Materials Letters 59 (2005) 3728 – 3731

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Synthesis and magnetic properties of NiS1 + x nanocrystallines

H.T. Zhang, G. Wu, X.H. Chen *
Hefei National Laboratory for Physical Sciences at Microscale and Department of Physics,
University of Science and Technology of China, Hefei, Anhui 230026. P.R. China

Received 10 May 2005; accepted 3 July 2005

Available online 20 July 2005

Abstract

Hexagonal a-NiS nanocrystals and Ni3S4 nanoplates have been prepared by a colloidal chemical process in oleylamine. X-Ray diffraction
(XRD), transmission electron microscope (TEM), field-emission scanning electron microscope (FESEM), and X-ray photoelectron
spectroscopy (XPS) were employed to characterize the products. The self-assembly hollow spheres by a-NiS nanocrystals are observed. XPS
study indicates that the products’ surface contains excess sulfur which would enhance the density of active sites on the catalyst surface for
hydrogenolysis process. Magnetization measurement indicates that the a-NiS and Ni3S4 are no longer antiferromagnetic; both of them show
paramagnetism due to the size effect.
D 2005 Elsevier B.V. All rights reserved.

PACS: 61.46; 81.10; 96.60; 75.60.C; 71.30

Keywords: Nanoparticles; Colloidal chemical synthesis; Nickel sulfide; Characteristic and properties; Magnetic materials; Insulator-metal transitions

1. Introduction rhombohedral (h-NiS, millerite) and high-temperature hex-

Nanoscale materials are being pursued extensively
because their crystal structures, optical, magnetic, electrical
and catalytic properties are strongly composition-, structure-
, size- and shape-dependent [1– 9]. Many methods have
been introduced to synthesize nanomaterials with aniso-
tropic shape and tunable structures. Among them, colloidal
chemical method is proven to be one powerful route to
crystal structure-, size- and shape-controlled nanoparticles.
In addition, many metastable materials can be formed in
colloidal chemical method at low temperature.
Nickel sulfides are important materials in technical
application and can be used as hydrogenation catalyst and a
possible transformation toughener [10 – 14]. It is well known
that nickel sulfides exhibit complicated compositional,
structural, and magnetic behaviors. Nickel sulfides have a
variety of compositions, including Ni3S2, Ni3+x S2, Ni4S3+x ,
Ni6S5, Ni7S6, Ni9S8, Ni3S4, and NiS [14 – 18]. Stoichiometric
NiS crystallizes in two structures: the low-temperature
agonal (a-NiS) crystal structures [19,20].The a-NiS is only
stable in high temperature range (> 600 -C). A metal-to-
semiconductor transition and paramagnetic-to-antiferromag-
netic transition occur at 264 K [21]. Therefore, anomalous
properties will be expected in the nanoscale nickel sulfides
due to a size effect compared to its bulk counterpart. It is
significant for basic research and technical applications.
Here we report one colloidal chemical method to ‘‘rod-like’’
a-NiS nanocrystals and their self-assembly hollow spheres,
and synthesis of Ni3S4 nanoplates. The morphologies of
products are characterized by transmission electron micro-
scope and field-emission scanning electron microscope. The
surface of both samples is analyzed by XPS. SQUID is
employed to study the magnetic properties of the products.
2. Experimental section
2.1. Materials

* Corresponding author. Tel./fax: +86 551 3601654. Organometallic precursor, nickel acetylacetone (Ni(acac)2),
E-mail address: chenxh@ustc.edu.cn (X.H. Chen). was prepared following the method reported previously
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.07.007
 H.T. Zhang et al. / Materials Letters 59 (2005) 3728 – 3731 3729

[22]. Elemental sulfur: (99.5%, Shanghai Chem. Co.).

Oleylamine: (Technical purity, Feixiang. Chem. Corp.).

2.2. Synthesis of a-NiS

2 mmol Ni(acac)2 and 2 mmol S were added to 20 mL

degassed oleylamine under N2. The reaction mixture was
slightly stirred and heated at 140 -C for 1 h, resulting in a
black colloidal solution. The products were separated upon
the addition of equal volume alcohol, and centrifuged. In the
end, the products were washed using alcohol and dichloro-
methane solvent for several times, and dried under vacuum
at room temperature.

