Journal of Environmental Chemical Engineering 8 (2020) 104249

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Journal of Environmental Chemical Engineering

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Na-cholate micelle mediated synthesis of polypyrrole nanoribbons for T

ethanol sensing
Arpita Adhikaria, Punam Tiwaryb, Dipak Ranac, Arijit Halderd, Jyotisko Natha, Arijita Basua,
Debojyoti Ghoshald, Pradip Kare,*, Amit Kumar Chakrabortyf,*, Dipankar Chattopadhyaya,*
a
Department of Polymer Science and Technology, University of Calcutta, 92 A.P.C. Road, Kolkata 700 009, India
b
Department of Electronics & Communications Engineering, National Institute of Technology, Durgapur, West Bengal, 713209, India
c
Departments of Chemical and Biological Engineering, Industrial Membrane Research Institute, University of Ottawa, 161 Louis Pasteur St., Ottawa, ON, K1N 6N5,
Canada
d
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700 032, India
e
Department of Chemistry, Birla Institute of Technology, Mesra, Ranchi, 835 215, Jharkhand, India
f
Department of Physics, and Centre of Excellence in Advanced Materials, National Institute of Technology, Durgapur, West Bengal, 713209, India

ARTICLE INFO ABSTRACT

Editor: G. Palmisano The low-level sensing of ethanol has gained enormous importance due to its application in human health
Keywords: monitoring, road safety, fermentation and food industries. In this investigation, we report the synthesis of rib­
Polypyrrole bonlike nanostructures of polypyrrole (PPY), a conducting polymer, using sodium cholate micelles as a soft
Ethanol sensor template. The PPY nanoribbons were found to exhibit good sensor response along with high degree of selectivity
Nanoribbon to ethanol vapour as opposed to several common volatile organic compounds (VOCs) showing its suitability as a
Selectivity selective sensing layer to detect ethanol from a mixture containing ethanol, methanol, 2-propanol, toluene, n-
hexane, and humidity. The sensing mechanism and its selectivity to ethanol vapor were explained by considering
a hydrogen bond type interaction of the eOH groups of ethanol molecules with large number of ]N or eNH
groups of the PPY available on the surface due to its nanoribbon morphology. Investigation of the cytotoxicity of
the PPY nanoribbons revealed good biocompatibility.

1. Introduction milk skin headspace; or the headspace of disease related cells. Precise
measurements of the concentrations of these VOCs present in these
With the progress of civilization, air pollution has become a serious body fluids thus offer a viable method for human health monitoring. In
threat to the living world. Various toxic gases are emitted primarily particular, consumption/inhaling of excess ethanol, a low molecular
from coal combustion, diesel vehicles, industrial process as well as weight VOC, has been suggested to have serious harmful effects in
oxidation of precursors such as sulfuroxides (SOx), nitrogen oxides human health [4]. Ethanol has also been identified as a biomarker for
(NOx) and volatile organic compounds (VOCs) [1]. The VOC family early diagnosis of diabetes in humans [5]. Detection of ethanol is of
encompasses saturated and unsaturated hydrocarbons, aromatic com­ enormous interest to traffic safety as it helps us to block drunk driving
pounds, alcohols, aldehydes, ketones and nitriles. The long or short- on the road. Many food and chemical industries also require monitoring
term emission of many VOCs in the air could be deleterious to the of ethanol for process control and safety. Thus the identification and
environment causing harmful effects to human health [2]. In the human detection of ethanol is of utmost importance not only for human health
body, specific biological occurrences resulting from an alteration of monitoring but also for control of indoor air pollution both at home and
metabolic pathways (principally related to lipid metabolism and cyto­ workplace, as well as for food and chemical industries [6–10]. In con­
chrome P450), are associated with the production of various VOCs such temporary times, the rampantly used analytical techniques for detec­
as acetone, ethanol, isopropanol, 2-butanone, benzene, toluene, tion of VOCs are Gas Chromatography (GC) and GCMS (GC-mass
hexane, and isoprene [3] which are eventually emitted through body spectrometry), which are not only cost-ineffective and but also not
fluids such as exhaled breath, urine headspace, saliva, blood headspace, portable. Sensors based on surface acoustic waves, quartz crystal

Corresponding authors.
⁎

E-mail addresses: pkar@[Link] (P. Kar), [Link]@[Link] (A.K. Chakraborty),

[Link]@[Link] (D. Chattopadhyay).

