mix with each other to
form alloy NPs when the size is below a critical value (rc).
For quantitative analysis, the enthalpy part of Gibbs free
energy should have major effect on the formation of alloy

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 View Online
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A

Fig. 18 Schematic illustrations of (a) synthesis of bimetallic core–shell or core–shell-like NPs from metal precursors and (b–d) methods for the
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synthesis and structural control of core–shell multimetallic NPs: (b) Underpotential deposition (UPD) and replacement, (c) electrochemical
de-alloying, and (d) reaction-driven process (adapted with permission from ref. 210. Copyright 2011 Wiley-VCH).

The enthalpy for the transformation of Au–Pt and Ag–Cu

bimetallic alloy NPs versus particle size has been calculated based
on this equation, using molecule dynamics (MD) simulation.227–229
The result shows that when the numbers of atoms in Au–Pt NPs
decrease to less than 7000, the alloy phase is preferred thermo-
dynamically;227 for the Ag–Cu system, this value is 1289 atoms and
for Cu–Ni, the value is 1  105 atoms (or about 15 nm in
diamter).228 Au–Pt bimetallic NPs composed of 561 atoms
(Pt147Au414 and Pt309Au252) under different temperatures were also
calculated using MD method.230 The results indicate that below the
melting point, randomly mixed alloy NPs are more stable than
those with core–shell structures.

Fig. 19 Illustration of change of energy and phase transformation of

5.4 Lattice structures
bimetallic NPs. In bimetallic NPs, lattice parameters often change due to the
interaction between two kinds of atoms upon treatment. For
phase. Considering the surface energy of NPs, the enthalpy PtPb NPs, their crystalline phase transformed from cubic to
(DHmix) of NPs can be described as:226 hexagonal with the time evolution during the synthesis.231,232
  A series of cubic phase Pt100xPbx alloy nanorods rich in Pt
p b d
Hmix ¼ Hmix 1 ð5Þ formed even if the initial mole ratio between Pt and Pb
D
precursors was close to unity (Fig. 20a and b). These cubic
where HPmix and Hbmix denote enthalpy of the NPs and bulk, phase nanorods eventually transformed into the hexagonal
respectively; d is the diameter of a single atom and D is the phase with reaction time or further increased temperature
diameter of a spherical NP. For the alloy NP, d is the mean (Fig. 20c and d). This phase transformation was attributed
atomic diameter calculated from Vegard’s law. Thus the to the hexagonal phase of the Pt50Pb50 nanorods being the
number of atoms (N) in the NP can be described as: stable form because it has the lowest Gibbs free energy among
rffiffiffiffi all the compositions of Pb–Pt bimetallic alloys (Fig. 20e).
d 3 1 In small bimetallic alloy NPs, lattice distortion may be
¼ ð6Þ
D N produced due to the mismatch between two kinds of metal
atoms. Such lattice distortion was observed using powder
By combining eqn (5) and (6), the enthalpy for forming
X-ray diffraction (XRD) in Ag44Pt56 NPs.233 In the XRD
bimetallic NPs (XB = 1  XA) can be calculated using the
pattern, its (111) diffraction shifts to 40.21 2y, which is
following equation:227
significantly higher than that of either FCC Pt or FCC Ag,
rffiffiffiffi!  rffiffiffiffiffiffiffiffiffiffiffi
3 1 1 or normal FCC AgPt alloy based on Vegard’s law. After Ag atoms
p b 3
DHmix ¼HAB 1   XA HAb 1  in the Ag44Pt56 NPs were removed by dealloying, the lattice
N NXA
structure of the remaining NPs came back to normal FCC Pt
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi! ð7Þ
lattice structure, as shown in Fig. 21. This observation suggests that
b 3 1
 ð1  XA ÞHB 1  the mismatch between Ag and Pt atoms in AgPt NPs induces the
Nð1  XA Þ
change in the crystal structures. In the distorted lattice, the

