Appl Phys A (2009) 96: 861–867
DOI 10.1007/s00339-009-5320-1
Structural transformation of MoO3 nanobelts into MoS2
nanotubes
Francis Leonard Deepak · Alvaro Mayoral ·
Miguel Jose Yacaman
Received: 5 June 2009 / Accepted: 22 June 2009 / Published online: 9 July 2009
© Springer-Verlag 2009
Abstract The structural transformation of MoO3 nanobelts
into MoS2 nanotubes using a simple sulfur source has
been reported. This transformation has been extensively
investigated using electron microscopic and spectroscopic
techniques including scanning electron microscopy (SEM),
transmission electron microscopy (TEM), high-resolution
transmission electron microscopy (HRTEM), electron dif-
fraction (ED), and energy-dispersive X-ray analysis (SEM-
EDAX and TEM-EDX). The method described in this report
will serve as a generic route for the transformation of other
oxide nanostructures into the chalcogenide nanostructures.
PACS 81.07.De · 61.46.Np · 61.48.De
1 Introduction
One-dimensional nanostructures, such as nanotubes, nano-
wires, and nanobelts, constitute an important and outstand-
ing set of nanomaterials with new emerging applications
[1, 2]. These nanomaterials can be prepared by a variety
of low temperature routes including solvothermal and hy-
drothermal methods as well as by high-temperature syn-
thesis, such as physical vapor deposition, thermal evapo-
ration, and laser ablation. Various nanomaterials of transi-
tion metal oxides, sulfides, nitrides, and carbides have been
F.L. Deepak
International Iberian Nanotechnology Laboratory, Avda Mestre
Jose Veiga, Braga 4715, Portugal
A. Mayoral · M.J. Yacaman ()
Department of Physics and Astronomy, University of Texas
at San Antonio, One UTSA Circle, San Antonio, TX 78249, USA
e-mail: miguel.yacaman@utsa.edu
Fax: +1-210-4584919
suitably prepared for various applications by these meth-
ods [3–7]. Of the various afore mentioned materials MoO3
is particularly attractive among the transition-metal oxides
due to its unusual chemistry produced by the multiple va-
lence states. There are two basic polytypes of MoO3 . The
first one, orthorhombic MoO3 (α-type), is a thermodynam-
ically stable phase, and the second one, metastable mono-
clinic MoO3 (β-type), has a ReO3 -type structure. The most
important structure characteristic of α-MoO3 is its structural
anisotropy where highly asymmetrical MoO6 octahedra are
interconnected with their edges along [001] direction and
interlinked with their corners along [100], resulting in the
so-called double-layer planar structure. An alternate stack
of these double-layered sheets along [010] will lead to the
formation of α-MoO3 , where van der Waals interactions are
the major binding means among the piled sheets. Nanostruc-
tured molybdenum oxide with high activity can be used in
a wide variety of applications, such as cathodes in recharge-
able batteries, field-emission devices, solid lubricants, su-
perconductors, thermoelectric materials, and electrochromic
devices [8–10]. In contrast to the structure of MoO3 , MoS2
is a quasi-two-dimensional (2D) compound. Atoms within a
layer are bound by strong covalent forces, while individual
layers are held together by van der Waals (vdW) interac-
tions. The stacking sequence of the layers can lead to the
formation of either a hexagonal polymorph with two layers
in the unit cell (2H), rhombohedral with three layers (3R),
or trigonal with one layer (1T).
We have been able to successfully synthesize MoO3
nanobelts by a simple thermal evaporation process and
have transformed them into MoS2 nanotubes using a sulfur
source, namely thiourea. Thus in the present report thiourea
serves as the sulfur source wherein an in-situ reduction-
