Delivered by Publishing Technology to: Hanyang University Library

IP: 166.104.189.118 On: Mon, 08 Jul 2013 12:56:39

Copyright American Scientific Publishers
R
E
S
E
A
R
C
H
A
R
T
I
C
L
E
Copyright 2013 American Scientic Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoscience and Nanotechnology
Vol. 13, 62496253, 2013
A Novel Methanol Sensor Based on Gas-Penetration
Through a Porous Polypyrrole-Coated
Polyacrylonitrile Nanober Mat
Tae-Sun Jun
1
, Thi Anh Ho
1
, Muhammad Rashid
2
, and Yong Shin Kim
1 2
1
Graduate School of Bio-Nano Engineering, Hanyang University, Ansan 426-791, South Korea
2
Department of Applied Chemistry, Hanyang University, Ansan 426-791, South Korea
In this work, we propose a novel chemoresistive gas sensor operated under a vertical analyte ow
passing through a permeable sensing membrane. Such a conguration is different from the use
of a planar sensor implemented under a conventional horizontal ow. A highly porous coreshell
polyacrylonitrilepolypyrrole (PAN@PPy) nanober mat was prepared as the sensing element via
electrospinning and two-step vapor-phase polymerization (VPP). Various analysis methods such as
SEM, TEM, FT-IR and XPS measurements were employed in order to characterize structural fea-
tures of the porous sensing mat. These analyses conrmed that very thin (ca. 10 nm) conductive
PPy sheath layers were deposited by VPP on electrospun PAN nanobers with an average diam-
eter of 258 nm. Preliminary results revealed that the gas penetration-type PAN@PPy sensor had
a higher sensor response and shorter detection and recovery times upon exposure to methanol
analyte when compared with a conventional horizontal ow sensor due to efcient and fast analyte
transfer into the sensing layer.
Keywords: Gas Sensor, Polypyrrole, Vapor-Phase Polymerization, CoreShell Nanober.
1. INTRODUCTION
Recently one-dimensional (1D) conducting polymer mate-
rials such as nanobers, nanotubes, and nanowires have
attracted a great deal of attention due to their facile
preparation procedures, design exibility, and good pro-
cessability when compared to inorganic nanomaterials.
1, 2
To improve and extend the functions of these organic
nanomaterials, one or more components are often com-
bined to form 1D conducting polymer composites for
various applications in the elds of electronics, sensors,
catalysis, and electromagnetic interference shielding. The
1D conducting polymer composites can be prepared by
various techniques, including electrochemical polymeriza-
tion, template-assisted polymerization, surfactant-directed
polymerization, and electrospinning.
3
Among these pro-
cessing routes, the electrospinning technique has proved to
be a simple and versatile method for producing very long
polymeric nanobers in the form of a nonwoven mat.
4, 5
Polypyrrole (PPy) is one of the most studied conducting
polymers because of its simple synthesis, low toxicity, and
good environmental stability. Electrospun PPy nanober

Author to whom correspondence should be addressed.

