Journal of Industrial and Engineering Chemistry 34 (2016) 61–65

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Synthesis and characterization of electrospun PAN/2D MoS2 composite

nanofibers
Xu Yu, Ho Seok Park *
School of Chemical Engineering, Sungkyunkwan University (SKKU), 2066 Seobu-ro, Jangan-gu, Suwon-si, Gyeonggi-do 440-746, Republic of
Korea

A R T I C L E I N F O A B S T R A C T

Article history: Ultrafine polyacrylonitrile/MoS2 (PM) nanofibers were fabricated by electrospinning. A homogeneous
Received 11 May 2015 dispersion of two-dimensional (2D) MoS2 nanosheets in polymer solution is crucial to obtain a uniform
Received in revised form 13 October 2015 distribution of nanofillers inside polymer matrices of nanofibers. Scanning electron microscopy and
Accepted 24 October 2015
transmission electron microscopy images of PM revealed that the rough surface morphology resulted
Available online 28 October 2015
from the content of MoS2. X-ray diffraction analysis confirmed the reduced crystallinity of PM composite
nanofibers. In contrast, the thermal properties of PM nanofibers improved, as confirmed by thermal
Keywords:
analyses. These results indicate that the nanofiber morphology and crystallinity of PM nanofibers are
Nanofiber
significantly affected by the content of MoS2, while their thermal properties are improved by the uniform
Nanocomposite
Electrospinning distribution of 2D nanofillers.
2D nanosheet ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Molybdenum disulfide reserved.

Introduction solution is extruded through a syringe to form a droplet at the

One-dimensional (1D) nanomaterials and their composites
that have notable properties and enhanced performance can
expand research areas such as material science and nanotechnol-
ogy [1–3]. It is difficult to achieve a uniform distribution of
nanofiller, which is embedded in 1D nanofibers [4], because of the
easy aggregation of nanofillers. More than 80% of the globally
available carbon nanofibers are derivatives of polyacrylonitrile
(PAN) owing to the high carbon yield and the well-aligned and
highly ordered fibrous structures constructed through polymeri-
zation, stabilization, carbonization, and graphitization
[5–7]. Therefore, the physical properties of PAN-based nanofiber
composites can be improved by the controlled incorporation of
nanofillers.
Electrospinning is a versatile technique to construct well-
aligned nanofibers with average diameters in the sub-micrometer
to nanometer range. Electrospun (E-spun) nanofibers have
attracted research interest for a wide range of applications in
reinforcement, tissue engineering, and electrochemical sensing [8–
11] owing to the high porosity of the mats and the large ratio of
surface area to volume or mass of the fibers. In this method, a PAN
* Corresponding author. Tel.: +82 31 299 4715.
E-mail address: phs0727@skku.edu (H.S. Park).
orifice, and a high voltage is applied to a viscoelastic fluid between
the syringe and the collector. When the voltage reaches the critical
value, the Taylor cone is deformed by the electrostatic force, and
continuous fibers are generated without polymer beads or
droplets. As this stable jet travels through the air, the fibers
undergo bending and elongation, and, long fibers with nanoscale
diameters are obtained on the current collector.
Molybdenum disulfide (MoS2), an atomically transition-metal
dichalcogenide with a unique layered structure caused by weak
van der Walls forces, has received attention for decades for its
potential applications in transistors [12], supercapacitors [13,14],
and lithium ion batteries [15–17]. Solution-exfoliated 2D single- or
few-layered MoS2 exhibits a typical hexagonal structure with
connections to neighboring layers by Mo–S bonds with a high
surface area. E-spun polymer nanofibers and metallic oxide
nanofibers such as TiO2, Al2O3, and MgO nanofibers [18–20] have
been widely studied to demonstrate that the fiber morphology
depends strongly on the distribution of nanofillers as well as
various process parameters. Although 1D polymer/MoS2 nanofi-
bers should exhibit excellent mechanical properties, the nanoscale
incorporation of 2D MoS2 into a 1D system has not yet been
explored. We successfully obtained e-spun PAN/MoS2 (PM)
nanofibers using a PAN solution with a uniform dispersion of
MoS2. The aim of the present paper is to characterize the structure
and thermal properties of the synthesized PM nanofibers.

