Materials Letters 64 (2010) 856–858

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Synthesis of WS2 nanosheets by a novel mechanical activation method

Zhuangzhi Wu, Dezhi Wang ⁎, Xiuqi Zan, Aokui Sun
Key Laboratory of Ministry of Education for Non-Ferrous Materials Science and Engineering, School of Materials Science and Engineering, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: WS2 nanosheets were synthesized by a novel mechanical activation method, in which a ball-milled mixture
Received 12 November 2009 of WO3 and S was adopted as reagent and then annealed at 600 °C for 2 h in an atmosphere of Ar. The final
Accepted 12 January 2010 products were characterized by XRD, SEM and TEM. It was found that the nanosheets were obtained with
Available online 18 January 2010
thickness of only about 10 nm, through the exfoliation from the sulfurized outer layers of tungsten trioxide.
The ball milling played a crucial role in the mechanical activation of reagents and promoted direct
Keywords:
Tungsten disulfide
production of WS2 without any intermediate products. The effect of temperature was also discussed.
Mechanical activation Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
Semiconductors
Nanomaterials

1. Introduction 2. Experimental

Tungsten disulfide (WS2) belongs to a class of transition metal A mixture of 5 g WO3 and 10 g S was energetically ball-milled at
dichalcogenide (TMDC) compounds, which are anisotropic materials 400 rpm (rotation per minute) in an argon atmosphere for 24 h in a
with strong bonding within the layers and weak interlayer interaction planetary ball mill. Then, 1 g ball-milled mixture and 5 g S were loaded
[1]. There is considerable interest in the development of new into two individual boats and quickly pushed into the hot zone of the
synthetic routes to prepare WS2 nanostructures because of their tube furnace with the latter in the upstream side. The boats were
novel and superior properties compared with their bulk structures. It annealed in an atmosphere of argon at 500 °C, 600 °C, 700 °C and
has been shown that the WS2 nanomaterials can be used as catalysts 840 °C for 2 h, respectively. Finally, black WS2 powder was collected
[2], lubricants [3], lithium battery [4], photoconductors [5], probes for after the system was cooled to room temperature.
scanning probe microscopy [6], shock absorbers [7], solar cell films X-ray diffraction (XRD) analysis was performed on a D/Max-2500
[8], and so on. X-ray diffractometer using CuKα radiation (λ = 0.154 nm). The
Following the first production of IF-WS2 by the reaction between the morphology and structure of the products were studied by a (FEI
oxide and H2S [9], various synthetic methods were explored to prepare Sirion 200) scanning electron microscope (SEM) and (Tecnai G2 20)
WS2 nanomaterials, including magnetron sputtering [8], thermal transmission electron microscope (TEM).
decomposition [10], laser ablation [11], chemical vapor deposition
[12], sonochemical synthesis [13] and hydrothermal/solvothermal 3. Results and discussion
route [14,15]. Recently, a one-step, environmentally friendly, solid
state, bulk fabrication of WS2 nanoplates was reported, in which a Fig. 1 shows the XRD patterns of the products obtained at 500 °C,
thermal reaction between micrometer-sized W with S vapor at 750 °C 600 °C, 700 °C and 840 °C, respectively. As shown in Fig 1 (a), the
was performed in a closed Swagelok reactor. However, the as-obtained reaction is not completed even after performed at 500 °C for 2 h. There
WS2 nanoplates were not regular and stacked too densely, which greatly is only a small typical (002) peak to reveal the existence of WS2, and
reduced the exposed surface area and active sites [16]. In this work, we most of the WO3 powder does not take part in the sulfurized reaction.
designed a novel mechanical activation method to synthesize regular When the temperature is up to 600 °C, pure WS2 is the only product
monodisperse WS2 nanosheets, in which a ball-milled mixture of WO3 and can be indexed to the hexagonal WS2 (JCPDS card No: 08-0237),
and S was used as reactant and then annealed at 600 °C for 2 h in an as shown in Fig. 2 (b). A higher temperature (700 °C) can improve the
atmosphere of Ar. Furthermore, the effect of temperature on the crystallinity of products. As a result, all the reflections in Fig. 2 (c) are
preparation was also discussed to reveal the possible formation enhanced because of the increased temperature. However, higher
mechanism. temperatures will also accelerate the evaporation of sulfur, resulting
in the lack of sulfur to supply sulfurization. Therefore, when the
annealing temperature is increased to 840 °C, there is not enough
⁎ Corresponding author: Tel: +86 731 88877221. sulfur to supply the reaction and an intermediate product of WO2 is
E-mail address: dzwang@mail.csu.edu.cn (D. Wang). observed in Fig. 1 (d).