mats with a high surface-to-volume ratio and porosity have
been extensively explored to achieve a highly sensitive
and fast response gas sensor at ambient temperature.
68
Since PPy is too stiff to be electrospun by itself, PPy
nanobers are usually prepared via the electrospinning of
a blending solution of PPy and another electrospinnable
polymer,
9, 10
or through the vapor-phase polymerization
(VPP) of pyrrole monomers on the surface of electrospun
oxidant-containing nanober templates.
11, 12
However, it is
often difcult to achieve selective PPy deposition on the
nanober surface using these methods. Another approach
is to deposit sheath PPy layers onto electrospun nano-
bers via a two-step VPP process, i.e., the successive
supply of oxidant and pyrrole molecules to the nanober
template.
13, 14
Compared with the one-step process, two-
step polymerization can allow for better exibility and
control when growing a thin conductive sheath layer.
Previously, we reported on the successful synthesis of
polyacrylonitrilepolypyrrole (PAN@PPy) nanobers with
a coreshell structure through the two-step VPP growth of
PPy on electrospun PAN nanobers.
15
Chemoresistive gas sensors based on conducting poly-
mers have conventionally been fabricated by forming
a sensing layer on the sensor substrate with a pair
J. Nanosci. Nanotechnol. 2013, Vol. 13, No. 9 1533-4880/2013/13/6249/005 doi:10.1166/jnn.2013.7693 6249
Delivered by Publishing Technology to: Hanyang University Library
IP: 166.104.189.118 On: Mon, 08 Jul 2013 12:56:39
Copyright American Scientific Publishers
R
E
S
E
A
R
C
H
A
R
T
I
C
L
E
A Novel Methanol Sensor Based on Gas-Penetration Through a Porous PPy-Coated PAN Nanober Mat Jun et al.
(A)
(B)
Fig. 1. Schematic illustrations of (A) a conventional horizontal ow
sensor fabricated on a planar sensor substrate and (B) the new
penetration-type sensor based on a porous PAN@PPy mat.
of interdigitated electrodes, as shown in Figure 1(A).
The gas-sensing characteristics are typically evaluated by
changing the concentration of gaseous target molecules
over the sensing layer with the aid of ow-control
equipment. However, since the sensor resistance directly
depends on the analyte concentration inside the sensing
layer rather than the gas-phase concentration, sensing char-
acteristics such as the sensor response and detection times
are strongly inuenced by analyte diffusion into the con-
ducting polymer and interactions between the sensing layer
and the analytes. Even for a porous conducting polymer
nanober mat, a considerable amount of time is needed
to reach a steady-state concentration prole within the
sensing layer, and the saturated concentrations are smaller
than the gas-phase concentration due to the slow nature of
Knudsen diffusion.
16
In this work, we prepared a free-standing PAN@PPy
nanober mat by two-step PPy deposition on electrospun
PAN as a sensing element in chemoresistive gas sensors.
The sensing characteristics of the PAN@PPy mat were
tested in a conguration where the analyte directly pene-
trates the porous mat in order to achieve fast analyte trans-
fer into the sensing layer. To the best of our knowledge, it
is the rst time that a penetration-type chemoresistive gas
sensor has been proposed. When compared with a con-
ventional planar sensor that operated under a horizontal
analyte ow, the penetration sensor was found to exhibit
higher sensitivity and shorter detection times.
2. EXPERIMENTAL DETAILS
The synthesis of PAN@PPy nanober mat was described
in detail in our previous work.
15
A homogenous electro-
spinning solution was rst prepared by dissolving 1.90 g
of PAN (M
n
= 150, 000 g mol
1
) in 20 mL dimethylfor-
mamide. A disposable plastic syringe with a metal nee-
dle was charged with the electrospinning solution. A high
voltage of 20 kV was then applied to the needle where
a solution was delivered at a ow rate of 0.6 mL/h by
a syringe pump. A cylindrical ring collector was posi-
tioned 15 cm apart from the needle tip, and rotated at a
speed of 250 rpm. The nanober mat was collected on
aluminum foil located on the collector. After the electro-
spinning process, a free-standing PAN nanober mat was
obtained by peeling off the Al foil. The PAN mat was sub-
sequently cut out in a rectangular shape with dimensions
of 3 3 cm
2
, and held by a Teon holder with a circu-
lar hole (diameter = 2 cm). The sample was dipped into
a butanol solution of 10 wt% ferric tosylate (FeTos) oxi-
dant for 15 min. The FeTos-treated mat was then soaked
in an ethanol solution for the removal of weakly-bounded
surplus oxidants, and then dried in an oven at 60