2.3. Synthesis of Ni3S4
2 mmol Ni(acac)2 and 12 mmol S were added to 20 mL
degassed oleylamine under N2. The reaction mixture was
slightly stirred and heated at 180 -C for 3 h, resulting in a
black colloidal solution. The products were separated upon
the addition of equal volume alcohol, and centrifuged. In the
end, the products were washed using alcohol and carbon
sulfide for several times, and dried under vacuum at room
temperature.
2.4. Characterization
Field-emission scanning electron microscope (FE-SEM)
images were observed with a JSM-6700F field emission
scanning electron microscope. Transmission electron micro-
scope (TEM) was conducted with a Hitachi H-800, high-
resolution (HR) TEM images and the corresponding
selected-area electron diffraction (SAED) were taken on a
JEOL-2010 high-resolution transmission electron micro-
scope operating at 200 KV. Products were characterized by a
Rigaku D/max-A X-Ray diffractometer (XRD) with graph-
ite monochromatized CuKa1 radiation in the 2h range of
20- – 80- with the step of 0.02 degree at room temperature.
The composition was determined by the Atomscan Advant-
Fig. 2. (a) TEM image of the as-prepared a-NiS nanocrystals; (b) the self-
assembled hollow spheres of a-NiS nanocrystals. Inset of (a): SAED
pattern of the a-NiS nanocrystals.
age inductively coupled plasma atomic emission spectrom-
eter (ICP). X-ray photoelectron spectroscopy (XPS) was
performed on a VGESCALAB MKII X-ray photoelectron
spectrometer, using nonmonochromatized Mg Ka X-rays as
the excitation source. The magnetic susceptibility measure-
ment in zero-field-cooling (ZFC) and field-cooling (FC)
process at an applied field of 1000 Gauss was carried out
with a superconducting quantum interference device
(SQUID) magnetometer (MPMS-5).
3. Results and discussions
Fig. 1a shows the XRD pattern of a-NiS, all the peaks can be
indexed as the hexagonal structure of a-NiS (JCPDS NO.75-0613).
No impurities such as Ni, NiOx or other nickel sulfides are detected
in the XRD pattern. XRD pattern of Ni3S4 is shown in Fig. 1b. All
peaks can be indexed as the cubic structure (JCPDS NO 76-1813).

