Solid State Communications 138 (2006) 538–541

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Selective synthesis and magnetic properties of FeSe2 and FeTe2

nanocrystallites obtained through a hydrothermal co-reduction route
Anping Liu a, Xiangying Chen b,*, Zhongjie Zhang b, Ying Jiang b, Chengwu Shi b
a
School of Materials Science and Engineering, Hefei University of Technology, Hefei, Anhui 230009, People’s Republic of China
b
School of Chemical Engineering, Hefei University of Technology, Hefei, Anhui 230009, People’s Republic of China
Received 18 January 2006; received in revised form 10 April 2006; accepted 10 April 2006 by E.V. Sampathkumaran
Available online 4 May 2006

Abstract
A hydrothermal co-reduction method has been developed to fabricate ferroselite (FeSe2) nanorods and frohbergite (FeTe2) nanocrystallites
using N2H4$H2O as the reductant. The experimental results indicate that the concentration of N2H4$H2O and the proportion of the starting
materials play important roles in obtaining pure FeSe2 and FeTe2 nanocrystallites. Meanwhile, the magnetic properties of the as-obtained FeSe2
and FeTe2 nanocrystallites are measured at room temperature.
q 2006 Elsevier Ltd. All rights reserved.

PACS: 61.66.Fn; 81.10.Dn

Keywords: A. Nanostructures; B. Chemical synthesis; C. Transmission electron microscopy

1. Introduction FeSe2, FeTe2 microcrystals and single crystals were fabricated

through hydrothermal-reduction route [8]; MSe2 (MZNi, Co,
Transition metal chalcogenides have drawn considerable Fe) were prepared by a solvothermal-reduction process [9].
attention owing to their important optical, electrical, and However, there are few reports on the mild synthesis and
transport properties [1,2]. Their conductive behavior ranges magnetic characterization of FeSe2 and FeTe2 nanocrystallites
from semiconductor to metallic, and they evidence a wide measured at room temperature.
range of magnetic properties [3,4]. In particular, transition Herein, we present a hydrothermal co-reduction method to
metal diselenides or ditellurides in the 3D series with pyrite or fabricate FeSe2 nanorods and FeTe2 nanocrystallites using
marcasite type structure (such as FeSe2 and FeTe2) exhibit 3D N2H4$H2O as the reductant. In particular, the magnetic
magnetic ordering and semiconductivity [5,6]. properties of as-prepared samples are measured at room
Currently, compared with the traditional solid-state syn- temperature.
thesis routes, the solution-phase approach has proved to be a
promising method for fabrication, shaping, sizing, and
2. Experimental section
orientation of various inorganic materials in aqueous solution,
which offers the advantages of enhanced purity, lower reaction
All chemicals were of analytical grade and used without
temperature, and higher film growth rate, as well as the
further purification.
possibility of acceleration of diffusion, adsorption, reaction
rate, and crystallization, especially under hydrothermal or
solvothermal conditions [7]. To date, many efforts have been 2.1. Synthesis of FeSe2 sample
made to prepare transition metal diselenides or ditellurides
nanocrystallites through solution-phase route. For example, In a typical experimental procedure, an aqueous solution of
40 mL was prepared by dissolving FeCl3$6H2O (75 mM),
Na2SeO3 (75 mM), hydrazine hydrate (N2H4$H2O, 1.5 M) in
* Corresponding author. Tel.: C86 551 2901460; fax: C86 551 2901450. distilled water under constant stirring. The mixture was then
E-mail address: [email protected] (X. Chen). transferred to a stainless Teflon-lined 50 mL capacity
0038-1098/$ - see front matter q 2006 Elsevier Ltd. All rights reserved. autoclave, which was further heated at 140 8C for 12 h. After
doi:10.1016/j.ssc.2006.04.008 cooling to room temperature naturally, the black products were
 A. Liu et al. / Solid State Communications 138 (2006) 538–541 539

filtered off, washed with distilled water and absolute ethanol

for several times, and dried in vacuum at 50 8C for 6 h.