C
for 1 h. The FeTos-coated mat was placed in a reaction
chamber connected to a reservoir containing liquid pyrrole
monomer. PPy growth was carried out with a reaction time
of 15 min at ambient temperature through the delivery of
pyrrole vapor into the chamber.
The morphology of the nanobers was evaluated by
scanning electron microscopy (SEM; S-4800, Hitachi)
and transmission electron microscopy (TEM; JEM-2100F,
JEOL). X-ray photoelectron spectroscopy (XPS; ESCA
2000, VG) was used to probe the atomic constituents and
chemical bonding states. The identication of chemical
functional groups was carried out via Fourier transform
infrared spectroscopy (FT-IR; Scimitar 1000, Varian). The
sheet resistance was measured by the four-point probe
(RS 8, Dasol Eng.) method, while the thickness and
weight of the nanober mats were measured with a digital
micrometer (ID-C112XBS, Mitutoyo) and a microbalance
(BM22, AND), respectively. The mat porosity P was cal-
culated with the following equation:
P(%) =
(J
0
J)
J
0
100 (1)
where J
0
is the density of a compact reference layer and
J is the apparent density of the porous nanober mat.
The J
0
values of 1.184 g cm
3
and 1.35 g cm
3
were
used as the compact densities of PAN and Tos-doped PPy,
respectively.
17
The PAN@PPy nanober mat was cut out into a circu-
lar shape with a 9 mm diameter for the penetration-type
sensor measurement. The mat was sandwiched between
two Teon grids, and two wire electrodes were inserted
between the mat and the grid (see Fig. 1(B)). This sen-
sor assembly was pressed and mounted on the inside of
a sealed detection chamber. For a comparison, an ordi-
nary PAN@PPy sensor was also prepared by attaching the
mat on a planar interdigitated Au/glass substrate with an
electrode gap of 300 jm. Gas-sensing measurements were
6250 J. Nanosci. Nanotechnol. 13, 62496253, 2013
Delivered by Publishing Technology to: Hanyang University Library
IP: 166.104.189.118 On: Mon, 08 Jul 2013 12:56:39
Copyright American Scientific Publishers
R
E
S
E
A
R
C
H
A
R
T
I
C
L
E
Jun et al. A Novel Methanol Sensor Based on Gas-Penetration Through a Porous PPy-Coated PAN Nanober Mat
carried out by blowing methanol vapors into the chamber
at a total ow rate of 200 or 1000 mL/min. Methanol con-
centrations in the range of 0.76.5% were introduced by
adjusting the relative ratio of the analyte ow rate to the
dilution N
2
ow rate. The chemoresistive responses of a
sensor were recorded by a source meter (2400, Keithley) at
room temperature. The sensor response R was calculated
using the following equation:
R(%) =
(R
max
R
0
)
R
0
100 (2)
where R
0
is the initial resistance of the sensor and R
max
is the saturated maximum resistance upon exposure to the
methanol analyte.
3. RESULTS AND DISCUSSION
3.1. Material Properties of the PAN@PPy Mats
A surface SEM image of an electrospun PAN mat
with a thickness of approximately 100 jm is shown in
Figure 2(A). The mat clearly presents a highly porous
structure consisting of randomly oriented 1D nanobers
with a smooth surface. The average diameter of the nano-
bers was found to be 258 nm. An SEM image taken after
the PPy deposition is displayed in Figure 2(B); a porous
nonwoven structure identical to that of the PAN mat was
observed. However, there were some distinct differences
in the nanober diameter, surface roughness and morphol-
ogy around the nanober junction regions. Through careful
SEM inspection, the PAN@PPy nanober diameter was
found to be increased by 10 nm, and the surface mor-
phology became rougher when compared with the PAN
sample. In addition, the nanobers were cross-linked at
the junction probably due to intensive PPy growth result-
ing from the preferential presence of FeTos oxidants at
the junction regions. These observations may support the
formation of a PPy sheath on the PAN nanober surface.
A more detailed examination of the microstructure of the
PAN@PPy nanobers was conducted by TEM analysis.
Figure 2(C) shows a low-resolution TEM image demon-
strating a coreshell structure of the PAN@PPy nanobers.
Even though the shell thickness is not uniform, the average
thickness value was about 10 nm.
The porosities and sheet resistances obtained from the
PAN and PAN@PPy mats are summarized in Table I,
together with the nanober diameters determined by SEM.
A slight reduction in porosity from 88% to 84% after the