sulfidization environment is generated and facilitated the
862
Fig. 1 Experimental setup used
for the synthesis of (a) MoO3
nanobelts and (b) MoS2
nanotubes
transformation of the MoO3 nanobelts into the MoS2 nan-
otubes. The entire process is extremely facile and large
quantities of the desired MoS2 nanotubes can be easily ob-
tained. The method employed in the present case will serve
to address various important applications of MoS2 nan-
otubes, like their use in field emission, hydrogen storage,
and catalysis [5–7]. Furthermore this general route will en-
able transformation of a variety of nanomaterials into well-
defined nanostructures for various useful applications.
2 Materials and methods
2.1 Synthesis of the MoO3 nanobelts by thermal
evaporation
The synthesis of the MoO3 nanobelts was carried out as fol-
lows: About 0.6 g of MoO3 (mpt = 795◦ C) was taken in an
alumina boat. This boat was placed in an alumina tube at the
heating zone of the horizontal furnace and heated to 1000◦ C
in flowing N2 (Flow Rate = 150–200 cc/min) (Fig. 1a). Pre-
viously cleaned silicon substrates were placed at regular in-
tervals in the outlet region of the alumina tube to collect the
as-deposited product obtained during the course of the reac-
tion. The reaction was carried out for 1 h after which it was
gradually cooled down to room temperature in flowing N2 .
Before every reaction the system was flushed with N2 for
0.5 h to remove any traces of oxygen. At the end of the re-
action the silvery white colored powder that was obtained
was collected and analyzed by various characterization tech-
niques.
2.2 Conversion of the MoO3 nanobelts into MoS2
nanotubes
The synthesis of the MoS2 nanotubes was carried out as fol-
lows: The substrates containing the MoO3 nanobelts were
placed at the hot zone of the furnace and 1 g of thiourea
(CSN2 H4 , mpt = 170–176◦ C) taken in an alumina boat was
F.L. Deepak et al.
placed at the upstream of the furnace and heated to 1000◦ C
in flowing N2 (Flow Rate = 100–150 cc/min) (Fig. 1b). The
reaction was carried out for 1 h after which it was gradually
cooled down to room temperature in flowing N2 . At the end
of the reaction the grey colored powder was obtained (MoS2
nanotubes) and collected from the Si substrates was used for
further analysis.
2.3 Characterization
Scanning electron microscopy (SEM) was performed in a
FEG Hitachi S-5500 ultrahigh-resolution electron micro-
scope (0.4 nm at 30 kV) with BF/DF Duo-STEM de-
tector. Transmission electron microscopy (TEM), selected-
area electron diffraction (SAED), and weak-beam dark-field
(WBDF) analysis were performed using a JEOL 1230 TEM
operating at 100 kV and a Tecnai 20 TEM equipped with
Schottky-type field-emission gun, ultrahigh-resolution pole
piece (Cs = 0.5 mm), and a scanning transmission electron
microscope (STEM) unit with high-angle annular dark-field
(HAADF) detector operating at 200 kV. For TEM analysis
the samples were dispersed in ETOH, sonicated for a minute
and placed on a holey carbon-coated copper grid.
3 Results and discussion
Shown in Figs. 2a and b are the SEM images of the MoO3
nanobelts synthesized by the thermal evaporation of MoO3
powder. The nanobelts have a diameter ranging from 200–
4000 nm and have lengths extending up to several tens
of microns. The arrow in Fig. 2a depicts the curled-up
nanobelts apart from the straighter ones seen uniformly
throughout. A closer look reveals the presence of buckling
in the nanobelts (marked with white arrows, Fig. 2b) under
the electron beam. However, the presence of long straight
nanobelts (diameter = 4 µm) are also seen uniformly as re-
