View Article Online / Journal Homepage / Table of Contents for this issue
Journal of Dynamic Article Links < C
Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 8195
www.rsc.org/materials
Anisotropic growth of palladium twinned nanostructures controlled by kinetics
and their unusual activities in galvanic replacement†
Published on 16 March 2012. Downloaded by Western Kentucky University on 29/10/2014 10:17:24.
Chengming Wang,‡a Lili Wang,‡a Ran Long,a Liang Ma,a Limin Wang,b Zhengquan Li*b and Yujie Xiong*a
Received 20th January 2012, Accepted 14th March 2012
DOI: 10.1039/c2jm30411b
Five-fold twinned structures are a class of important members in the
family of metallic nanocrystals with face-centered cubic (fcc)
structures, which can anisotropically grow into nanowires when their
{100} facets are protected. In this communication, we first discover
their unique growth mode that generates a new structure of palla-
dium nanocrystals potentially enclosed by high-index facets, when
the growth kinetics is manoeuvred.
Shape control of a metal nanocrystal has been a central theme of
research in nanotechnology, as its physical and chemical properties
can be easily tuned by tailoring the shape.1 Among various
morphologies, nanocrystals enclosed by high-index facets are of
particular interest, as they are generally considered as better candi-
dates for catalytic applications than their counterparts bounded by
low-index ones.2 High-index facets possess a larger number of low-
coordination atoms on the surface which can serve as active sites for
species adsorption and reaction activation.2 Driven by the high
chemical activities of high-index facets, much effort has been made to
promote their formation on nanocrystal’s surfaces in the past years.
The majority of the developed methods are to select appropriate
capping agents with relatively long chains that can be more easily
accommodated on less closely packed high-index facets, while having
relatively weak binding to the {100} and {111} facets, such as the
cetyltrimethylammonium (CTA+) ions that have been explored
recently.3 All of these studies are based on the manipulation of the
surface energies of various facets on single-crystal structures.
The use of long-chain capping agents can effectively promote the
formation of high-index facets; however, it raises another concern
that the existence of these macromolecules on the surface may have
a significant impact on their chemical activities in further applica-
tions. Given this consideration, we shall explore whether the growth
of high-index facets could be facilitated via a different route. Recent
work by the Xia research group highlights the possibility of
a
Hefei National Laboratory for Physical Sciences at the Microscale,
University of Science and Technology of China, Hefei, Anhui 230026, P.
R. China. E-mail: yjxiong@ustc.edu.cn; Fax: + 86 551 3606657; Tel: +
86 551 3606657
b
Department of Materials Physics, Zhejiang Normal University, Jinhua,
Zhejiang 321004, P. R. China. E-mail: zqli@zjnu.edu.cn
† Electronic supplementary information (ESI) available: detailed
experimental procedure. See DOI: 10.1039/c2jm30411b
‡ Both authors contributed equally to this work.
This journal is ª The Royal Society of Chemistry 2012
COMMUNICATION
generating high-index nanocrystals in another system: five-fold
twinned structures could grow into anisotropic structures, which
display rice-like shape and contain {611} facets on the surface, other
than nanowires whose side faces are enclosed by {100} facets.4 Five-
fold twinned structures possess concave surfaces on one side of each
planar defect where newly formed atoms can be easily added to grow
along one dimension,5 enabling them to spontaneously form aniso-
tropic structures as long as the kinetics is appropriately controlled.
High-index facets can be left on the nanocrystal’s surface when the
atomic addition is uneven along the growth axis.
Herein, we report a facile synthetic approach to a new nano-
structure of palladium—anisotropic twinned structures with uneven
diameters along the short axis (namely nanotapers owing to their
unique tapered pod-like shape). We conclude that reaction kinetics
plays an important role in controlling the anisotropic growth of
twinned structures, resulting in the production of nanotapers or
nanowires. As expected, the taper-like shape of the obtained nano-
structures makes them unusually chemically active as compared with
{100} facet-enclosed nanocubes. The palladium nanotapers can react
with HAuCl4 aqueous solution through galvanic replacement,
whereas the nanocubes remain very inactive under the conditions for
the replacement.
In a typical synthesis, palladium nanotapers were grown from
a simple reaction system where Na2PdCl4, poly(vinyl pyrrolidone)
(PVP, M.W. z 55 000) and KI were dissolved in water in an auto-
clave at 150  C. The commercially available PVP is terminated with
hydroxyl groups, so it can serve as a mild reducing agent like a long-
chain alcohol.6 Meanwhile, PVP was also used as a stabilizer to
prevent the agglomeration of nanoparticles. KI is selected to play
a dual-function role in the synthesis: i) to replace the chloride in
[PdCl4]2 by iodide and lower the electrical potentials of the palla-
dium precursors for slow reaction;7,8 ii) to selectively adsorb on {100}
facets and manipulate the growth of various facets.8,9
Such a simple reaction system can generate a new nanostructure of
palladium. Fig. 1 shows typical scanning and transmission electron
microscopy (SEM and TEM) images of the samples prepared from
this synthesis. It is clear that all the nanocrystals are five-fold twinned,
and more than 90% of the nanocrystals have been grown into
anisotropic structures. Typically, the anisotropic structures exhibit
tapered pod-like shapes which consist of a relatively sharp tip and
a ca. 45 nm diameter bottom. The average length is 75 nm along the
long axis. Sharp edges and corners can be easily identified on the
surface of each nanocrystal by the SEM image (Fig. 1a). As shown in
J. Mater. Chem., 2012, 22, 8195–8198 | 8195
 View Article Online