VPP deposition suggested that PPy polymerization pre-
dominantly occurred on the surface of the PAN nanobers
without lling internal voids in the mat. The change in
sheet resistance indicated the synthesis of conductive PPy
layers on insulating PAN nanobers. In the penetration-
type sensor measurements, gaseous molecules could pass
through the PAN@PPy mat without a signicant ow
resistance due to its highly porous structure.
(B)
(A)
(C)
Fig. 2. SEM images of (A) as-electrospun PAN nanobers and
(B) coreshell PAN@PPy nanobers. A TEM image of a single
PAN@PPy nanober is shown in (C).
The formation of PPy on the PAN nanobers was also
conrmed by FT-IR analysis. Figure 3 shows two FT-
IR spectra obtained for PAN and PAN@PPy nanober
samples. The upper PAN@PPy spectrum clearly reveals
additional PPy characteristic peaks in the region of 500
1,200 cm
1
. These peaks may be attributed to CN
stretching or CH in plane deformation at 1190 cm
1
,
Table I. The nanober diameter, porosity, and sheet resistance of the
PAN and PAN@PPy nanober mats.
Nanober Estimated Sheet
Sample ID diameter (nm) porosity (%) resistance (kD/sq)
PAN 25830 88.0
PAN@PPy 26820 84.0 72.7
J. Nanosci. Nanotechnol. 13, 62496253, 2013 6251
Delivered by Publishing Technology to: Hanyang University Library
IP: 166.104.189.118 On: Mon, 08 Jul 2013 12:56:39
Copyright American Scientific Publishers
R
E
S
E
A
R
C
H
A
R
T
I
C
L
E
A Novel Methanol Sensor Based on Gas-Penetration Through a Porous PPy-Coated PAN Nanober Mat Jun et al.
Fig. 3. FT-IR spectra of electrospun PAN and coreshell PAN@PPy
nanobers.
CH band in plane vibration or NH in-plane defor-
mation at 1034 cm
1
, CH out-of-plane ring deformation
at 813 cm
1
and CC out-of-plane ring deformation or
CH rocking at 680 cm
1
.
18, 19, 20
Such results could pro-
vide direct evidence for PPy synthesis via a two-step VPP
process.
Wide-scan XPS spectra obtained for PAN and
PAN@PPy mats are shown in Figure 4. In the case of the
PAN sample, the main constituent elements were found to
be carbon and nitrogen atoms. In addition, a small amount
of oxygen impurities were also observed probably due to
the incorporation of oxygen moieties from the solvent and
water molecules in the atmosphere. On the other hand,
there were two additional peaks in the PAN@PPy spec-
trum at binding energies of 165 eV and 230 eV that were
assigned to S 2s and S 2, respectively. The O 1s peak
intensity was enhanced by more than three times, and there
was no recognizable peak due to Fe atoms. These results
suggest that tosylate anions were incorporated into the oxi-
dized PPy mat by means of electrostatic interactions rather
than existing as FeTos.
Fig. 4. Wide-scan XPS spectra of electrospun PAN and coreshell
PAN@PPy nanobers.
3.2. Methanol-Sensing Properties of a
Penetration-Type PAN@PPy Sensor
The methanol-sensing performance of the porous
PAN@PPy mat was evaluated in the penetration cong-
uration. Figure 5 shows a typical time-proled response
curve of the penetration-type sensor at room temperature
when the methanol analyte was injected for 180 s fol-
lowed by a 300 s recovery period. The methanol concen-
tration was increased successively from 0.7 to 6.5%, as
designated by the numerical values in Figure 5. The sen-
sor exhibited both an increase in resistance upon exposure
to methanol and reversible detection behavior. For exam-
ple, the sensor resistance increased from 5.28 to 5.67 kD
under 3.4% CH
3
OH exposure, which corresponded to the
sensor response of 7.5% in Eq. (2). The inset displays a
plot of sensor response with respect to the CH
3
OH con-
centration. The response variation was well interpreted by
the linear expression: R(%) =1.278 Conc.(CH
3
OH,%) +
2.918. The correlation coefcient in the linear regression
analysis was 0.9965, illustrating a good linear relation-
ship between the concentration and the response magni-
tude over the concentration range of 0.76.5%. In addition,
the response and recovery times, as dened by the time to
reach a 90% position of a saturated limiting value (T
90
),
were found to be 20 and 42 s, respectively. The resis-
tance increase response could be explained by the electron-
donating character of the CH
3
OH analyte and the -type
semiconducting nature of PPy. The interactions between
Tos-doped PPy and CH
3
OH might be described by the
redox (de-doping) reaction: PPy
+
/Tos