[Link]
Received 5 May 2020; Received in revised form 23 June 2020; Accepted 4 July 2020
Available online 04 July 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

microbalance, capacitance, resistance, etc. overcome the portability or To overcome the above problem, the utility of the soft templates
cost issues but often suffer from shortcomings due to low sensitivity, made of surfactants, organic acids, gel, etc., has been reported by a
selectivity, reproducibility, impediment from humidity, insufficient number of groups [37]. For example, Anilkumar and Jaykannan [38]
stability, or varying responses due to sensor aging. Thus, the need for a reported synthesis of various types of nanostructured PANI using soft
highly sensitive portable and low-cost VOC sensor persists. template method. Ma et al. [39] synthesized PANI dendrites using mi­
In the pursuit for a low-cost portable sensor, chemiresistive sensors, celle of sodium lauryl sulfonate (SLS) as the soft template. Inverse
which relies on a semiconducting material that exhibits a sharp change emulsion polymerization of aniline was performed in the toluene
in its electrical resistance when exposed to a gas or VOC, have received medium with a simultaneous presence of a mixture of dodecylbenzene
large research attention in the recent times [6–10]. Semiconductor sulfonic acid (DBSA) and cetyltrimethyl ammonium bromide (CTAB) as
metal oxides (SMOs) form the main class of materials that have been the surfactant system. The oxidative polymerization of aniline was
most widely explored for developing this type of sensor as SMOs are achieved by deploying ammonium peroxodisulfate as an oxidant, a
chemically very stable, mostly low-cost and abundantly found in nature dopant in hydrochloric acid and a soft template provided by a rhamno
[4,11–13]. Further, the sensitivity of these sensors were improved by lipid biosurfactant produced by Pseudomonas aeruginosa SP4. This re­
resorting to a nanostructured design of the SMO as this enhances the action methodology helped in attaining nanorod and nanotube mor­
surface area of the sensor material (SMO) although the major limitation phology of polyaniline with average diameters in the range of
of SMO based sensor is their relatively poor selectivity to different VOCs 121 ± 12 nm to 152 ± 13 nm [40]. Adhikari et al. recently reported a
[12]. soft template approach to produce rodlike PPY-silver nanocomposite
Conducting polymers viz., polyaniline (PANI), polypyrrole (PPY), and showed its acetone sensing abilities [21].
polythiophene (PTH), etc. are a class of materials which can be good In view of the above, in this work we report the development of an
candidates for a wide range of applications [14–18] and are especially ethanol sensor based on nanoribbons of PPY prepared using sodium
suitable for chemiresistive sensors as they provide good environmental cholate biosurfactant as a soft template. Three batches of PPY were
stability, redox reversibility, good electrical conductivity, doping de­ synthesised by changing the growth conditions of which the nanor­
doping property which is responsible for high sensitivity towards var­ ibbon morphology showed the largest surface area and consequently
ious toxic gases and VOCs [19–23]. Kar et al. [24] synthesized pro­ showed good performance as a sensor with high selectivity and sensi­
cessable poly(m-aminophenol)(PmAP) film which was cast from tivity to ethanol at room temperature. Further, the cytotoxicity tests
dimethyl sulfoxide solution and doped with sulfuric acid which showed were conducted for all the three batches of samples which indicated the
good response to various aliphatic alcohol vapors. Among various nanoribbon morphology to be the most biocompatible thus suggesting
conductive polymers, polyaniline (PANI) and polypyrroles (PPY) are its good potential as a low cost ethanol sensor.
largely explored for various applications including sensors due to their
relatively higher chemical stability and ease of synthesis [25]. Li et al. 2. Materials and methods
[26] reported polyaniline/protoporphyrin nanocomposite based trie­
thylamine sensor with a high response and fast response time of 2.1. Materials
2−4 [Link] and Wang [27] reported a PANI(IO)/Au/Al2O3 composite as