can grow into five-fold twinned nanowires when the reaction rate is
increased (see Fig. 2a–b). It implies that a relatively slow reaction is
the key to uneven atomic addition to the nanocrystal’s surface during
crystal growth. This feature has been further confirmed by switching
the reducing agent PVP (M.W. z 55 000) to PVP (M.W. z 29 000)
(see Fig. S2†). This change does not alter the reaction environment
much (e.g., viscosity of the reaction system); however, the reaction
becomes faster given that the amount of reducing agents should be
directly proportional to the number of PVP chains as the end
Published on 16 March 2012. Downloaded by Western Kentucky University on 29/10/2014 10:17:24.

hydroxyl groups are the only functional parts for reduction.6 As

a result, the reaction also yields mainly five-fold twinned nanowires
instead of nanotapers. Overall, all the kinetics-dependent experiments
performed by varying various parameters confirm that the reaction
kinetics is critical to the formation of tapered pod-like structures.
Thus, we can conclude that the uneven atomic addition along the
short axis should be ascribed to an insufficient supply of freshly
formed atoms when the twinned structures anisotropically grow
along the long axis. When the reaction is slow enough, there is no
sufficient atomic stock that can be successively provided for atomic
addition to the nanocrystal’s surface. As a result, the diameters along
the short axis would significantly shrink during anisotropic growth,
leading to the formation of tapered pod-like structures.
It is worth noting that KI is another key component for kinetic
control. The iodide ions can replace the chloride in [PdCl4]2 to form
[PdI4]2 , which in turn lowers the potential of the palladium species.7,8
A direct benefit from the potential reduction is to ensure the slow

Fig. 1 (a) SEM and (b) TEM images of Pd anisotropic twinned nano-
structures prepared at 150  C. Panels d–f show the high-resolution TEM
images of the sample.

the TEM images (Fig. 1b–f), twin planes can be observed in the
projected images, indicating that the structures are twinned. More
careful characterization by high-resolution TEM reveals that this
anisotropic structure is five-fold twinned, similar to that of nanowires
that we have previously investigated.10 Since the diameters of this
structure are uneven along the short axis, the side faces should be
different from those in nanowires (i.e., {100} facets). Instead,
according to the simulation in the literature (see Fig. S1†),4 they
should be high-index facets such as {611}. More detailed high-reso-
lution characterizations (Fig. 1f) identify that the side faces of
a nanotaper can be assigned to {611} facets according to the
projection angle (13 ) between the surface and the {100} facets (see
Table S1†). It is worth noting that the slope of taper growth varies
from one to another, depending on the growth kinetics. As a result,
the side faces should be assigned to different high-index facets in each
nanocrystal. For example, the side face in Fig. 1d can be assigned to
(311) according to the projection angle of 25 . Nevertheless, the
uneven growth mode along the long axis clearly reveals that the
surface facets are high-index facets rather than {100}.
In the anisotropic growth of twinned structures, the reaction
kinetics has been determined to be a major factor.9 To investigate the
effect of kinetics on the anisotropic growth, we have performed
controlled experiments by altering several synthetic components.
Among the components, the reaction temperature is a very critical
parameter that we can tune to manipulate the reaction kinetics, as the Fig. 2 SEM and TEM images of Pd nanostructures prepared under the
reaction rate constant should have an exponential relationship with same conditions as that in Fig. 1, except: (a, b) at higher temperature of
the temperature according to the Arrhenius equation.11 The experi- 180  C; (c–f) in the presence of the double amount of KI. The blue circle
ment at higher temperature (180  C) shows that twinned structures in panel c highlights a typical nanotaper with higher aspect ratio.