2.2. Synthesis of FeTe2 sample

In a typical experimental procedure, an aqueous solution of

40 mL was prepared by dissolving FeCl3$6H2O (75 mM),
Na2SeO3 (75 mM), hydrazine hydrate (N2H4$H2O, 4.5 M) in
distilled water under constant stirring. The mixture was then
transferred to a stainless Teflon-lined 50 mL capacity
autoclave. The autoclave was heated at 140 8C for 12 h, and
then cooling to room temperature naturally. The black products
were filtered off, washed with distilled water and absolute Fig. 2. TEM images of FeSe2 (a) and FeTe2 (b) samples.
ethanol for several times, and dried in vacuum at 50 8C for 6 h.
single-crystal nature of the FeSe2 nanorods. The TEM image in
2.3. Characterization Fig. 2(b) indicates that the as-prepared FeTe2 sample consists
of irregular nanocrystallites with single-crystal characteristics.
X-ray powder diffraction (XRD) patterns were recorded on Fig. 3 shows the magnetic hysteresis curves for the FeSe2
a Japan Rigaku D/max-gB X-ray diffractometer with Cu Ka and FeTe2 samples measured at room temperature. The
radiation (lZ1.54187 Å). Transmission electron microscopy hysteresis loop for FeSe2 is shown in Fig. 3(a), which has the
(TEM) images were obtained on a Hitachi H-800 transmission saturation magnetization (Ms), remanent magnetization (Mr),
electron microscope with an accelerating voltage of 200 kV. and coercivity (Hc) values of ca. 0.25, 0.022 emu/g, and
The magnetic measurement was carried out in a vibrating 129.67 Oe, respectively. Meanwhile, Fig. 3(b) is the typical
sample magnetometer (VSM) (BHV-55, Riken, Japan). hysteresis loop for FeTe2, which has the saturation magnetiza-
tion (Ms), remanent magnetization (Mr), and coercivity (Hc)
3. Results and discussion values of ca. 2.19 emu/g, 0.61 emu/g, and 164.62 Oe,
respectively. To our knowledge, the hysteresis loops for
Fig. 1 is the typical XRD patterns of the as-obtained FeSe2 pure-phase FeSe2 and FeTe2 samples were not previously
and FeTe2 samples. The reflection peaks in Fig. 1(a) can be reported in the literature. Even so, it is believed that the
indexed as orthorhombic FeSe2 with cell parameters of aZ excellent magnetic properties of the as-obtained FeSe2 and
4.822, bZ5.768, and cZ3.590 Å, which are in agreement with FeTe2 samples with relatively high coercivity could be utilized
the reported values (JCPDS 21-0432, aZ4.800, bZ5.776, and as building blocks in future industries.
cZ3.585 Å). Meanwhile, The reflection peaks in Fig. 1(b) can As a promising method for preparing nanomaterials under
be indexed as orthorhombic FeTe2 with cell parameters of aZ mild conditions, the so-called co-reduction approach originates
5.310, bZ6.266, and cZ3.872 Å, which are consistent with from Wurtz reaction, through which many important inorganic
the reported values (JCPDS 14-0419, aZ5.29, bZ6.27, and materials such as diamond, SiC were successfully fabricated
cZ3.86 Å). No obvious impurity phase can be detected. [10]. Recently, N2H4$H2O is used as reducing agent to obtain
Representative TEM images of FeSe2 and FeTe2 samples nanomaterials including MnSe2, NiTe, CoTe and so on when
are shown in Fig. 2. It is seen in Fig. 2(a) that the as-prepared applying the co-reduction method [3a,5b]. In this study, we
FeSe2 sample is composed of a large number of nanorods. The extend this method to prepare pure phase FeSe2 and FeTe2
corresponding ED pattern (the inset in Fig. 2(a)) reveals the nanocrystallites using FeCl3, Na2SeO3 or Na2TeO3 as the
120

211
111

2.0
122
031
011

130

1.0
200
020

202
Intensity (a.u.)

112

M (emu/g)
320
212

(b)
310
220

221
210
121

0
111

(a)
211
120

–1.0
101

031

122
131
011

(b)
110

121

310
200

220

–2.0
311
210

320

(a)

–10.0k –5.0k 0.0 5.0k 10.0k

10 20 30 40 50 60 70 H (Oe)
2θ (degree)
Fig. 3. Magnetic hysteresis curves measured at room temperature for FeSe2 (a)
Fig. 1. XRD patterns of the as-obtained samples: FeSe2 (a) and FeTe2 (b). and FeTe2 (b) samples.
540 A. Liu et al. / Solid State Communications 138 (2006) 538–541

$ $
* *
(d)
* $ $ *
*
Intensity (a.u.)