http://dx.doi.org/10.1016/j.jiec.2015.10.030
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
62 X. Yu, H.S. Park / Journal of Industrial and Engineering Chemistry 34 (2016) 61–65
Experimental
Chemicals
Chemical reagents of polyacrylonitrile (PAN), molybdenum
disulfide (MoS2), n-butyl lithium, hexane and dimethylformamide
(DMF) were obtained from Sigma–Aldrich Chemical Co., Germany.
All chemicals were used without further purification.
Preparation of 2D MoS2 powder
In a chemical exfoliation process to synthesize MoS2, 200 mg of
bulk MoS2 was placed in a three-neck flask and dispersed in hexane.
The temperature was increased to 90 8C in an oil bath, and then 5 mL
of n-butyl lithium were added. The mixture was kept for three days
under N2 atmosphere. After three days, the solution was filtrated and
repeatedly washed using hexane to remove impurities. The as-
obtained solid was diluted with deionized (DI) water with bath
sonication for 6 h. The dispersion was centrifuged three times at
4500 rpm to remove excess lithium in the LiOH and unexfoliated
MoS2. A 2D MoS2 powder was obtained by freeze-drying.
Preparation of PM nanofibers
Two grams of polyacrylonitrile (PAN, MW = 150,000) powder
with the stoichiometric ratio of MoS2 powder were dispersed in 8 g
of dimethylformamide (DMF), stirred overnight at room tempera-
ture and subsequently sonicated for 2 h to obtain a homogeneous
PAN/MoS2 solution. The pure PAN polymer solution was prepared
by the same method. The PAN/MoS2 (PM) solutions were called
PM-2, PM-4, PM-6, and PM-8 with respect to the concentration of
MoS2 (2%, 4%, 6%, and 8%).
The as-prepared PM solution was placed in a 20-mL plastic
syringe, and a syringe pump was used to control the flow rate of
injection. To obtain ultrafine nanofibers, the flow rate of the
polymer solution was controlled in the range of 0.1 to 0.5 mL h 1
by the syringe pump, and the distance between the nozzle and the
collector was fixed at 12 cm during the electrospinning process.
The applied voltage was 15 kV; a stainless steel needle was used to
connect the positive of the power source, and the collector was
connected to the negative of the power source. The obtained PM
nanofibers were stabilized at 200 8C (5 8C min 1) for 2 h in air, and
then the sample was transferred to a tube furnace for carboniza-
tion at 800 8C (5 8C min 1, N2) for 8 h.
Fig. 1. (a) Schematic illustration of the preparation of PAN/MoS2 electrospun polymer nanofibers. (b) Illustration of the instability of the electrostatic force.
Characterization of PM nanofibers
Scanning electron microscopy (SEM) images were obtained
using a field emission scanning electron microscope (Philips SEM
535M) equipped with a Schottky-based field emission gun.
Transmission electron microscopy (TEM) images were collected
on a JEM-3010 HR TEM (300 kV). X-ray diffraction (XRD) patterns
were collected using a general area detector diffraction system
(GADDS) (l = 1.5406 Å) at 2u between 108 and 708. Thermogravi-
metric analysis (TGA) was carried out using a Dupont 2200 thermal
analysis station. Differential scanning calorimetry (DSC, DuPont TA
2000), calibrated with indium, was used to monitor the changes in
the thermal properties. For TEM investigation, carbonized nano-
fibers were dispersed in DI water using bath sonication for 8 h. The
well-dispersed solution was dropped on a carbon-coated grid and
then kept in air to naturally evaporate the solvent.
Results and discussion
It is well known that the homogeneity of a polymer solution is
crucial in electrospinning to obtain a uniform diameter distribu-
tion of 1D fibers. Fig. 1a illustrates the detailed process for
controlling the location of MoS2 embedded in 1D nanofibers. Two-
dimensional MoS2 and PAN as the raw materials were dissolved in
DMF under magnetic stirring to form a homogeneous colloidal
electrospinnable solution. The nozzle of the syringe was connected
to the positive terminal of the voltage power, and the collector was
connected to the negative terminal. After the electrospinning step,
1D PM nanofibers were obtained without the formation of beads or
aggregation. The location of MoS2 was affected by the compatibili-
ty of the two components and the solvent evaporation during the
electrospinning process.
During the electrostatic spinning process, the Coulombic
repulsion of fibers with electrostatic charges bends the fibers.
By neglecting the elongation and refinement of the fiber bundles,
the charges can be seen as the cause of stability by considering the
limitations imposed by Coulomb’s law without an external electric
field. The mechanism for the formation of spiral fibers is shown in
Fig. 1b. First, we assume that the fibers have three points of charge;
the effect of the Coulomb force on the two endpoint charges leads
to the repulsion of the two endpoints at the same time, such that
the charge at b moves. With the movement of charge b, the
repulsive force is reduced, and both endpoint charges are closer to
each other. When the distance between the three charges is equal
 X. Yu, H.S. Park / Journal of Industrial and Engineering Chemistry 34 (2016) 61–65 63

Fig. 2. (a) and (b) Low and high magnification SEM images of pristine PAN nanofibers. (c) and (d) Low and high magnification SEM images of PM-4. (e) and (f) Low and high
magnification SEM images of PM-8.