vealed in the same figure (marked by black arrows, Fig. 2b).
The presence of the respective elements of Mo and O is
Structural transformation of MoO3 nanobelts into MoS2 nanotubes
Fig. 2 (a) SEM image of the MoO3 nanobelts. (b) Close-up view of
the MoO3 nanobelts. (The white arrow in the figure shows the buck-
led nanobelts whereas the black arrow shows the straight nanobelts.)
(c) EDX spectra of the MoO3 nanobelts showing the characteristic el-
ements present
verified by carrying out energy-dispersive X-ray analysis
(EDAX) on the individual nanobelts. Figure 2c thus reveals
the characteristic and distinct Mo-K and L lines as well as
863
O-K line confirming its presence in the individual nanobelts.
The elemental composition derived from the EDAX spec-
trum correspond to a 1:3 atomic ratio between Mo and O.
The presence of the respective elements is further confirmed
by carrying out elemental mapping for Mo and O. Shown in
Figs. 3b–d are the O-K, Mo-K, and Mo-L elemental maps of
the nanobelts shown in Fig. 3a. These maps clearly confirm
the presence of Mo and O in the nanobelts.
The low-magnification TEM images of the nanobelts are
shown in Figs. 4a and b. The diameter of the nanobelts
shown in Fig. 4a is ∼0.1 µm whereas those shown in Fig. 4b
have diameters extending up to 2 µm. The strain in the
nanobelts is revealed by the apparent contrast seen on the
surface of these nanobelts (Fig. 4b). Figure 5 displays a typ-
ical image of the as-synthesized nanobelts with rectangu-
lar shapes. The diameter of these nanobelts was found to be
about 150 nm whereas the length extended up to about 3 µm.
As observed in Fig. 5a, the nanobelts are uniformly straight
with constant width along their entire length. The analysis of
the nanobelts by transmission electron microscopy and high-
resolution transmission electron microscopy revealed a good
crystallinity in the whole area. By HRTEM observation the
lattice fringes corresponding to the d(001) ≈ 0.35 nm planes
and d(100) ≈ 0.38 nm planes are clearly identified (Fig. 5b).
In thinner areas, close to the edges, it was also possible to
appreciate the lattice fringes corresponding to the (002) and
(200) planes (Fig. 5c). The selected area electron diffraction
(SAED) pattern recorded on top of the nanobelt, along the
[010] orientation, was indexed assuming the orthorhombic
symmetry corresponding with the α-MoO3 crystal (Fig. 5b
inset). The SAED together with the HRTEM images suggest
that the nanobelts grow along the [001] direction (shown by
the white arrow in Fig. 5b). Both HRTEM and SAED analy-
sis on the nanobelts reveal them to be single-crystalline in
nature. EDX analysis was carried on HAADF-STEM mode
to fully confirm the composition of the nanobelts whereby it
was possible to conclude that the MoO3 phase was present
uniformly throughout the entire nanobelt with an atomic
ratio of the constituent elements of Mo and O being 1:3
(Fig. 6).
Shown in Fig. 7a are the SEM images of the MoS2
nanotubes prepared by reacting the MoO3 nanobelts with
thiourea. The corresponding bright-field (BF-STEM) and
dark-field (DF-STEM) scanning transmission electron mi-
croscope images are shown in Figs. 7b and c. The images
reveal clearly the apparent hollow nature of the nanotubes as
can be seen from the contrast in the images. The MoS2 nan-
otubes in general have a diameter of 20–100 nm and lengths
extending up to a micron. In order to verify the presence of
Mo and S in the nanotubes, we have carried out high-spatial-
resolution energy-dispersive X-ray analysis (SEM-EDAX)
elemental mapping and spectroscopy on the individual nan-
otubes. The elemental maps of the nanotube (Mo-L and S-K
864 F.L. Deepak et al.

