See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/301665045

Controllable Synthesis of Cu-Ni Core-Shell Nanoparticles and Nanowires with

Tunable Magnetic Properties

Article  in  Chemical Communications · May 2016

DOI: 10.1039/C6CC02868C

CITATIONS READS

20 627

7 authors, including:

Huizhang Guo Xiang Liu

ETH Zurich Xiamen University
65 PUBLICATIONS   2,217 CITATIONS    25 PUBLICATIONS   668 CITATIONS   

SEE PROFILE SEE PROFILE

Deqian Zeng Dong-Liang Peng

Guangxi University Xiamen University
61 PUBLICATIONS   2,237 CITATIONS    298 PUBLICATIONS   8,231 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

phosphors View project

Single atom catalysts View project

All content following this page was uploaded by Huizhang Guo on 09 February 2018.

The user has requested enhancement of the downloaded file.

 View Article Online
View Journal

ChemComm
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: H. Guo, J. Jin, Y.
Chen, X. Liu, D. Zeng, L. Wang and D. Peng, Chem. Commun., 2016, DOI: 10.1039/C6CC02868C.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/chemcomm
 Page 1 of 4 Please do not adjust margins
ChemComm
View Article Online
DOI: 10.1039/C6CC02868C

Journal Name

COMMUNICATION

Controllable Synthesis of Cu-Ni Core-Shell Nanoparticles and

Nanowires with Tunable Magnetic Properties
Received 00th January 20xx,
Published on 26 April 2016. Downloaded by ETH-Zurich on 29/04/2016 15:15:35.

Accepted 00th January 20xx Huizhang Guo, Jiarui Jin, Yuanzhi Chen,* Xiang Liu, Deqian Zeng, Laisen Wang and Dong-Liang

ChemComm Accepted Manuscript

Peng*
DOI: 10.1039/x0xx00000x

www.rsc.org/

Cu seeds are used to direct the epitaxial growth of Ni shell to form
Cu-Ni core-shell cubes, tetrahexahedrons and nanowires. The
controllable epitaxial growth of Ni shell on Cu core provides
selectively exposed surfaces and morphologies as well as tunable
magnetic properties.
The majority effort towards the development of shaped
hetero-nanostructures has been focused on nanocrystals of
1-5
noble metals, chalcogenides or oxides. Fully non-noble
6-8
metallic hetero-nanostructures with controlled shape and
interfaces are less well studied. Morphology-controllable
synthesis of non-noble metallic nanocrystals, however, is of
significant importance considering their unique magnetic and
catalytic properties, as well as cost efficiency compared to
noble metals.9,10 Among them, Cu-based nanomaterials have
attracted significant interest with their applications in
conductive electrodes,11,12 plasmonic property,13 and
catalysis.14,15 However, their ability against oxidation limits the
wider utilization of Cu-based nanomaterials. Ni or Cu-Ni shell
was applied to improve the anti-oxidation property of Cu
nanomaterials.16,17 Furthermore, the unique magnetic and
catalytic properties of Ni nanocrystals also received a great
deal of interests.18,19 Cu-Ni alloy was used as the substrate for
the growth of 2D materials such as boron nitride grain.20
Controlling the morphology and component of Cu-Ni binary
metallic nanostructures may enable us to study the unique
physical and chemical properties. Especially, construction of a
core-shell structure offers an attractive strategy for fabrication
of nanomaterials with novel or enhanced properties.21,22
Epitaxial seeded-growth is one of the most efficient strategies
for the synthesis of core-shell nanocrystals.23-26 Although some
work has been conducted on the chemical synthesis of Cu-Ni
27-29
core-shell nanoparticles, studies are limited on the
controllable synthesis of Cu-Ni core-shell nanocrystals with
specific shapes as well as the investigation on the correlated
magnetic properties.
In this study, we report the controllable synthesis of Cu-Ni
core-shell nanocubes, tetrahexahedron nanocrystals and
nanowires. By controlling the epitaxial growth of Ni shell on Cu
nanocrystal seeds, the shape of Cu-Ni core-shell nanoparticles
may evolve from cubes to tetrahexahedrons. Core-shell
nanowires with either a corn-like morphology or smooth
surfaces have also been obtained. The as-prepared Cu-Ni core-
shell nanocrystals can possess selectively exposed surfaces and
tunable magnetic properties, which provides advantages for
their catalytic and magnetic applications.
To synthesize Cu-Ni core-shell nanocubes, {100} terminated
Cu nanocubes with an average edge length of 46.3±6.0 nm (Fig.
1a and Fig. S1) were synthesized at first via a
disproportionation reaction13 and then used as seeds for the
epitaxial growth of Ni shell (for details see ESI†). A
heterogeneous nucleation of Ni occurred on the surface of Cu
guaranteed the formation of core-shell structure. When
limited nickel acetylacetonate (Ni(acac)2, 0.05 mmol) was
applied, the epitaxial growth of Ni on these Cu nanocubes gave
Cu-Ni core-shell nanocubes (Fig. 1b). The Ni shell has the
tendency to grow along the <100> directions, i.e. parallel to
the <100> directions of Cu as illustrated in Fig. 1b due to the
lattice match which causes a minimum interface free energy.
The appearance of Moiré fringes on each individual particle
indicates the overlay of two distinct crystal phases.24 The
formation of Moiré fringes can be attributed to the difference
in the crystalline plane interval between Cu core and Ni shell.
For example, the measured spacing between two stripes
(indicated by arrows in Fig. 1b) from a cube is about 6.8 nm,
which is very close to the value (6.9 nm) calculated using the
equation: D=d1d2/(d2−d1), where D is the spacing between two
stripes, and d1 and d2 correspond to the lattice spacing of Cu
{200} planes and Ni {200} planes, respectively. EDS analysis (Fig.
S2) on single particles shows that the center is dominated by
Cu while the edge is rich in Ni, revealing a core-shell structure.