to each other, the charge system tends to be stable, and charge b
stops moving. Finally, there is no dithering amplitude change of the
fibers at this time.
The morphology of pristine PAN and PM nanofibers was
characterized by SEM. Pristine PAN nanofibers with low mechani-
cal strength were welded together and dried in a vacuum oven at
80 8C for 4 h, as shown in Fig. 2a and b. The results show that the
pristine PAN nanofibers had relatively smooth surfaces and a
uniform diameter distribution with a range from 200 to 240 nm.
The enhanced robustness of the PM composite nanofibers was
affected by the MoS2 content. Compared to the pristine PAN
nanofibers, the average diameters of the PM-4 (250–280 nm) and
PM-8 (270–300 nm) nanofibers increased slightly with the loading
of MoS2. The irregularities began to form on the nanofiber surface
when the concentration of MoS2 was higher than 8%, which is
attributed to the plentiful distribution of MoS2. PM-8 exhibited a
roughness surface without the formation of beads, as shown in
Fig. 2e and f. Because of its rough surface, PM-8 had a higher
surface area to volume ratio. These results suggest that the
formation of a rough morphology of PM nanofibers depends on the
MoS2 content loaded in a compatible polymer matrix. Therefore, a
homogeneous solution is a crucial factor to form well-aligned
bead-free PM nanofibers, even at a high MoS2 loading.
It was difficult to confirm the deposition of MoS2 in the
nanofibers in the SEM images, and thus TEM was performed to
investigate the structure and MoS2 distribution. Fig. 3a and b
shows TEM images of pristine PAN nanofibers, which exhibited a
smooth and transparent surface with no aggregation. As MoS2
nanosheets were embedded on and beneath the surface of PAN
nanofibers, the surface of the nanofibers became rough, as shown
in Fig. 3c, which increased the surface area of the fiber mat. The 2D
MoS2 nanosheets were deposited discontinuously, although they
began to aggregate and form small particles on the surface when
the concentration of MoS2 was higher than 8% (Fig. 3e and f)
because of the restacked layer structure of MoS2. These results
demonstrate that the PAN stabilized the 2D MoS2 nanosheets in

Fig. 3. (a) and (b) Low and high magnification TEM images of pristine PAN nanofiber. (c) and (d) Low and high magnification TEM images of PM-4. (e) and (f) Low and high
magnification TEM images of PM-8.
64 X. Yu, H.S. Park / Journal of Industrial and Engineering Chemistry 34 (2016) 61–65

(a) (b)
2D MoS2 (002) (100)
Bulk-MoS2 Pristine PAN
(002) PM-2

Intensity (a.u.)
PM-4

Intensity (a.u.)
Intensity (a.u.)
(110) PM-6
PM-8

(103)
(100) (006)

10 20 30 40 50
2θ

10 15 20 25 30 35 40 45 50 10 20 30 40 50 60 70

2θ 2θ

Fig. 4. (a) XRD pattern of 2D MoS2. (Inset: XRD pattern of bulk MoS2). (b) XRD patterns of pristine PAN, PM-2, PM-4, PM-6 and PM-8.

the homogeneous electrospinnable solution and resulted in a the pristine PAN nanofiber exhibited two apparent equatorial
relatively uniform distribution of MoS2 nanosheets along the as- peaks at 2u = 17.078 and 2u = 27.68, which were indexed to the
spun fibers, especially when the MoS2 concentration was not too (1 0 0) and (1 1 0) reflection peaks, respectively [22]. The intensity
high. The MoS2 nanosheets presented severely non-uniform of the (1 0 0) diffraction peak dramatically decreased, and the
distributions with increasing MoS2 concentration and began to (1 1 0) peak disappeared with increasing MoS2 concentration,
aggregate at high concentrations, which clearly demonstrated the which is attributed to the deposition of mono- or few-layered MoS2
existence of a large amount of MoS2. homogeneous electrospin- between the PAN chains. The apparent reduction in fiber
nable solution and result a relatively uniform distribution of MoS2 crystallinity was due to the enhanced content of MoS2, which
nanosheets along the as-spun fibers, especially when the MoS2 inhibited the chain ordering process.
concentration is not too high. The MoS2 nanosheets display Oxidative stabilization is a crucial step to convert polymer
severely non-uniform distributions with increasing MoS2 concen- nanofibers to carbon nanofibers to obtain dimensional stability by
tration, and begin to form aggregation at high concentration, which physical and chemical reactions during high-temperature thermal
strongly demonstrate the existence of a large amount of MoS2. treatment. The detailed explanation of the thermal behavior of the
The structure of the electro-spun PM composites was charac- as-spun PM nanofibers was confirmed by thermogravimetric
terized by X-ray diffraction (XRD), as shown in Fig. 4. The analysis (TGA) using a heating rate of 10 8C min 1 with a
synthesized 2D MoS2 showed a weak and broad (002) diffraction temperature range from room temperature to 800 8C in nitrogen
peak at 2u = 14.78 compared to bulk MoS2 [21], which suggests that atmosphere, as shown in Fig. 5a. The first slight weight loss (1–
the 2D MoS2 was a single or monolayer structure with a 4.5%) occurred near 50–120 8C because of the evaporation of the
degradation in crystallinity. In the powder XRD diffraction pattern, residual solvent from the nanofiber mat (Fig. 5a, inset). A dramatic