Fig. 3 (a) SEM image of the MoO3 nanobelts with the corresponding elemental maps for oxygen (b) (O-K elemental map) and molybdenum (c),
(d) (Mo-K and Mo-L elemental maps)

Fig. 4 Low-magnification
transmission electron
microscope (TEM) images of
the molybdenum oxide
nanobelts

elemental maps) clearly revealed the presence of Mo and S composition of Mo and S in the nanotubes is ascertained to
in the nanotubes. Further EDAX spectra of the MoS2 nan- be close to 1:2.
otubes revealed the presence of the characteristic and dis- A TEM image taken at low magnification of the as-
tinct Mo (K, L) and S (K) lines. From the EDX spectra the synthesized MoS2 nanotubes obtained by the reaction of
Structural transformation of MoO3 nanobelts into MoS2 nanotubes
Fig. 5 (a) Low-magnification TEM image of an α-MoO3 nanobelt.
(b) HRTEM image of the nanobelt shown in (a). Inset in (b) shows the
SAED pattern. The white arrow in (b) denotes the growth direction of
Fig. 6 (a) STEM-HAADF image of a MoO3 nanobelt. (b) EDX analysis of the nanobelt showing the characteristic Mo and O lines (the Cu peaks
correspond to the microgrid used). The data quantified is shown in the inset
thiourea with the MoO3 nanobelts is presented in Fig. 8a.
The lengths of these nanotubes reached values of up to
1.5 µm with maximum diameters of about 100 nm. A dif-
ferent contrast can also be appreciated in different sections
of the nanotubes suggesting they might be partially filled.
Figure 8b shows a HRTEM image of a nanotube of 35 nm
diameter, wherein the (002) planes can be easily identified
running parallel to tube growth. A close-up view of the edge
of the nanotube confirmed the d-spacing to be ∼0.65 nm
(Fig. 8c) [11–15].
In STEM-HAADF the electrons which are incoherently
scattered are collected to form the image. Therefore, if it is
assumed that the probe does not affect the image, the con-
trast will be dependent on the thickness of the particle and on
the atomic number of the elements. Hence, empty nanotubes
should give a different contrast than those which are filled.
The STEM-HAADF image of the MoS2 nanotubes (Fig. 8a)
is presented in Fig. 9a. Magnified images of one of the nan-
otubes are shown in Figs. 9b and c, where it can be observed
that there is a different contrast on the nanotube. This proves
865
the nanobelt along the [001] direction. (c) HRTEM image of the edge
of the nanobelt, where the d002 and d200 are clearly observed
that nanotubes are partially filled with amorphous MoS2 .
The EDX analysis confirmed the MoS2 composition along
the entire nanotube and the absence of oxygen, which could
remain from the oxide (Fig. 9d). The profile lines recorded
(Fig. 9e) shows a similar behavior between the Mo and S
and the changes on their intensity might be related with the
changes of the sample thickness.
It would be of interest to understand the possible mech-
anism for the formation of the MoS2 nanotubes from the
MoO3 nanobelts. Initially on heating thiourea, it generates
H2 S in situ. In the present case thiourea serves as a single
source for both reduction and sulfidization thus eliminat-
ing the individual steps [16–21]. According to the current
growth model of MoS2 nanotubes, the starting material, an
oxide nanoparticle, reacts with H2 S gas which leads to the
growth of a complete sulfide shell engulfing the entire oxide
nanoparticle. Within a very short time the hydrogen diffu-
sion into and the oxygen diffusion out of the nanoparticles
leads to the reduction of the oxide core. In the second stage
of the reaction, sulfur diffuses into the core and slowly con-
866 F.L. Deepak et al.

Fig. 7 (a) SEM image, (b) bright-field scanning transmission electron microscope (BF-STEM), and (c) dark-field scanning transmission electron
microscope (DF-STEM) images of the MoS2 nanotubes

Fig. 8 (a) TEM image of a

collection of MoS2 nanotubes.
(b) HRTEM image of MoS2
nanotube growing along the
c-axis. (c) A closer image of the
(002) layers of MoS2

verts the remaining oxide into sulfide, which becomes hol-
low at the end of the process. The rate-determining step in
this process is related to the intercalation of sulfur in the top-
most sulfide layers and its slow diffusion towards the growth
front inside the nanoparticle [22, 23].
4 Conclusions
An elegant method for the structural transformation of
MoO3 nanobelts into MoS2 nanotubes using a simple sulfur
source has been elucidated. The transformation of the oxides
Structural transformation of MoO3 nanobelts into MoS2 nanotubes
Fig. 9 (a) and (b) STEM-HAADF of the MoS2 nanotubes.
(c) HRSTEM image of one of the nanotubes. The red line marked
represents the EDX profile line; whereas the red square shows the
drift correction made during the analysis. (d) EDX analysis carried
nanobelts to the sulfide nanotubes has been systematically
studied by various electron microscopy and spectroscopy
techniques. This general route would greatly enable a large
scale investigation in the case of other similar oxide–sulfide
nanostructures. The presence of such nanostructures in large
quantities would promote various applications.
Acknowledgement We would like to thank the Welch foundation
for financial support.
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