the sensing electrode and obtained the sensitivity, response and re­ Pyrrole (procured from Sigma-Aldrich Inc) was vacuum distilled,
covery times of 5.90 × 10−4 ppm-1, 1.0–3.0 and 3.0–10.0 min, respec­ purged with nitrogen and wrapped with aluminium foil to prevent any
tively to acetone vapor. Hamilton et al. [28] electrochemically syn­ photolytic influence and stored in a refrigerator at4 °C. Ammonium-per-
thesized polypyrrole and investigated the influence of different growth sulphate and hydrochloric acid from Merck India Ltd. were used.
parameters on their sensing performance. Castro et al. [29] fabricated a Emplura supplied methanol and isopropyl alcohol. Ethanol and toluene
new type of e-nose consisting of only five sensors made of hierarchically were purchased from Himedia and Proanalyst. Triple distilled water
structured conducting polymer nanocomposites (CPC). The ability of wasused.
the sensor to detect nine organic solvent vapors (isopropanol, tetra­
hydrofuran, dichloromethane, n-heptane, cyclohexane, methane, 2.2. Polypyrrole synthesis
ethanol, water and toluene) as well as biomarkers for lung cancer de­
tection in breath evaluation was demonstrated. PPY was synthesized following the chemical oxidative polymeriza­
Nanostructured morphology of conducting polymers like nanotubes tion method by first dissolving 16 mM sodium cholate in 50 mL 1.25 M
[30], nanowires [31], nanorods [25], have been reported to exhibit HCl solution under mechanical stirring in ice-cold condition for 15 min
enhanced optical and electronic properties which could not be attained till it formed a homogeneous solution. Then, 0.058 mM pyrrole
by their bulk counterparts [32]. Especially, a nanostructured mor­ monomer was added under the stirring condition to the as prepared
phology could enhance the sensitivity and selectivity of a conductive aqueous surfactant solution and stirred for a further period of 15 min.
polymer based sensor as it would have larger surface area allowing for APS dissolved in water was added to this mixture to initiate the PPY
larger interaction with analyte VOC/gas molecules. In this regard, a polymerization process. The ratio of the concentration of monomer to
great deal of effort has been invested to unravel various morphological an oxidizing agent was kept at 1:1 (mmol/mmol). The polymerization
arrangements of conducting polymers. The use of a template is probably process was continued for 5 h at around 0−5 °C temperature (in an ice
the most versatile technique to synthesize nanostructured conducting bath). At the completion of polymerization, the black polypyrrole was
polymers. Template guided synthesis includes hard and soft template washed with acidified (1.25 M HCl) triple distilled water followed by
methods. The hard-template synthesis consists of a physical template as acetone washing till the filtrate becamecolorless. The washed PPY was
a scaffold for the growth of conducting polymers [33]. The nanosized dried prior to characterization.
channel in the form of anodized alumina oxide (AAO) and mesoporous Polymerization of pyrrole monomer was realized via standard che­
silica/carbon templates along with colloidal particles comprise the hard mical oxidation resorting to the template guided synthesis as shown in
template scaffold [34,35]. The most commonly employed hard tem­ Scheme 1. The impact of critical micellar concentration (CMC) on the
plates include AAO, block co-polymers, porous silicate, mesoporous morphology of synthesized PPY was assessed by altering the sodium
zeolites, etc. This method is very effective for the synthesis of nanos­ cholate concentration. The choice of surfactant concentration was made
tructured conducting polymer with a particular diameter and mor­ on the basis of the micellar aggregation range (CMC of sodium cholate
phology [36]. In the case of hard templates, the post-synthetic pur­ spans the range of 9−14 mM) [41]. The variation of sodium cholate
ification step is very tedious as the template removal may destroy the concentration for the synthesis of PPY samples A and B has been out­
nanostructured polymer. lined in Table 1. Sample B has been synthesized with 7 mM sodium

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

Scheme 1. Schematic presentation of sodium cholate guided synthesis of nanoribbon shaped PPY.