8196 | J. Mater. Chem., 2012, 22, 8195–8198 This journal is ª The Royal Society of Chemistry 2012
 View Article Online

reduction of palladium precursors for the uneven atomic addition

along the short axis. Moreover, a more important function of iodide
is that it can selectively adsorb onto the {100} facets of palladium
nanocrystals and promote their formation on the nanocrystal’s
surface.8–10 As Fig. S1† reveals, {611} facets can be considered as the
vector sum of five {100} facets and one {111} facet.4 In this sense, the
percentage of {100} facets is definitely dominant in the structure of
the nanotapers. Hence we believe that the addition of KI makes an
important contribution to the shape formation of nanotapers by
Published on 16 March 2012. Downloaded by Western Kentucky University on 29/10/2014 10:17:24.

promoting {100} facets. On the other hand, it is anticipated that

increasing the concentration of iodide should be able to greater tune
the percentage of {100} facets. To confirm this feature, we have
performed the synthesis in Fig. 1 by doubling the amount of added
KI. Fig. 2c–f show SEM and TEM images of the obtained product,
revealing that the aspect ratio of most nanotapers has been greatly
increased and some nanowires can be found in the product. It indi-
cates that the increase in the iodide concentration has tuned the
growth mode of the nanocrystals towards the formation of nano-
wires. Thus, an appropriate percentage of {100} facets on the surface
is very critical for the synthesis of nanotapers. Certainly, the amount
of KI holds the key to controlling the ratio of {100} to {111} facets.
Taken together, these two factors result in the appearance of taper-
like structures—slow reduction for insufficient stock supply and the
control of an appropriate {100} percentage by iodide.
Given that the structures of the nanotapers possess high-index
facets on the surface, they should exhibit higher chemical activities
than their low-index counterparts. Direct evidence for identifying this
difference comes from their capability of reacting with HAuCl4
solution through galvanic replacement. According to the electrical
potentials (1.002 V for [AuCl4] /Au versus 0.591 V for [PdCl4]2 /Pd),
atomic palladium should be able to react with HAuCl4 solution via
the galvanic replacement below.
3Pd(s) + 2[AuCl4] (aq) + 4Cl (aq) / 3[PdCl4]2 (aq) + 2Au(s)
However, in practice, palladium nanocrystals enclosed by low-
index facets could not undergo this replacement without the
introduction of bromide to further enlarge the potential difference.12
Most likely, the barrier for this replacement lies in the difficulty of
the starting pitting process (i.e., localized corrosive etching) on
a perfect nanocrystal.13 Fig. S3† shows high-resolution TEM
images and energy-dispersive X-ray spectra (EDS) of palladium
nanocubes bounded by {100} facets treated with HAuCl4 solution,
confirming that galvanic replacement could not occur on the
nanocubes. In contrast, Fig. 3 shows that our taper-like nano-
structures can perform this galvanic replacement. High-resolution
TEM (Fig. 3c–d) identifies the existence of gold islands formed on
the nanotaper surface with a thickness of ca. 4 nm. The EDS
spectrum reveals that there is around 10% (atomic percentage) gold
in the nanostructures after the replacement. It is assumed that this
unusual chemical property of nanotapers is related to their high-
index surface. The high-index facets have less densely packed and
coordinated surface atoms, and in most cases, possess lots of
terraces and steps, which makes them highly reactive in chemical
reactions.14 In the present case, we have also observed the presence
of terraces and steps on the surface of the nanotapers (see
Fig. S4†), which are most likely responsible for the unusual
chemical reactivity of the nanotapers. Owing to the presence of gold
Fig. 3 (a) SEM image, (b) TEM image, (c, d) high-resolution TEM
images, (e) EDS spectrum and (f) UV-vis spectrum of the sample in Fig. 1
after galvanic replacement with HAuCl4.
in the nanostructures, the samples start to exhibit a surface plasmon
resonance (SPR) band located at 400 nm. Thus, from another
perspective, the galvanic replacement here enables the production of
bifunctional nanostructures with both catalytic and plasmonic
features, which may allow the investigation of palladium-catalyzed
reactions with SPR spectroscopy or surface-enhanced Raman
spectroscopy (SERS) in the future.
In conclusion, a facile synthetic approach has been developed to
synthesize palladium nanotapers potentially enclosed by high-index
facets. We have revealed that the reaction kinetics holds the key to
tuning the growth mode of the nanocrystals while the selective
capping effect makes a contribution to facet control. The anisotropic
growth of twinned structures here provides a new approach for
constructing a high-index surface without the need to use long-chain
capping agents. These nanocrystals exhibit superior chemical activi-
ties compared to their low-index counterparts, as proven in the
galvanic replacement. It is anticipated that this work opens a door
for the development of new synthetic methods for metallic nano-
crystals with high-index facets for various applications such as
catalysis.
This work was financially supported by the National Natural
Science Foundation of China (No. 21101145, J1030412), the
Fundamental Research Funds for the Central Universities (No.
WK2340000017), the Recruitment Program of Global Experts and
the CAS Hundred Talent Program. ZL acknowledges the financial
support from the National Nature Science Foundation of China
(No. 20901068) and Zhejiang Qianjiang Talent Project (No.
2010R10028).