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Fig. 20 TEM images of Pb–Pt nanorods synthesized at 180 1C after
the reaction for (a, b) 5 and (c, d) 45 min, respectively. The lattices in
HR-TEM images could be assigned to (b) cubic and (d) hexagonal
phases of platinum lead. (e) Schematic illustration of relative levels of
energy for the cubic and hexagonal phase PtPb nanorods. (Adapted
with permission from ref. 231. Copyright 2008 Wiley-VCH.)
Fig. 21 Illustration showing the surfaces of the (111) planes and
corresponding XRD patterns of AgPt NPs before and after acid
treatment, respectively. (Reprinted with permission from ref. 233.
Copyright 2011 the Royal Society of Chemistry.)
electronic structure of the surfaces changed correspondingly, which
leads to improved catalytic activity.
6. New developments on NP electrocatalysts for
energy applications
Metal and metal alloy nanostructures are often used as
catalysts. In recent years, with the increasing environmental
This journal is c The Royal Society of Chemistry 2012
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concerns, there is a demand for new technology that does not
rely on fossil fuels. In this context, polymer electrolyte
membrane fuel cells (PEMFCs) have been examined as a class
of devices to provide clean and sustainable power by directly
converting chemical energy stored in fuel molecules such as
hydrogen into electric energy.12,17,30,110,234–240 In a PEMFC
various chemicals including hydrogen, methanol, formic acid
and even ethanol, are fed as fuels at the anode side and
electrochemically oxidized. Oxygen is electrochemically
reduced on catalytic surfaces through oxygen reduction
reaction (ORR) at the cathode. Based on the type of fuels,
PEMFCs can be categorized into direct hydrogen fuel cells
(DHFC), direct methanol fuel cells (DMFC), direct formic
acid fuel cells (DFAFC) and so on. For each type of cell, the
requirement for catalytic nanostructures is different, as
illustrated in Fig. 22. Thus, controlling the various structural
parameters is critical for the development of new catalysts with
high activity and stability.241–243
Metal and metal alloy NPs, Pt-containing ones in particular,
are the choices for many of the electrocatalytic applications.
Obtaining long-lasting, active catalysts, whose properties are
strongly influenced by surface geometric and electronic
factors, is not straightforward.244–252 For instance, in ORR
and methanol oxidation reaction (MOR), Pt alloy NPs are
often used and the maximum mass-specific activity is strongly
size, shape and composition dependent.244,253 In the following
subsections, several recent approaches for the design of highly
active ORR and other Pt-based catalysts will be discussed.
The design of catalysts often involves the following four
aspects: (i) preparing polyhedral NPs bounded by the facets
which show facet-dependent high catalytic activity, (ii) making
nanostructures in NPs to increase the surface-to-volume ratio,
(iii) using an alloying technique to incorporate non-precious
metals into the nanostructures, and (iv) texturing bimetallic
nanostructures.
6.1 Electrocatalysts of single metal nanostructures
Highly dispersed Pt or Pd NPs on carbon have been the choice
of catalysts in various types of fuel cells for quite a while. The
active components are often made of quasi-spherical NPs with
the diameter ranging from about 2 to 10 nm. Besides the need
for high activity, the degradation of such single component
Fig. 22 Illustration of nanostructures of Pt-based NPs developed as
the electrocatalysts for various types of fuel cells.
Chem. Soc. Rev.
 View Online

catalysts is another major problem due to the ripening and
grain growth of the metal particles and the corrosion of carbon
supports during operation.254 Various nanostructures, such as
nanowires/nanotubes,128,140,255–261 nanosheets,157,262–265 and
multipods29,84,130,266–270 have been examined to address the
durability and activity issues.
In addition, research efforts have been devoted to the
development of high-index facet Pt and Pd catalysts since
the report of high performance for ORR by Pt tetrahexahedral
nanocrystals.105–107,185,186,191,271,272,31 The high-index facets
are shown to have a high percentage of low-coordinated
atoms, steps, edges, and kinks on the surface of these
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A
truncated octahedron populations of 70%, 90% and 100%
were obtained, with the remaining particles being cubes
enclosed by {100} facets (Fig. 24). The Pt3Ni catalyst with
100% truncated octahedra, i.e., the sample with the highest
portion of (111) surface among the three, shows the highest
ORR catalytic activity, which was about 4-times higher in area
specific activity than the Pt/C catalysts.
Recently, both cubic and octahedral Pt–M (M = Co, Fe,
Ni, Pd) alloy catalysts (on carbon supports) were prepared
from nanocrystals synthesized using the GRAILS method and
through surface activation using a short-chain amine.116 As
shown in Fig. 25, the Pt3Ni octahedral NP catalysts were

