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Applied Surface Science 241 (2005) 218–222

www.elsevier.com/locate/apsusc

Size-controlled synthesis of nickel nanoparticles


Y. Houa,b, H. Kondohb, T. Ohtab,*, S. Gaoa
a
State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and
Molecular Engineering, Peking University, Beijing 100871, China
b
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

Abstract

A facile reduction approach with nickel acetylacetonate, Ni(acac)2, and sodium borohydride or superhydride leads to
monodisperse nickel nanoparticles in the presence of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO). The
combination of HDA and TOPO used in the conventional synthesis of semiconductor nanocrystals also provides better control
over particle growth in the metal nanoparticle synthesis. The size of Ni nanoparticles can be readily tuned from 3 to 11 nm,
depending on the ratio of HDA to TOPO in the reaction system. As-synthesized Ni nanoparticles have a cubic structure as
characterized by power X-ray diffraction (XRD), selected-area electron diffraction (SAED). Transmission electron microscopy
(TEM) images show that Ni nanoparticles have narrow size distribution. SQUID magnetometry was also used in the
characterization of Ni nanoparticles. The synthetic procedure can be extended to the preparation of high quality metal or
alloy nanoparticles.
# 2004 Elsevier B.V. All rights reserved.

PACS: 81.05.Y; 75.50.K; 61.46

Keywords: Synthesis; Nickel; Nanoparticles; Magnetism

1. Introduction attracted much interest due to the potential application


in magnetic recording technology [3,4]. A flexible
With increase interest in fabricating nanodevices synthetic route is indispensable to exploit magnetic
with nanosized blocks, much attention has been storage materials. So far, a number of physical and
focused on exploiting a general route to control size chemical routes have also been applied to produce
and morphology of nanoscale materials [1,2]. In nanoscale magnetic materials, including mechanical
recent years, nanoscale magnetic materials have grinding, sonochemistry, organometallic precursor
pyrolysis, metal melt reduction in micelle phase,
and electrochemical deposition, etc. [5]. However, the
* Corresponding author. Tel.: +81 3 5841 4331;
fax: +81 3 3812 1896.
size distribution of the products is not ideal. Recent
E-mail address: ohta@chem.s.u-tokyo.ac.jp (T. Ohta), developments of the organometallic route to produce
gaoson@pku.edu.en (S. Gao). high quality semiconductor nanocrystals included the

0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.09.045
Y. Hou et al. / Applied Surface Science 241 (2005) 218–222 219

