Escolar Documentos
Profissional Documentos
Cultura Documentos
Department of Biomedical Engineering, Washington University, St. Louis, Missouri 63130, United States, State Key Laboratory for Physical Chemistry of Solid
Surfaces and Department of Chemistry, Xiamen University, Xiamen, Fujian 361005, People's Republic of China, State Key Laboratory of Silicon Materials and
Department of Materials Science and Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China, ^Department of Materials Science,
University of Texas at Dallas, Richardson, Texas 75083, United States, zInstitute of Physics, Chinese Academy of Sciences, Beijing 100190, People's Republic of China,
and #Department of Nanobio Materials and Electronics, World Class University, Gwangju Institute of Science and Technology, Gwangju 500-712, Korea. rPresent
address: Georgia Institute of Technology, Atlanta, Georgia 303322.
The limitation associated with lattice mismatch has become one of the most signicant constraints in generating bimetallic
coreshell nanocrystals, particularly for the
preparation of coreshell nanocrystals with
a single-crystal structure and well-dened
shapes. Attempts to use epitaxial growth to
produce bimetallic coreshell nanocrystals from two metals with lattice mismatch
greater than 5% have been met with limited
success so far. For example, the shells are
often characterized by a polycrystalline
structure, and the nal products often take
a spherical shape or dendritic morphology
due to the lack of an epitaxial relationship
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* Address correspondence to
younan.xia@bme.gatech.edu.
Received for review December 22, 2011
and accepted February 3, 2012.
Published online February 03, 2012
10.1021/nn2050278
C 2012 American Chemical Society
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between the core and the shell.1719 Recently, a number of groups have started to address this issue. To this
end, Tsuji and co-workers demonstrated the syntheses
of Au@Cu and Au@Ni coreshell nanoparticles, where
the lattice mismatches were 11.4% and 13.6%, respectively.20,21 Our group also reported a facile method
for epitaxial growth of Ag on Pd nanocubes, in which
the nucleation and growth of Ag could be controlled
on one, three, or six of the equivalent {100} faces of a
Pd cubic seed.22 As a major advancement, these
studies demonstrated the ability to generate bimetallic
coreshell nanocrystals from two metals with lattice
mismatches greater than 5%. However, there was
essentially no control over the thickness of the shell
and the nal shape taken by the product. In addition,
the growth mechanism was also unclear.
In this work, we chose the Pd and Cu pair as a model
system to investigate the formation of coreshell
nanocrystals from two metals with lattice mismatch
greater than 5%. We have successfully prepared Pd@Cu
coreshell nanocubes via the reduction of CuCl2 by
glucose in the presence of Pd seeds and hexadecylamine
(HDA), a selective capping agent for the {100} facets of
Cu.23 The edge length of the as-obtained Pd@Cu core
shell nanocubes could be easily controlled by varying
the proportion of the seed relative to the precursor. Our
studies indicate that the formation of Pd@Cu coreshell
nanocubes followed a localized epitaxial growth mechanism, by which Cu atoms rst nucleated only on a few
of the many faces of a Pd seed. At a later point, the newly
formed Cu atoms started to nucleate and grow on other
faces of the seed until its entire surface was covered by a
complete shell of Cu. The Pd@Cu coreshell nanocrystals evolved into a cubic shape due to a strong anity of
HDA for the Cu(100) surface.
simply introducing some Pd nanocubes into the solution as the seeds. By separating nucleation and growth
into two dierent tasks, we can achieve a better control
over the size and shape of resultant nanocrystals.2528
Figure 1B shows SEM image of the as-obtained Pd@Cu
coreshell nanocubes synthesized using the standard
procedure. All of them were cubic in shape, only with
slight truncation at the corners (see Supporting Information). The size of the Pd@Cu coreshell nanocubes
could be easily tuned by varying the amount of Pd seeds
added with other parameters being kept the same as in
the standard procedure. For example, by using 1.5, 1.0,
and 0.5 mL of the Pd seeds, the resultant Pd@Cu core
shell nanocubes were 50, 75, and 100 nm, respectively, in
edge length (Figure 1BD). Thanks to their good uniformity in size and shape, some of the coreshell nanocubes also crystallized into two- and three-dimensional
lattices on the Si substrates during solvent evaporation.
The TEM images in the insets clearly show that there was
a Pd seed inside each coreshell nanocube.
We used TEM, high-angle annular dark-eld scanningtransmission electron microscopy (HAADF-STEM),
high-resolution TEM (HRTEM), and energy dispersive
X-ray (EDX) analysis to characterize the morphology,
structure, and composition of the 75-nm Pd@Cu
coreshell nanocubes prepared using the standard
procedure. The Pd seed within the Cu shell could be
easily resolved under TEM and HAADF-STEM due to the
dierence in contrast between Pd and Cu (Figure 2A,B),
conrming the formation of a coreshell structure.
Interestingly, we found that most of the Pd seeds
within the coreshell nanocubes were not located in
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Figure 2. Morphology, structural, and compositional characterizations of the 75-nm Pd@Cu coreshell nanocubes:
(A) TEM image, (B) HAADF-STEM image, (C, D) HRTEM
image, (E) HAADF-STEM image, and EDX mapping (inset),
and (F) line-scan prole. In panel E, the inset was taken from
the boxed region, with the green and red colors corresponding to Pd and Cu, respectively.
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Figure 7. (A,B) SEM images of Pd cuboctahedra and octahedra that served as the seeds for the epitaxial deposition of
Cu shells. (C,D) TEM images of the resultant Pd@Cu coreshell nanocubes. The insets show TEM images of individual
nanocrystals at higher magnications. The scale bars in the
insets are 20 nm.
cores, respectively. As shown in Figure 8, Moir patterns similar to that observed in the case of Pd cubic
seeds were also observed. The Moir patterns also
conrm that the overgrowth was epitaxial and conned to the 111 directions to give {100} facets on the
surface of the Pd@Cu coreshell nanocubes. The Pd
seed was also found to be deviated from the center of
each coreshell nanocube due to the involvement of a
localized epitaxial growth mechanism (Supporting Information, Figure S2). In addition to the eect of shape,
we also studied the eect of size for the cubic Pd seeds
in this synthesis. In a comparison study, 6-nm Pd cubes
were introduced into the reaction as the seeds while
other conditions were kept the same as the standard
procedure. As shown in Supporting Information, Figure S3,
EXPERIMENTAL SECTION
Chemicals and Materials. Sodium tetrachloropalladate (II)
(Na2PdCl4, 99.998%), copper chloride dihydrate (CuCl2 3 2H2O),
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nanocubes prepared using conditions dierent from the standard synthesis. This material is available free of charge via the
Internet at http://pubs.acs.org.
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