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

Please do not adjust margins

 Please do not adjust margins
ChemComm
COMMUNICATION
Published on 26 April 2016. Downloaded by ETH-Zurich on 29/04/2016 15:15:35.
Fig. 1 (a) and (b) are the TEM images of Cu nanocubes and Cu-
Ni core-shell nanocubes, respectively; (c) and (d) are the
HAADF and EDS line-scan profile of Cu-Ni core-shell polyhedral
nanoparticles, respectively; (e), (f) and (g) are the HAADF
image, elemental map of Cu and elemental map of Ni of a
single polyhedral nanoparticle, respectively.
For the observation on the evolution of the morphology of Ni
shell, the amount of Ni(acac)2 was increased to 0.2 mmol
without changing other synthetic conditions (for details see
ESI†). From the high-angle annular dark-field (HAADF) image
(Fig. 1c), all particles adopt the morphology of polyhedrons.
The core-shell structure is confirmed by EDS line-scan analysis
(Fig. 1d). The HAADF image (Fig. 1e) demonstrates that the
polyhedron nanoparticle consists of six rectangular pyramids
on the {100} facets of Cu nanocube. Therefore, the
morphology can be described as tetrahexahedron. The core-
shell structure is further confirmed by EDS mapping on a single
particle. As shown in Fig. 1f and 1g, Cu is observed mainly in
the center, whereas Ni is basically distributed at the edge
region, which suggests a core-shell structure. The reason why
the shape of Cu-Ni core-shell nanoparticles evolve from cubes
to polyhedrons can be understood using the illustration shown
in Fig. S3. At first, Ni shell will adopt {100} facet as the main
exposed surfaces because of the lattice match. As Ni shell
becomes thicker, the effect of Cu core will be weakened, and
the facets with lower reticular density (high surface energy)
will grow at a faster speed compared to the one with higher
2 | J. Name., 2012, 00, 1-3
Please do not adjust margins
Page 2 of 4
View Article Online
DOI: 10.1039/C6CC02868C
Journal Name
ChemComm Accepted Manuscript
Fig. 2 TEM images (a, d, g and j), SAED patterns (b, e, h and k)
and simulated morphologies (c, f, I and l) of Cu-Ni core-shell
nanoparticles viewed along the [011], [112], [111] and [100]
zone axes of Cu seed. The Ni shell and Cu core are presented in
blue and pink, respectively, in the schematic drawing of the
core-shell nanoparticle.
reticular density. As a result, the main exposed surfaces of Ni
shell are {111} facets, which agrees with the Gibbs–Wulff
crystal growth law.
To further investigate the structure of the as-prepared Cu-Ni
core-shell nanoparticles, TEM images, corresponding selected
area diffraction patterns (SAED) patterns, and simulated
morphologies from different directions were acquired and
shown in Fig. 2. The nanoparticle displays an olivary shape in
TEM image (Fig. 2a) when observed along the [110] zone axis
of Cu core. From the SAED pattern (Fig. 2b), the diffraction
spots from the seed (Cu) and shell (Ni) are well resolved for
the higher index planes such as {400} and {311} (see the inset
of Fig. 2b). Notably, the boundary between core and shell is
parallel to {100} planes, which is coincident with the
aforementioned epitaxial growth. When the same
nanoparticle is tilted to the [112] zone axis, a cut-corner
square is observed (Fig. 2d-2f). On the other hand, if we
This journal is © The Royal Society of Chemistry 20xx
 Page 3 of 4 Please do not adjust margins
ChemComm
View Article Online
DOI: 10.1039/C6CC02868C
Journal Name COMMUNICATION
Published on 26 April 2016. Downloaded by ETH-Zurich on 29/04/2016 15:15:35.