structures, all of which are potentially active sites.273–275 A
cubic Pt concave nanocrystal, which is composed of 24
identical kite-shaped {411} faces, is a good example
(Fig. 23).186 The exposed high-index {411} facets in the
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bounded by {111} facets and the Pt3Ni cubic NPs bounded by
{100} facets. The Pt3Ni octahedral NP has a higher activity
than that of cubes towards the ORR. A five-time improvement
in ORR specific activity over the Pt/C catalysts was found for

concave Pt nanocrystals were attributed to the excellent the octahedral Pt3Ni nanocrystals.
electrocatalytic activity in the oxidation of both formic acid
and ethanol.186 6.3 Bimetallic heterostructures with three-dimensional
nanostructures

6.2 Alloy nanocrystal electrocatalysts Construction of bimetallic heterostructures and three-dimensional

nanostructures is an efficient approach to integrating different
One important strategy to improve the performance of electro- functionalities in one structure. To this end, a simple nonaqueous
catalysts is to alloy Pt with a second metal element. Several method was developed for making Pt-on-Pd bimetallic nano-
reviews have covered the subject of Pt-based alloy NPs as dendrites consisting of a dense array of Pt branches on a Pd core,
electrocatalysts for PEMFCs.30,83,276,277 Thus, this subsection as shown in Fig. 26a–d.17 These Pt-on-Pd heterostructures possess
mainly discusses the recent advancements of selected Pt-based much improved catalytic property toward ORR and better
alloy catalysts. long-term stability than those of Pt/C catalysts (Fig. 26e–f). The
Major advances have been made in the development ORR improved properties were attributed to the favored interfacial
Pt alloy catalysts in recent years, especially since Stamenkovic
and co-workers demonstrated experimentally the large difference
in ORR specific activity between Pt3Ni and Pt extended single
crystal surfaces, and among the three low-index surfaces of this
alloy.37 The Pt3Ni (111) surface has the proper electronic structure
and atomic arrangement in the near-surface region for catalyzing
the ORR. That research work shows the Pt3Ni (111) surface can
be about 90-fold more active than the typical high-quality Pt/C
catalysts and has a turnover frequency (TOF) of 2800 e site1 s1.
Detailed analysis shows the composition of the outermost layer of
the three catalysts was identified, that is, containing almost
exclusively Pt atoms. The middle atomic layer was Ni-enriched
with 52% Ni and then the inner-most layer was enriched with Pt,
which was accounted for 87% of the atoms in the layer. The
appealing aspect of this result is that the Pt3Ni (111) surface
shows much higher catalytic activity than other surfaces, such as
9-fold improvement in area-specific activity than the (100) surface
and 3.6-fold higher than the (110) surface.
During the past several years, substantial research efforts
have been directed toward the shape and composition controls
of Pt-based alloy NPs in search for the catalyst that closes the
gap in activity between the value for existing catalysts and
the high performance demonstrated for the extended single
Fig. 23 (a) TEM image, (b) SAED pattern, and (c) drawing of an
crystalline surfaces. So far the solution phase process based on
individual concave Pt nanocrystal oriented along the [110] direction.
solely the traditionally long-carbon chain surfactant capping
(d) HRTEM image of the region indicated by the box in (a). (e) Model
agents has been able to produce the Pt–Ni alloy NPs with the of atomic arrangement corresponding to the surface region indicated
proper compositions.278 With the traditional reductants, by the box in (d). Cyclic voltammetry (CV) curves for (f) formic acid
only truncated-octahedral Pt3Ni catalysts were obtained. and (g) ethanol by the concave Pt nanocrystals, Pt black, and Pt/C
Nevertheless, the results demonstrated that by changing the (E-TEK). (Reprinted with permission from ref. 186. Copyright 2011
synthesis conditions, three kinds of Pt3Ni catalysts with American Chemical Society.)

Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
 View Online
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A

Fig. 24 TEM images of Pt3Ni nanocrystals with truncated octahedron

populations of (a) 70%, (b) 90%, and (c) 100%. (d) High-resolution
TEM image of a catalyst particle showing the (111) lattice. (e) Area
(mA cm2 Pt) and (f) mass (A mg1 Pt) specific ORR activities for the
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Pt3Ni and reference Pt catalysts. (Reprinted with permission from

ref. 278. Copyright 2010 American Chemical Society.)

Fig. 25 (a–d) TEM micrographs of (a,b) cubic and (c,d) octahedral

Pt3Ni NPs. Comparison of electrocatalytic properties of cubic and
octahedral Pt3Ni nanocrystals: (e) area and (f) mass specific activities.
(Reprinted with permission from ref. 116. Copyright 2011 American
Chemical Society.)
structures between Pt and Pd supports, as well as the larger than
usual overall particle size of Pt-on-Pd nanostructures, which
prevented the small Pt from rapid dissolution during the
ORR. An aqueous method was also developed for making such
bimetallic structures, in which the truncated octahedral nano-
crystals of palladium with an average size of 9 nm was used as
seed crystals to direct the dendritic growth of Pt upon the
reduction of K2PtCl4 by L-ascorbic acid in an aqueous solution.12
This aqueous phase produced Pt-on-Pd heterostructures also
exhibited relatively large surface areas and active facets toward
the ORR. A wet-chemical approach was further developed for the
synthesis of high-quality 3D Pt-on-Pd bimetallic nanodendrites
supported on graphene nanosheets.22 The electrochemical data
indicated that the graphene/bimetallic nanodendrite hybrids
exhibited much higher electrocatalytic activity toward methanol
oxidation reaction than Pt black and Pt/C catalysts. Pt monolayer
on Pd NP catalysts were later shown to have much improved
durability under selected testing conditions.279
In addition to Pt-on-Pd nanoparticles, Pt-on-Au,13,16,21,280,281
Pt-on-Ru,19 and Pt-on-Co282 heterostructures were synthesized
Fig. 26 TEM and HR-TEM micrographs of (a,b) Pt-on-Pd bimetallic
NPs and (c,d) their carbon-supported catalysts after the thermal
treatments. (e) CV, (f) hydroxyl surface coverage (YOH), (g) ORR
polarization curves, and (h) specific kinetic current densities (ik) for
carbon-supported Pt-on-Pd and Pt catalysts, respectively. (Reprinted
with permission from ref. 17. Copyright 2009 American Chemical
Society.)
and studied. Improved performance in electrochemical catalysis
has been observed in these systems. Besides the bimetallic
heterostructures, a few tri-metallic structures with dendrite-
on-particle morphology have been made and shown to be more
active than the bimetallic nanostructures.283–285 For example,
Au@Pd@Pt triple-layered, core–shell structured NPs, which
consisted of Au core, Pd inner layer, and Pt nanoporous outer
shell, showed higher catalytic performance than that of Au@Pt
core–shell NPs for methanol oxidation reaction.285
7. Summary and outlook
This paper discusses a range of preparation methods
and selected examples of metal and alloy nanostructures that
are active for electrocatalysis. Now a pool of synthetic
methodologies are available and our understanding on the
key fundamental concepts on nucleation and growth of facet-
controlled nanocrystals in the presence of surfactants are

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.

greatly improved, laying the foundation for further develop-
ment of better electrocatalysts used for some important
chemical reactions, such as ORR. Noticeably, symmetry-
reduced cubic phase metallic nanocrystals can now be
obtained through the control of reaction kinetics in the
presence of surfactants without the need for additional
reagents to generate the conditions favoring the formations
of defect and thus anisotropic growth. Furthermore, better
understanding of the controls of surface strain and accessi-
bility to the full range of compositions at the nanometer scale
should add new capability for us to design necessary structures
for catalyzing chemical reactions that go well beyond the
Published on 15 November 2012 on http://pubs.rsc.org | doi:10.1039/C2CS35319A
electrochemical conversion.
Acknowledgements
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This work was supported in part by U.S. National Science
Foundation (Grant No.: DMR- 0449849 and CHE- 1213926
to HY) and (Grant No.: 51071116, 51271135 and 51201122).
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