combination of trioctylphosphine oxide (TOPO)-TOP, The resulting mixture was heated to 180 8C and kept
pure hexadecylamine (HDA) or HDA–TOPO-TOP as at this temperature for 30 min under Ar atmosphere.
the stabilizing agents [6]. During this process, the color change from light
Some combinations of TOPO and oleic acid [1], yellow to dark was observed, indicating the formation
oleic acid and oleylamine [2], ACA and TOP [4] have of nickel particles. The resulting solution was allowed
also been applied to produce magnetic nanocrystals to cool to room temperature. Ni nanoparticles were
via the decomposition of organometallic precursors. extracted from the solution upon adding ethanol.
However, the organometallic precursors are volatile The as-prepared products were redispersed in hexane
and thermally unstable, gradually releasing toxic CO or octane. Particle size and morphology were studied
and metal at ambient temperature. The simple using a Hitachi 800 transmission electron microscope
reduction route should be considered to produce (TEM). TEM samples were prepared by dropping the
monodisperse magnetic metal nanoparticles [7,8]. hexane dispersion of nanoparticles on a carbon-coated
Reduction synthesis of Co, Ni nanocrystals in the copper grid. Powder X-ray diffraction (XRD) patterns
presence of the alkylphosphine oxide-alkylphosphine of the samples were recorded with a Rigaku D/max
combination was reported recently [9]. Compared 2000 X-ray diffractometer equipped with a Cu Ka
with other magnetic metals such as Co, FePt, etc., radiation source (l = 0.15418 nm).
relatively few works have been done on the fabrication
of monodisperse Ni nanoparticles. Previously, we
prepared monodisperse Ni nanoparticles in mono- 3. Results and discussion
surfactant (HDA) system without other solvents [10].
Considering the growing demand of metal nanocrys- It is well known that strong intermolecular forces,
tals, we tried to improve the TOPO–oleic acid by such as van der Waals attraction, p–p interaction, etc.,
introducing HDA into the metal colloidal synthesis contribute to the aggregation of nanoparticles. As for
system. Herein we describe the size-controlled magnetic nanoparticles, magnetic dipole–dipole inter-
synthesis of nickel nanoparticles through the mod- action makes this kind of attraction stronger. Thus it is
ification of surfactants, such as HDA–TOPO–oleic a challenge to obtain monodisperse magnetic nano-
acid. The solution reduction of Ni(acac)2 (acac = particles dispersion. Different ligands, such as
acetylacetonate) by sodium borohydride or super- polymer and surfactants, have been used to modify
hydride in dichlorobenzene was employed to produce the surface of nanoparticles for stabilization and to
nickel nanoparticles. Surfactants were used to control the particle growth. In our experiments, a
control the growth of nanocrystals and coat the mixture of TOPO and/or HDA was used to control the
nanoparticles to prevent them from further oxidation particle size, stabilize nanoparticle dispersion and
and aggregation. limit further oxidation on the particle surface. Oleic
acid is an excellent stabilizing agent. But when it is
employed alone, it binds so tightly to particle surfaces
2. Materials and methods that the particle growth is impeded. TOPO can control
the growth rate of nanoparticles because of the
HDA (90%) and TOPO (99%) were purchased coordination with metal. If it is used alone, however, it
from Aldrich, Ni(acac)2, sodium borohydride and cannot prevent nanoparticles from growing aggre-
oleic acid were analytic grade reagents. All of them gates. The combination of TOPO–oleic acid proves
were used without further purification. the steadily growth of the particles [4], but was not
The synthesis was conducted using a standard very effective to produce smaller size nickel nano-
airless technology. In a typical procedure, 0.2 g of particles even if the concentration of TOPO was
Ni(acac)2 was dissolved in 5 ml of o-dichlorobenzene increased to 2.4 g in the present system. The long
at 100 8C, and quickly injected into the mixture inc- chain alkylamine such as hexadecylamine has stronger
luding 40 ml of dichlorobenzene, 0.5–1.5 g of TOPO, ligand ability with metal on the surface of nanometals
designed amount of HDA, and 0.15 g of sodium bor- than TOPO. By introducing HDA, we obtained nearly
ohydride at 120–160 8C during vigorously stirring. monodisperse smaller nickel nanoparticles.
220 Y. Hou et al. / Applied Surface Science 241 (2005) 218–222

by using Scherrer’s formula. To obtain smaller Ni


nanoparticles, HDA was introduced into the above
solution. In the case of molar ratio 1:4 for TOPO to
HDA, the XRD pattern of the product shows broad-
ening of the peaks which correspond to the size of
5 nm by Scherrer’s formula. While in the case of only
HDA, the X-ray reflections (2 0 0) and (2 2 0) in the
sample (c) are further broadened and attenuated by the
stacking faults along c-axis. The size of this sample
was calculated to be 3 nm by Scherrer’s formula.
The size and morphology of the Ni nanoparticles
Fig. 1. XRD patterns for the samples prepared in different amounts were characterized by TEM. As shown in Fig. 2, the
of: (a) 1.5 g of TOPO, (b) 1.5 g of TOPO + 4.0 g of HDA and (c) average size of Ni nanoparticles corresponding to the
4.0 g of HDA. samples in Fig. 1 is 11, 5 and 3.7 nm, respectively,
which is in good agreement with the calculated values
by Scherrer’s formula. The size distributions of nickel
To study the influence of HDA on the size of Ni nanoparticles are shown in Fig. 2d–f. The appearance
nanocrystals, we kept the total amount of the solvent, of some darker particles results from an enhanced
Ni(acac)2, sodium borohydride and oleic acid con- diffraction contrast due to their orientation with
stant. In the case of 1.5 g TOPO, high crystalline respect to the electron beam. The selected-area
nickel particles were obtained. As shown in Fig. 1a, electron diffraction (SAED) patterns in the inset
the XRD pattern shows the feature of cubic nickel reveals that the samples are crystalline or semi-
structures, whose size is calculated to be about 11 nm crystalline. With increase of HDA, the size of nickel