+CH
3
OH (o

)
[PPy-CH
3
OH(o

)]
+
/Tos

.
8, 21, 22
The transfer of electrons
from electron-donating CH
3
OH to positively-charged PPy
backbone led to the formation of neutral polymer chains,
thus resulting in a decrease in the hole carrier density, i.e.,
a resistance increase.
Fig. 5. Response curve of the core-shell PAN@PPy mat in the gas-
penetration conguration upon successive exposure to the methanol
analyte. The methanol concentrations are designated by the numerical
number in % units. The inset shows a plot of the sensor response versus
methanol concentration.
6252 J. Nanosci. Nanotechnol. 13, 62496253, 2013
Delivered by Publishing Technology to: Hanyang University Library
IP: 166.104.189.118 On: Mon, 08 Jul 2013 12:56:39
Copyright American Scientific Publishers
R
E
S
E
A
R
C
H
A
R
T
I
C
L
E
Jun et al. A Novel Methanol Sensor Based on Gas-Penetration Through a Porous PPy-Coated PAN Nanober Mat
Fig. 6. Cyclic response curve of the coreshell PAN@PPy sensor in the
horizontal ow conguration for 3.7% methanol exposure.
In order to compare the detection characteristics of the
penetration-type sensor with those of the ordinary pla-
nar sensor, similar methanol-sensing measurements were
also carried out for a PAN@PPy/Au/glass device under a
horizontal gas ow. Figure 6 shows a response curve of
the horizontal ow sensor upon three sequential exposures
to 3.7% methanol. The average magnitude of the sensor
response was found to be 2.8%, which was much lower
than the value of 7.5% obtained with the penetration sen-
sor at a methanol concentration of 3.4%. In addition, when
compared with the response curve of the penetration sen-
sor, the sensor resistance did not reach a stable plateau
during the methanol supply time of 180 s. Incomplete
restoration to the initial level was also observed during
the subsequent 300 s recovery period. These preliminary
results demonstrated that the sensing performance of the
porous PAN@PPy mat could be superior in the analyte-
penetration conguration when compared to the usual pla-
nar sensor with a horizontal ow. In a separate study,
however, the sensing characteristics of the penetration sen-
sors were found to be strongly dependent on material prop-
erties of the PAN@PPy nanober mat and the electrical
contact conditions between the mat and the wire. There-
fore, it is required to optimize a PAN@PPy nanober mat
structure and to achieve stable electrical contacts for the
fabrication of reliable and sensitive sensors.
4. CONCLUSIONS
Free-standing nonwoven PAN@PPy nanober mats were
prepared by electrospinning and two-step VPP processes.
The mat was tested for the rst time as a sensing element
in the gas-penetration conguration since it was chemore-
sistive and gas-permeable due to its high porosity (larger
than 80%). It was found that the gas sensor can operate
under the vertical ow conditions if the sensing layer has
a porosity that is sufciently high so as to allow pene-
tration of the analyte through the structure. Furthermore,
fast and efcient analyte transfer results in excellent gas-
sensing performances for the gas-penetration sensor. This
novel sensor may serve to expand the applicability of gas
sensors due to its simple structure and exibility.
Acknowledgments: This research was supported by
Basic Science Research Programs through the National
Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science and Technology (NRF-
2012R1A1A2005473 and NRF-2012-0009838).
References and Notes
1. Y.-Z. Long, M.-M. Li, C. Gu, M. Wan, J.-L. Duvail, Z. Liu, and
Z. Fan, Prog. Polym. Sci. 36, 1415 (2011).
2. A. Malinauskas, J. Malinauskiene, and A. Ramanavicius, Nanotech-
nology 16, R51 (2005).
3. X. Lu, W. Zhang, C. Wang, T.-C. Wen, and Y. Wei, Prog. Polym.
Sci. 36, 671 (2011).
4. Z.-M. Huang, Y.-Z. Zhang, M. Kotaki, and S. Ramakrishna, Comp.
Sci. Technol. 63, 5253 (2003).
5. A. Greiner and J. H. Wendorff, Adv. Polym. Sci. 219, 107 (2008).
6. H. Bai, L. Zhao, C. Lu, C. Li, and G. Shi, Polymer 50, 3292 (2009).
7. J. Jang and J. Bae, Sens. Actuator B 122, 7 (2007).
8. Y. Wang, W. Jia, T. Strout, A. Schempf, H. Zhang, B. Li, J. Cui, and
Y. Lei, Electroanalysis 21, 1432 (2009).
9. I. S. Chronakis, S. Grapenson, and A. Jakob, Polymer 47, 1597
(2006).
10. Y.-W. Ju, J.-H. Park, H.-R. Jung, and W.-J. Lee, Electrochim. Acta
52, 4841 (2007).
11. S. Nair, S. Natarajan, and S. H. Kim, Macromol. Rapid Commun.
26, 1599 (2005).
12. S. Nair, E. Hsiao, and S. H. Kim, J. Mater. Chem. 18, 5155 (2008).
13. A. Laforgue, and L. Robitaille, Chem. Mater. 22, 2474 (2010).
14. L. Ji, Z. Lin, Y. Li, S. Li, Y. Liang, O. Toprakci, Q. Shi, and
X. Zhang, Polymer 51, 4368 (2010).
15. T.-S. Jun, T.-A. Nguyen, Y. Jung, and Y. S. Kim, J. Nanosci. Nano-
technol. 12, 5967 (2012).
16. N. Matsunaga, G. Sakai, K. Shinamoe, and N. Yamazoe, Sens. Actu-
ators B 83, 216 (2002).
17. B. A. Lunn, J. Unsworth, N. G. Booth, and P. C. Innis, J. Mater. Sci.
28, 5092 (1993).
18. T. K. Viahnuvardhan, V. R. Kulkarni, C. Basavaraja, and S. C.
Raghavendra, Bull. Mater. Sci. 29, 77 (2006).
19. H. Eisazadeh, World J. Chem. 2, 67 (2007).
20. Q. Gao, Y. Wang, D. He, C. Ju, L. Gao, and M. Fu, J. Nanosci.
Nanotechnol. 11, 9836 (2011).
21. D.-U. Kim and B. Yoo, Sens. Actuators B, 160, 1168 (2011).
22. A. Joshi, S. A. Gangal, and S. K. Gupta, Sens. Actuators B 156, 938
(2011).
Received: 31 July 2012. Accepted: 21 February 2013.
J. Nanosci. Nanotechnol. 13, 62496253, 2013 6253