ChemComm Accepted Manuscript

Fig. 4 ZFC-FC curves (a and b) obtained in a measuring field and
cooling field of 100 Oe and magnetic hysteresis loops (c and d)
of the Cu-Ni core-shell nanoparticles prepared using Ni
precursors of 0.05 mmol (a and c) and 0.2 mmol (b and d).

crystalline structure corresponding to fcc Cu with a [110]

growth direction. XRD analysis (Fig. S4) also confirms the
presence of fcc Cu and Ni. The EDS line-scan analysis (Fig. 3c)
reveals strong Cu signals in the nanowire center and strong Ni
signals at the edge, revealing a core-shell structure. The
presence of Cu in the core and Ni at the shell also can be
clearly seen from the EDS spectra recorded from the nanowire
center and edge (Fig. 3d).
Fig. 3 Electron microscopic characterization of corn-like Cu-Ni
A possible mechanism for the growth of corn-like Cu-Ni
core-shell nanowires. (a) SEM image; (b) TEM image with SAED
nanowires is illustrated in Fig. 3e. At first, metal precursors
pattern (inset). The diffraction spots belonging to fcc Cu in the
CuCl2·2H2O and Ni(acac)2 may react with oleylamine to form
[-110] zone axis are outlined using white lines; (c) EDS line-
stable complexes. At the desired reaction temperature, a small
scan profile along with the HAADF image; (d) EDS spectra from 2+ 0
amount of Ni ions are reduced into Ni atoms. Since the
the nanowire center and edge; (e) Schematic illustration of the 2+
redox pair potential of Ni /Ni(-0.246 V) is smaller than that of
formation mechanism. 2+ 0 2+
Cu /Cu(0.337 V), these Ni species would rapidly reduce Cu
0
ions into Cu atoms via galvanic replacement reactions. This
acquire the TEM image from same nanoparticle along [111]
kind of galvanic replacement was previously observed in
zone axis, a hexagon is observed (Fig. 2g-2i). Viewing from 8
formation of Cu-Ni nanoplates. Then Cu nuclei would be
[100] direction, we observe a square (Fig. 2j-2l). Based on the 0
formed from these Cu atoms and develop into multi-twined
above results, we propose a structure model of
crystal seeds which will grow into nanorods/nanowires with
tetrahexahedron for the as-synthesized Cu-Ni core-shell
the extension of reaction time. The shape selective formation
nanoparticles, in which six rectangular pyramids grow from the
of Cu nanowire is owing to the generation of five-twined
{100} facets of Cu nanocube.
nucleus in the nucleation stage, and the surface selective
The Cu-Ni core-shell nanowires were prepared by injecting a
binding of chloride ions on the {100} facets of Cu nanocrystals
mixture of 5 mL of oleylamine, 0.5 mmol of Ni(acac)2 and 0.3 6,11 2+
in the growth. At this stage, the concentration of Cu ions
mmol of CuCl2·2H2O into 6 mL of 1-octadecence via a syringe 0
o is greatly reduced due to the formation Cu nanowires and Ni
pump at 185 C for 3 h (for details see ESI†). The SEM image 0
atoms begin to accumulate. Once the concentration of Ni
(Fig. 3a) shows that these nanowires have widths in the range
atoms surpassed the critical nucleation concentration, Ni
of 90-140 nm and lengths which may be up to several tens of
clusters begin to form on the surfaces of Cu nanowires. These
micrometers. Their morphology is not like many commonly
Ni clusters can further grow into larger Ni nanoparticles and
reported core-shell nanowires which have smooth surfaces.
eventually form a corn-like morphology. We can also obtain
Abundant particles with dimensions varying from 30 to 60 nm
Cu-Ni core shell nanowires with smooth surfaces (see Fig. S5)
deposit on the surfaces of nanowires, forming a hierarchical
just by changing the stirring speed. This indicates that the
corn-like morphology. Fig. 3b shows the TEM image of a single
nanowire. SAED pattern recorded from this nanowire reveals a