Fig. 2. TEM images of samples with various sizes (a) 11 nm, (b) 5 nm, (c) 3 nm, respectively. The size distributions of the samples are shown in
the bottom of corresponding TEM image, respectively (d)–(f). The insets show the selected diffraction patterns of the samples (samples (a)–(c)
from Fig. 1).
Y. Hou et al. / Applied Surface Science 241 (2005) 218–222 221

nanocrystals decreases. It is worthwhile noting that the The temperature dependence of the magnetization was
introduction of HDA strongly decreases the size of measured by using zero-field cooling (ZFC) and field-
nanoparticles to 3.7 nm and narrows the size distri- cooling (FC) procedures. The blocking temperature of
bution of nanoparticles, as described above. Ni nanoparticles with the size of 3, 11 nm was found to
The formation of Ni nanoparticles from the redox be 12 K and 80 K, respectively. The coercivity of the
reaction in the present system is a very complicated 3 nm nanoparticles at 5 K is about 200 Oe, whereas
process. The process begins with rapid nucleation and the coercivity at 300 K is nearly negligible, corre-
growth of nuclei into smaller clusters. HDA and sponding to the superparamagnetism [18]. More
TOPO were used as the capping agents to tune the detailed magnetic studies are currently under way.
growth of nanoclusters. It is generally accepted that
HDA and TOPO reversibly coordinate with surface
metals into the ‘‘intermediate’’, followed by the limit
4. Conclusion
growth of metal nuclei [11]. In contrast to the linear
structure of HDA, TOPO has bulky end groups, which
We have developed a facile and chemical reduction
probably protect the surface of nuclei from coating
route to synthesize size-controlled nickel nanoparti-
with surfactants, leading to high surface free energy.
cles. The surfactants including HDA and/or TOPO
This is why the particles grow to larger sizes and
were used to control the particle size. In particular, the
crystallization easily occurs in contrast to experiments
introduction of HDA is an effective approach to obtain
with fatty acids [4]. The capping agents allow the
smaller monodisperse metal nanoparticles. This
particles to be dissolved in non-polar solvent and
approach provides useful information for the synthesis
also prevent agglomeration and oxidation of the
of other metal nanoparticles.
particles.
TOPO–oleic acid has been applied to obtain Co
nanorods, which may be attributed to the metastable
hcp structure, through dynamic control process Acknowledgements
recently [1]. In fact, we prepared anisotropic Ni
nanocrystals by selecting the type of surfactants in the This work was in part supported by the State Key
solvothermal reduction environment [12]. In the case Project for Fundamental Research of China
of TOPO and/or HDA, however, we could not observe (G1998061305), the National Science Fund for
anisotropic structures of Ni nanocrystals. There are Distinguished Young Scholars of China (20125104),
several possible factors to hinder the formation of a the Chinese Postdoctoral Science Fund, Japan Society
low dimensional structure. First, Ni nanocrystals have for the Promotion of Science (JSPS) and the 21st
a strong tendency to form particles with fcc structure Century COE Program from the Ministry of Educa-
which is the most stable for bulk Ni. Second, it is tion, Culture, Sports, Science and Technology. We
necessary to use suitable stabilizers for controlling the thank for the helpful discussion with Dr. Yunhui
facet growth to obtain the low dimensional structures. Huang in Tokyo Institute of Technology.
The combination of TOPO and/or HDA seems
difficult to control the growth of one certain facet
of Ni nanocrystals.
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