(a) (b)
100 100 100
Weight (%)

90 98

80 90
96
Weight (%)
Weight (%)

70
94
60 80 100 120 140 160
Temperature (°C) 80
50 Pristine PAN Pristine PAN
PM-2 PM-2
40 PM-4 PM-4
PM-6 70
30 PM-6
PM-8 PM-8
20
100 200 300 400 500 600 700 800 270 280 290 300 310 320
Temperature (°C) Temperature (°C)
(c) (d)
Pristine PAN Pristine PAN
PM-2
Heat Flow (mW/mg)
Heat Flow (mW/mg)

PM-4
PM-2 PM-6
PM-8
PM-4

PM-6

PM-8

100 200 300 400 500 600 700 800 260 280 300 320 340
Temperature (°C) Temperature (°C)

Fig. 5. (a) TGA curves of pristine PAN, PM-2, PM-4, PM-6 and PM-8. (Inset: high magnification TGA curves from 50 to 120 8C). (b) High magnification TGA curves of pristine
PAN, PM-2, PM-4, PM-6 and PM-8 from 50 to 120 8C. (c) and (d) Low and high magnification DSC curves of pristine PAN, PM-2, PM-4, PM-6 and PM-8.
 X. Yu, H.S. Park / Journal of Industrial and Engineering Chemistry 34 (2016) 61–65
weight loss occurred around 285 8C owing to the thermal
decomposition of PAN. However, the PM composite nanofibers
showed weight loss at slightly higher temperatures compared
with pristine PAN nanofibers, and the percentage of mass loss of
PM nanofibers decreased with the MoS2 concentration. The mass
loss slowed from 310 to 800 8C, and the PM nanofibers (0, 2%, 4%,
6%, and 8%) yielded residuals of 30.2%, 37.5%, 41.9%, 44.1%, and
46.2%, respectively. The result is attributed to (1) the transforma-
tion of the nanofibers to the graphitic structure of carbon
nanofibers and (2) the existence of 2D MoS2. These studies
demonstrated that the thermal stability of PAN/MoS2 hybrid
nanofiber increased because of the presence of the 2D MoS2
nanostructural material.
In order to further investigate the thermal stability, DSC
thermograms were obtained in a nitrogen atmosphere, as shown in
Fig. 5c. Exothermic chemical reactions occur during the thermal
treatment of PAN nanofibers, such as cyclization of nitrile groups
and dehydrogenation. The electro-spun pristine PAN nanofibers
displayed relatively sharp and large exothermic peaks at 286.5 8C,
which is in excellent correspondence with the typical DSC
prototype of a PAN homopolymer [7,23]. The exothermic peak is
attributed to the cyclization of the nitrile group of PAN in the
oxidative stabilization process. According to the high-resolution
curves in Fig. 5d, the exothermic peaks of nanofibers (PM-2, PM-4,
PM-6, and PM-8) shifted to higher temperatures of 289.9 8C,
292.3 8C, 296.1 8C, and 300.3 8C, respectively, which is in accor-
dance with the TGA analysis. The exothermic peaks shifted to
higher temperatures with the concentration of 2D MoS2, and the
linear shift was due to the embedding of 2D MoS2 in the fibers,
which acted as an inhibitor to slow the cyclization reaction of the
nitrile groups.
Conclusions
Electrospinning is a versatile technique and was used to
fabricate well-aligned PM nanofibers. The composite nanofibers
combined the advantages of polymer nanofibers and 2D MoS2. SEM
and TEM of the PM nanofibers showed a rough morphology with
diameters of 250–300 nm and the existence of MoS2 in uniform
and continuous nanofibers. XRD analysis revealed the degradation
65
of crystallinity with increasing concentration of MoS2, and the TGA
and DSC results demonstrated the improvement in the thermal
properties of PM nanofibers by embedding the 2D MoS2 on and
beneath the surface of the nanofibers. This assembly method may
thus provide a useful route to fabricate nanofiber mats for binder-
free electrodes of batteries.
Acknowledgements
We acknowledge financial support by the National Research
Foundation of Korea Grant funded by the Ministry of Science, ICT &
Future Planning of the Korean Government (20090063004 and
NRF-2010-C1AAA001-0029018).
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