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 Please do not adjust margins
ChemComm
COMMUNICATION
formation of Cu-Ni core-shell nanowires is also a kinetics-
related process.
The zero-field cooled (ZFC) and field-cooled (FC)
temperature-dependent magnetization curves of the Cu-Ni
core-shell nanoparticles prepared using a content of Ni(acac)2
of 0.05 mmol and 0.2 mmol are presented in Fig. 4a and 4b,
respectively. It can be seen that the nanocube sample
(prepared using 0.05 mmol Ni(acac)2) which has a thinner layer
of Ni shell exhibit room-temperature superparamagnetic
characteristics with a blocking temperature (TB) of about 125 K
while the polyhedral sample (prepared using 0.2 mmol
Ni(acac)2) which has a thicker layer of Ni shell has room-
temperature ferromagnetic properties. Such a difference on
Published on 26 April 2016. Downloaded by ETH-Zurich on 29/04/2016 15:15:35.
magnetic properties is also revealed in the hysteresis loops (Fig.
4c and 4d). The measured coercivity values for the nanocube
sample are 554 and 0 Oe at 5 and 300 K, respectively while
those for the polyhedral sample are 636 and 126 Oe at 5 and
300 K, respectively. A larger saturated magnetization is also
observed for the polyhedral sample, indicating a thicker
magnetic layer in the core-shell structure. For the Cu-Ni core-
shell nanowires, the divergence temperature of magnetization
in the ZFC-FC curves is even higher than 300 K (Fig. S6a),
indicating that the nanowires are ferromagnetic at room
temperature. The presence of magnetic hysteresis at 300 K
confirms the room-temperature ferromagnetic characteristics
(Fig. S6b). The growth of ferromagnetic Ni shells over Cu cores
makes the diamagnetic Cu nanowires magnetically responsive
when an external magnetic field is applied. This useful
property offers convenience for applications such as magnetic
assemble of nanocrystals and the recycling of bimetallic
catalysts.
In summary, we have used Cu nanocube and nanowire seeds
to direct the epitaxial growth of Ni shell on Cu core. Cu
nanocube can regulate the conformal growth of Ni along <100>
directions to produce core-shell cubes. As the thickness of Ni
shell increases, the growth rate of Ni along <100> directions
becomes higher than that along <111> directions to give
tetrahexahedron nanocrystals. We have also prepared Cu-Ni
core-shell nanowires with either coarse or smooth surfaces.
This work provides a strategy for the synthesis of Cu-Ni core-
shell nanocrystals with selectively exposed surfaces and
morphologies as well as tunable magnetic properties.
This work was partially supported by the National Natural
Science Foundation of China (Grant Nos. 51471137, 51371154
and 51571167), the National Basic Research Program of China
(Grant No. 2012CB933103) and the Program for New Century
Excellent Talents in University of Ministry of Education of
China (NCET-13-0497).
Notes and references
1 S. G. Kwon and T. Hyeon, Acc. Chem. Res., 2008, 41, 1696.