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 8195–8198 | 8197

Notes and references
1 Y. Xia, Y. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem., Int. Ed.,
2009, 48, 60.
2 (a) G. A. Somorjai, Science, 1985, 227, 902; (b) Y. Xiong, B. J. Wiley
and Y. Xia, Angew. Chem., Int. Ed., 2007, 46, 7157.
3 (a) T. Ming, W. Feng, Q. Tang, F. Wang, L. Sun, J. Wang and
C. Yan, J. Am. Chem. Soc., 2009, 131, 16350; (b) Y. Yu, Q. Zhang,
X. Lu and J. Y. Lee, J. Phys. Chem. C, 2010, 114, 11119.
4 Y. Zheng, J. Tao, H. Liu, J. Zeng, T. Yu, Y. Ma, C. Moran, L. Wu,
Y. Zhu, J. Liu and Y. Xia, Small, 2011, 16, 2307.
Published on 16 March 2012. Downloaded by Western Kentucky University on 29/10/2014 10:17:24.
5 C. Lofton and W. Sigmund, Adv. Funct. Mater., 2005, 15, 1197.
6 Y. Xiong, I. Washio, J. Chen, H. Cai, Z.-Y. Li and Y. Xia, Langmuir,
2006, 22, 8563.
7 Handbook of Chemistry and Physics ed. R. C. Weast, CRC Press, Boca
Raton, FL, 60th edn., 1980.
8198 | J. Mater. Chem., 2012, 22, 8195–8198
View Article Online
8 Y. Xiong, H. Cai, B. J. Wiley, J. Wang, M. Kim and Y. Xia, J. Am.
Chem. Soc., 2007, 127, 3665.
9 X. Huang and N. Zheng, J. Am. Chem. Soc., 2009, 131, 4602.
10 Y. Xiong, H. Cai, Y. Yin and Y. Xia, Chem. Phys. Lett., 2007, 440,
273.
11 Y. Xiong, J. M. McLellan, J. Chen, Y. Yin, Z.-Y. Li and Y. Xia, J.
Am. Chem. Soc., 2005, 127, 17118.
12 (a) H. Zhang, M. Jin, J. Wang, W. Li, P. H. C. Camargo, M. J. Kim,
D. Yang, Z. Xie and Y. Xia, J. Am. Chem. Soc., 2011, 133, 6078; (b)
H. Zhang, M. Jin, H. Liu, J. Wang, M. J. Kim, D. Yang, Z. Xie, J. Liu
and Y. Xia, ACS Nano, 2011, 5, 8212.
13 J. Chen, J. M. McLellan, A. Siekkinen, Y. Xiong, Z.-Y. Li and Y. Xia,
J. Am. Chem. Soc., 2006, 128, 14776.
14 (a) X. Xia, J. Zeng, B. McDearmon, Y. Zheng, Q. Li and Y. Xia,
Angew. Chem., Int. Ed., 2011, 50, 12542; (b) M. Jin, H. Zhang,
Z. Xie and Y. Xia, Angew. Chem., Int. Ed., 2011, 50, 7850.
This journal is ª The Royal Society of Chemistry 2012