Intensity (a.u.)
*
(c) # (b)
* * * *
&
(b) # #
&
&
# (a) & & & &
(a) # # &

10 20 30 40 50 60 70
10 20 30 40 50 60 70
2θ (degree)
2θ (degree)
Fig. 4. XRD patterns of the as-obtained FeSe2 sample with different
Fig. 6. XRD patterns of the as-synthesized samples with the initial proportion
concentration of N2H4$H2O: (a) 3 M; (b) 4.5 M; (c) 6 M; (d) 7.5 M.
(1:1) of (a) FeCl3 and Na2SeO3; (b) FeCl3 and Na2TeO3.
starting materials. To our knowledge, it is the first time to
can be obtained in Fig. 5(a) and (b). And XRD patterns of pure-
prepare pure-phase FeSe2 and FeTe2 nanocrystallites using the
phase FeTe2 same as that of in Fig. 1(b) are shown in Fig. 5(c)
co-reduction method. The freshly formed Fe, Se or Te reduced
and (d) when adjusting the concentration of N2H4$H2O as 6 or
by N2H4$H2O are highly active and maybe further combine 7.5 M.
together to produce FeSe2 and FeTe2 nanocrystallites under Meanwhile, the influence of initial proportion of starting
hydrothermal conditions in the autoclave. materials on the phase is also studied. Some reflection peaks of
In this study, the detailed amount of N2H4$H2O on the phase FeSe (denoted as &, JCPDS Card no. 85-0735) are observed in
of the products was investigated by adjusting its concentration Fig. 6(a) when the initial FeCl3 and Na2SeO3 proportion of 1:1.
as 1.5, 3, 4.5, 6, or 7.5 M based on the XRD characterization. And some reflection peaks of FeTe (denoted as *, JCPDS Card
Fig. 4 shows the XRD patterns of the as-obtained FeSe2 sample no. 65-2808) occur in Fig. 6(b) when the initial FeCl3 and
with different concentration of N2H4$H2O. When enhancing Na2TeO3 proportion of 1:1. That is to say, pure-phase FeSe2
the concentration of N2H4$H2O in the solution using FeCl3 and and FeTe2 nanocrystallites can be obtained only when the
Na2SeO3 as the starting materials, some unexpected reflection corresponding concentration of N2H4$H2O is of 1.5, 4.5 M,
peaks occur compared with the XRD pattern in Fig. 1(a). The respectively, keeping other reaction conditions unchanged. In a
reflection peaks (denoted as #) in Fig. 4(a)–(c) can be indexed word, the above experimental results demonstrate that the
as FeSe (JCPDS Card no. 85-0735) when the concentration of concentration of N2H4$H2O and the proportion of the starting
N2H4$H2O is of 3, 4.5, and 6 M, respectively. When the materials in the solution play vital roles in obtaining pure FeSe2
concentration of N2H4$H2O is of 7.5 M in Fig. 4(d), the as- and FeTe2 nanocrystallites.
prepared sample is composed of (SeO3)4 (denoted as $, JCPDS
Card no. 72-1661) and Fe3O4 (denoted as *, JCPDS Card no.
28-0491). When the concentration of N2H4$H2O in the solution 4. Conclusion
containing FeCl3 and Na2TeO3 is of 1.5 or 3 M, FeTe2 sample
with impurity of FeTe (denoted as #, JCPDS Card no. 65-2808) In summary, ferroselite (FeSe2) nanorods and frohbergite
(FeTe2) nanocrystallites are successfully fabricated through the
co-reduction approach. The concentration of N2H4$H2O and
the proportion of the starting materials on the phase of the
(d)
products are discussed. And the magnetic properties of the
samples are measured at room temperature. This simple
Intensity (a.u.)

(c) synthesis route might be extended to other inorganic materials

with excellent properties.
# ##
(b) # # #
Acknowledgements
# ##
(a) # # # Financial support from Hefei University of Technology is
acknowledged.
10 20 30 40 50 60 70
2θ (degree) References

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