2 M. H. Huang and P.-H. Lin, Adv. Funct. Mater., 2012, 22, 14.
3 Y. Xia, Y. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem., Int.
Ed., 2009, 48, 60.
4 Y. Zeng, R. Hao, B. Xing, Y. Hou and Z. Xu, Chem. Commun.,
2010, 46, 3920.
4 | J. Name., 2012, 00, 1-3
Please do not adjust margins
View publication stats
Page 4 of 4
View Article Online
DOI: 10.1039/C6CC02868C
Journal Name
5 L. Zhang, J. Wu, H. Liao, Y. Hou and S. Gao, Chem. Commun.,
2009, 45, 4378.
6 H. Guo, Y. Chen, H. Ping, J. Jin and D.-L. Peng, Nanoscale,
2013, 5, 2394.
7 Y. Zhang, W. Huang, S. E. Habas, J. N. Kuhn, M. E. Grass, Y.
Yamada, P. Yang and G. A. Somorjai, J. Phys. Chem. C,
2008, 112, 12092.
8 H. Guo, Y. Chen, H. Ping, L. Wang and D.-L. Peng, J. Mater.
Chem., 2012, 22, 8336.
9 J. Park, E. Kang, S. U. Son, H. M. Park, M. K. Lee, J. Kim, K. W.
Kim, H. J. Noh, J. H. Park, C. J. Bae, J. G. Park and T.
Hyeon, Adv. Mater., 2005, 17, 429.
10 R. Hao, R. Xing, Z. Xu, Y. Hou, S. Gao and S. Sun, Adv. Mater.,
ChemComm Accepted Manuscript
2010, 22, 2729.
11 H. Guo, N. Lin, Y. Chen, Z. Wang, Q. Xie, T. Zheng, N. Gao, S.
Li, J. Kang, D. Cai and D.-L. Peng, Sci. Rep., 2013, 3, 2323.
12 D. Zhang, R. Wang, M. Wen, D. Weng, X. Cui, J. Sun, H. Li and
Y. Lu, J. Am. Chem. Soc., 2012, 134, 14283.
13 H. Guo, Y. Chen, M. B. Cortie, X. Liu, Q. Xie, X. Wang and D.-L.
Peng, J. Phys. Chem. C, 2014, 118, 9801.
14 H. Guo, X. Liu, C. Bai, Y. Chen, L. Wang, M. Zheng, Q. Dong
and D.-L. Peng, ChemSusChem, 2015, 8, 486.
15 M. Biswas, A. Saha, M. Dule and T. K. Mandal, J. Phys. Chem.
C, 2014, 118, 22156.
16 J. Song, J. Li, J. Xu and H. Zeng, Nano Lett., 2014, 14, 6298.
17 J. Chen, J. Chen, Y. Li, W. Zhou, X. Feng, Q. Huang, J.-G.
Zheng, R. Liu, Y. Ma and W. Huang, Nanoscale, 2015, 7,
16874.
18 C. Jiang, Z. Shang and X. Liang, ACS Catal., 2015, 5, 4814.
19 X. Kong, Y. Zhu, H. Zheng, X. Li, Y. Zhu and Y.-W. Li, ACS
Catal., 2015, 5, 5914.
20 G. Lu, T. Wu, Q. Yuan, H. Wang, H. Wang, F. Ding, X. Xie and
M. Jiang, Nat. Commun., 2015, 6, 6160.
21 D. Wang and Y. Li, Adv. Mater., 2011, 23, 1036.
22 M. B. Gawande, A. Goswami, T. Asefa, H. Guo, A. V. Biradar,
D.-L. Peng, R. Zboril and R. S. Varma, Chem. Soc. Rev.,
2015, 44, 7540.
23 S. E. Habas, H. Lee, V. Radmilovic, G. A. Somorjai and P.
Yang, Nat. Mater., 2007, 6, 692.
24 M. Jin, H. Zhang, J. Wang, X. Zhong, N. Lu, Z. Li, Z. Xie, M. J.
Kim and Y. Xia, ACS Nano, 2012, 6, 2566.
25 F. Liu, Y. Hou and S. Gao, Chem. Soc. Rev., 2014, 43, 8098.
26 F. Liu, J. Zhu, W. Yang, Y. Dong, Y. Hou, C. Zhang, H. Yin and S.
Sun, Angew. Chem. Int. Edit., 2014, 53, 2176.
27 K. J. Carroll, S. Calvin, T. F. Ekiert, K. M. Unruh and E. E.
Carpenter, Chem. Mater., 2010, 22, 2175.
28 T. Yamauchi, Y. Tsukahara, T. Sakata, H. Mori, T. Yanagida, T.
Kawai and Y. Wada, Nanoscale, 2010, 2, 515.
29 G. Guisbiers, S. Khanal, F. Ruiz-Zepeda, J. Roque de la Puente
and M. José-Yacaman, Nanoscale, 2014, 6, 14630.
This journal is © The Royal Society of Chemistry 20xx