Fig. 1. X-ray diffraction patterns of the products: (a) a-NiS, (b) Ni3S4. Fig. 3. HRTEM images of the a-NiS nanocrystals.
3730 H.T. Zhang et al. / Materials Letters 59 (2005) 3728 – 3731
Fig. 4. FE-SEM image of the as-prepared Ni3S4 nanoplates. Inset: enlarged
image of the Ni3S4 nanoplates. Scale bars represent 100 nm.
According to the ICP analysis, the nickel to sulfur ratios for a-NiS
and Ni3S4 are 1 : 1.01 and 1 : 1.31, respectively.
Fig. 2a shows the TEM image of a-NiS nanoparticles. It is clear
that the nanoparticles are non-spherical but more or less ‘‘rod-like’’.
The nanoparticles have sizes of 4  10 nm. The ED pattern taken
on them confirms that the a-NiS nanoparticles are the hexagonal
phase. More interesting, the nanoparticles self-assemble to hollow
spheres in the alcohol-hexane solution. Fig. 2b shows two typical
hollow spheres. The hollow spheres have diameters of 150 – 250
Fig. 5. (a) XPS spectra for Ni 2p3/2 core-level, (b) XPS spectrum for S 2p
core-level of the formed samples.
nm. Though the mechanism of the self-assembly is unclear, the
‘‘rod-like’’ shape of the nanoparticles possibly plays some roles in
the formation of the hollow spheres.
Detailed micro-structure of the nanoparticles was character-
ized by the HRTEM. Systemic HRTEM study indicates that all
nanoparticles are single-crystal. The nanocrystals aggregate
randomly, therefore, both the microstructures of the tips and
lateral surfaces of the ‘‘rod-like’’ nanocrystals could be observed.
Typical HRTEM image of one tip is shown in Fig. 3a. The
fringes have a distance of 2.57 Å, corresponding to the d
spacing of {101} planes. Fig. 3b shows the HRTEM image of
lateral side of one nanocrystal. The fringes along the side have a
distance of 2.93 Å, corresponding to the d spacing of {100}
planes.
To study the effect of the ratio of sulfur to nickel acetylacetone
on the products’ structure and morphology, a series of experiments
was conducted. Some impurities, such as Ni3S2 and Ni7S6, appear
when the sulfur to nickel acetylacetone ratio decreases to less than
1 : 1. In addition, it was found that Ni3S4 was formed instead of NiS
when the sulfur to nickel acetylacetone ratio was enhanced to 6 : 1.
The shape of products changes to two-dimensional nanoplates
from the ‘‘rod-like’’ nanoparticles. Fig. 4 shows the FESEM image
of Ni3S4 nanoplates, indicating that the nanoplates have plane sizes
of 120 – 200 nm and thickness of 8 – 12 nm.
It is well known that nanomaterials have large specific surface,
which is very important to the catalytic property of materials. XPS
Fig. 6. Temperature dependence of magnetization for (a) a-NiS and (b)
Ni3S4 in FC (filled symbols) and ZFC (open symbols) processes under an
applied field of 1000 Gauss. Insets: the corresponding M – H curves at 5 K.
 H.T. Zhang et al. / Materials Letters 59 (2005) 3728 – 3731
was employed to analyze the products’ surface. Fig. 5a shows the
Ni 2p3/2 core-level spectra of the samples. The binding energies of
Ni 2 p3/2 core-level for a-NiS and Ni3S4 are 853.4 and 854.3 eV,
respectively, which are consistent with the reported value for
NiS1 + x (Ni 2p3 in NiS 852.80 eV, in Ni2S3 854.30 eV). Fig. 5b
shows the S 2p core-level spectra of the two samples. The binding
energies of S 2p for a-NiS and Ni3S4 are 162.0 and 162.5 eV,
respectively, consistent with the reported values (S 2p in NiS
162.20 eV) [23]. It indicates that the binding energies of Ni 2p3/2
and S 2p for a-NiS are smaller than those for Ni3S4. The peak areas
of Ni 2p3/2 and S 2p give the Ni : S ratios of 1 : 1.79 and 1 : 1.5 for
a-NiS and Ni3S4, respectively. The results reveal that surfaces of
a-NiS contain relatively more sulfur than that of Ni3S4 because the
size of a-NiS nanoparticles is much smaller. These results suggest
that the surface of both samples contains excess sulfur, which
would enhance the density of active sites on the catalyst surface for
hydrogenolysis process [14].
The temperature dependences of magnetization measured under
the ZFC and FC processes at an applied field of 1000 Gauss are
shown in Fig. 6. Fig. 6a shows the temperature dependence of
magnetization for the as-prepared a-NiS nanocrystals. The magnet-
ization of a-NiS increases with decreasing temperature in both
ZFC and FC processes, indicating a paramagnetic behavior, in
contrast to antiferromagnetism for its bulk material. It suggests that
the long-range antiferromagnetic ordering was destroyed in the
nanoscale materials. The paramagnetic behavior might arise from
the so-called finite-size effect and/or modification of the bulk state
due to surface effect [24,25]. Compared to the magnetic behavior
of NiS bulk measured, the magnetization of the as-prepared a-NiS
is six times larger than that of the bulk at room temperature [21]. In
addition, magnetization of the as-prepared nanoscale a-NiS is
about five hundred times larger than that of bulk materials at 5K
[21]. Such enhanced magnetization are often observed in nanoscale
materials due to the size effect [26]. Inset of Fig. 6a shows the
magnetization versus applied magnetic field (M – H) curve for the
as-prepared a-NiS nanocrystals. The hysteresis loop reveals that
the a-NiS nanoparticles have remanent magnetization of 0.00012
emu/g, and coercivity of 155 Oe. The results indicate that there are
some weak ferromagnetic interactions, which arise from the
uncompensated spins in the surface due the larger ratio of surface
atoms to bulk atoms, exist at low temperature range. Anomalous
magnetic properties were also observed on CoO and NiO nano-
particles [27,28]. The temperature dependence of magnetization, as
shown in Fig. 6b, for the as-prepared Ni3S4 nanoplates, shows the
similar behavior as a-NiS nanocrystals. No hysteresis is observed
in the M – H curve as shown in the inset of Fig. 6b for Ni3S4
nanoplates. To our knowledge, there is no report on the magnetic
properties of bulk Ni3S4. Therefore, we cannot compare the
magnetization of the nanoplates to the bulk.
4. Conclusion
In summary, metastable hexagonal a-NiS nanocrystals
and two-dimensional Ni3S4 nanoplates were successfully
prepared through a colloidal chemical process. It is found
that the composition and crystal structure can be tuned
through the modulating Ni(acac)2 : S ratio. Interestingly, the
self-assembly hollow spheres by a-NiS nanocrystals are
observed. XPS study indicates that the surfaces of both
3731
samples contain excess sulfur which would enhance the
density of active sites on the catalyst surface for hydro-
genolysis process. Magnetization measurement indicates
that both the a-NiS and Ni3S4 nanoplates are no longer
antiferromagnetic; both of them show paramagnetism due to
the size effect. In addition, weak ferromagnetic interactions,
which arise from the increasing uncompensated surface
spins, exist in the a-NiS nanocrystals.
Acknowledgements
This work was supported by the National Science
foundation of China, and the Knowledge Innovation Project
of Chinese Academy of Sciences.
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