Table 1 2.4. Fabrication of gas sensing set up

Polypyrrole samples synthesized using various surfactant concentrations.
Sample designation Properties A thin film of the polymer was cast on a clean glass substrate from a
dispersion of 5 mg of PPY polymer in 2 mL toluene. The wet polymer
Surfactant (sodium cholate) conc. Oxidant film was dried in a vacuum desiccator for 12 h. The glass substrate
coated with the polymer film was mounted in the sensing chamber.
A 16 mM (above CMC) APS
B 7 mM (below CMC) APS
Electrical leads were connected to the film from an external source
C 0 mM (No surfactant) APS meter (Keithley 2450) interfaced with a computer for automated re­
cording. The indigenous sensing setup (Fig. 1) comprised of three inlets
out of which one was linked to nitrogen gas flow, the second to air and
cholate (below CMC) and sample C is devoid of any sodium cholate. the third to the analyte gas to be sensed. The influx of the gas into the
sensing chamber was powered by a diffusion pump reinforced by a
2.3. Characterization of PPY samples rotary pump. To sense humidity, the chamber was evacuated to a
permissible pressure of 0.17 mbar followed by the introduction of
X-PETRO Panalytical diffractometer was used resorting to Cu Kα humid air (of specific humidity) until the attainment of atmospheric
(λ = 1.5406) as X-ray source at a scan rate of 1° min−1, 40 KV voltage pressure. The incumbent fluctuation in resistance underlying the pro­
and 30 mA current to accomplish the XRD analysis of PPY samples. cess was recorded with a digital multimeter. The moisture content in
Perkin-Elmer Spectrum Two FT-IR spectrophotometer was used to
carry out the FTIR analysis of PPY samples amalgamated in KBr pellets
with a wave number sweep within 400−4000 cm−1. In order to eval­
uate the interaction of PPY nanoribbons with the analyte the FTIR
spectra (Thermo Nicolet Nexus 870 Spectrophotometer) and UV–vis
(Mikropack UV–vis-NIR, DH 2000) were recorded using dilute disper­
sion of the samples in respective analyte, viz., ethanol, methanol, water,
etc.
To detect and analyse the surface morphology of PPY samples SEM
studies were conducted with the help of ZEISS EVO 18. A Pt coating was
applied on the samples and consequently surmounted on a specimen
stub prior to examination under a microscope.
The detailed morphological studies of the PPY samples were con­
ducted via TEM. The sample preparation for TEM studies involved the
casting of PPY suspensions on copper grids coated with carbon followed
by aerial evaporation of the liquid.
Quantachrome Autosorb-iQ adsorption instrument was used to
measure the surface area of the samples at ambient pressure taking the
degassed samples at 77 K maintained by a liquid-nitrogen bath. Ultra-
pure (99.9999 %) N2 and He were used for the purpose. Samples were
degassed by heating at 70 °C under reduced pressure for 8 h prior to N2
gas sorption measurement. From the N2 gas sorption data, the surface
area was calculated using Brunauer–Emmett–Teller (BET) theory in the
range of relative pressure 0.01–0.3 and the porous nature of samples
was determined by size distribution curve, calculated by Barrett-
Joyner-Halenda (BJH) theory. Fig. 1. Schematic of the set-up for gas sensing measurement.

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

the air was monitored by a humidity sensor (HTC) and authenticated by

[Link]. Ethanol and other VOCs were introduced by heating
a glass vessel containing the VOC (to 100 °C) that was connected at the
mouth of the third inlet. The obtained vapor was then jettisoned into
the pre-evacuated sample chamber after which nitrogen gas was in­
troduced as an inert carrier.
The associated formulae for analysis are enlisted below
Vl
C= × 106
Vc (1)
where ‘C’ is the concentration of vapor of VOCs (in ppm), Vl and Vc are
the volumes of the evaporated ethanol and the chamber, respectively.
The response (R) of the sensor was defined as,