0167-577X/$ – see front matter. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2010.01.040
 Z. Wu et al. / Materials Letters 64 (2010) 856–858 857

WS2 nanosheets, in which the WS2 nanosheets are produced by the

exfoliation of the outer sulfurized layers.
Typical TEM images of the WS2 nanosheets are shown in Fig. 3. The
nanosheets are stacked loosely and a part of them are slightly curved.
A selected-area electron diffraction pattern is also taken and well-
indexed as a pure hexagonal structure of 2H-WS2. Meanwhile, the
SAED pattern is not a ring but several sets of spots with the same
direction of c-axis. It means that the orientations of c-axis may not be
a random arrangement but rather lie at particular angles to each
other, and these nanosheets are stacked along c-axis with slight angle
rotation. As shown in Fig. 3 (b), the nanosheets align parallel along the
same orientation, but there are still slight angle shifts.
Generally, the sulfurization of WO3 is controlled by the proposed
“outside-in” growth mechanism of MS2 nanoparticles [9,12,19],
including the formation of an incipient closed sulfide shell and the
synergy between the reduction and sulfurization processes, producing
the hollow fullerene or tubular nanostructures. However, in this case,
Fig. 1. XRD patterns of the products obtained at different annealing temperatures: the ball-milled composite powders (WO3 and S) generate novel thin
(a) 500 °C; (b) 600 °C; (c) 700 °C; °C.
nanosheets with thickness of 10 nm. Moreover, there are no interme-
diate products (WO3 − x) obtained in the sulfurization at 500 °C, which
A typical SEM image of the obtained WS2 nanosheets is depicted in means that the internal reaction of the ball-milled composite powders is
Fig.2 (a). The nanosheets are almost monodisperse, which are different not stepwise but a direct one, resulting in the direct production of WS2.
from the WS2 nanoplates with close stacking [16]. Because such laterally This abnormal phenomenon can be attributed to the mechanical
confined 2D crystals are unstable and easy to scroll up into closed activation effect of the ball-milled reactants. The exact reaction and
structures owing to increased peripheral dangling bonds [17], the WS2 activation mechanisms have not been resolved, and a further study is in
nanosheets are also slightly curved, as shown in Fig. 2 (b). Furthermore, progress and will be reported elsewhere.
the thickness of the nanosheets is only about 10 nm, much thinner than
the reported nanoplates [16,18]. To get a better understanding of the 4. Conclusions
formation mechanism, the products obtained at 500 °C are also
observed (Fig. 2 (d)). It is obvious that only part of the quasi-spherical The WS2 nanosheets were successfully prepared via a novel
WO3 particles are sulfurized into lamellar WS2 nanosheets, and most of mechanical activation method, through the exfoliation of the outer
them still keep the primary quasi-spherical structure. This incomplete sulfurized layers of WO3. The thickness of the nanosheets is only about
reaction is also revealed by Fig. 1 (a). Moreover, as shown by the arrow, 10 nm. Moreover, the temperature plays a crucial role in the formation
there is a WO3 particle covered by a piece of WS2 nanosheet, of WS2 nanosheets, and the sulfurization reaction can only be completed
demonstrating that the sulfurization is performed from outside to at proper temperatures (600–700 °C), resulting in the formation of
inside, corresponding with the traditional “outside-in” growth mech- nanosheets. Furthermore, these nanosheets are stacked along the same
anism [9,12,19]. A possible formation mechanism can also be concluded orientations but with slight angle shift. This simple novel strategy can be
according to the coexistence of inner WO3 quasi-spheres and exterior extended to synthesize other nanomaterials.

Fig. 2. SEM images of WS2 products obtained at 600 °C (a–c) and 500 °C (d).
858 Z. Wu et al. / Materials Letters 64 (2010) 856–858

Fig. 3. TEM images and SAED pattern (inset) of the WS2 nanosheets.

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