R = (Ra/Rg) (2)

where, Ra and Rg are the electrical resistances of the sensor in vacuum,

and in the VOC. Fig. 3. FTIR spectra ofthree PPY samplesA (above CMC), sample B (below
The time required to attain 90 % of the total resistance variation CMC) and sample C (no surfactant).
during gas inflow and outflow was coined as the response time and
recovery times, respectively. wave number range of 500−4000 cm−1. The characteristic peaks in
close proximity to 1550 cm−1 and 1441 cm−1 depicted in Fig. 3 cor­
3. Results and discussion respond to symmetric (C]C) and antisymmetric (C]N) stretching vi­
brations, respectively [42,43]. Vibrations owing to CeH deformation
3.1. X-ray diffraction of PPY nanostructure and CeH stretching are exhibited by the appearances of the char­
acteristic peak around 1054 cm−1 and 1313 cm−1 respectively [42].
X-ray diffraction pattern of three different PPY samples (sample A The peak observed at around 1174 cm−1 is a manifestation of CeH
(above CMC), sample B (below CMC) and sample C (no surfactant)) stretching vibration. NeH and C–H bond vibrations are responsible for
fabricated by varying the concentrations of surfactant and deploying a broad band within the 3000−3500 cm−1range [25]. The absence of
ammonium persulfate (APS) as oxidant has been depicted in Fig. 2. The sodium cholate surfactant in the synthesized PPY nano-structures can
amorphous nature of the synthesized PPY can be confirmed from the be confirmed from the fact that peaks of sodium cholate at around
broad scattered peak in the range 24°-26° [25]. The obtained result is in 3394, 2933, 2855, 1585, 1409 and 1080 cm−1have disappeared.
coherence with the reported structure from the literature. The addition
of sodium cholate does not affect the amorphous nature of the PPY
3.3. Morphology analysis by SEM and TEM
nanostructure can be concluded from the fact that any characteristic
peak corresponding to sodium cholate is absent in the XRD spectra.
Fig.4A and B represent SEM & TEM images of PPY nanostructures
synthesized in various surfactant concentrations. It is found that PPY
3.2. FTIR analysis
synthesized in 16 mM surfactant concentration exhibits ribbonlike
structure (Fig. 4A, Sample A), 7 mM and 0 mM surfactant concentration
To ensure that the polymerization has taken place, FTIR analysis
shows the spherical structure (Fig. 4A, Samples B and C). The formation
was conducted for three samples (sample A, B, C has been synthesized
of PPY nanoribbon can be explained on the basis of the template ap­
above CMC, below CMC, and in the absence of surfactant) spanning the
proach. In this process, sodiumcholate acts as a surfactant, which forms
rodlike micelle above CMC (16 mM concentration). The micelle acts as
a soft template. The nanoribbons are synthesized on the surface of the
template and after the dissolution of template, PPY of required nanor­
ibbon shapes (Fig. 4A, Sample A) is obtained. The synthesis of PPY in
the presence of a soft template, which acts as structure-directing mo­
lecules are well reported. The synthesis of PPY in the presence of so­
dium cholateas a surfactant is not only a novel idea but also gives good
uniformity in the morphology of nanoribbon. After the polymerization
of the pyrrole, the surfactants got removed from PPY during washing
and filtration process. The addition of sodiumcholate is responsible for
the formation of the nanoribbon. The amount of sodiumcholate has
played a crucial role in controlling the morphology of PPY. As the CMC
of sodiumcholate is 9−14 mM, it forms micelle above CMC. So, at
16 mM concentration, it forms micelle, which acts as a structure-di­
recting molecule of PPY. Below CMC, i.e., at 7 mM concentration so­
dium cholate cannot form a micelle. So, PPY synthesized below CMC
and without surfactant got spherical structure.

3.4. Sorption property

Sensing performances of sensor materials are strongly dependent on

their surface properties and hence we measured the N2 sorption prop­
Fig. 2. The XRD patterns of three PPY samples A (above CMC), sample B (below erties of all three PPY samples. Ambient pressure N2 sorption experi­
CMC) and sample C (no surfactant). ments (Fig. 5a) show classical type II adsorption isotherm for all the

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

Fig. 4. SEM [a,b,c] and TEM [d,e,f] micrographs of three PPY samples: sample A (above CMC), sample B (below CMC) and sample C (no surfactant).

compounds. Sample A has the highest N2 uptake (∼175 mL) whereas Table 2
sample C has the least uptake of ∼54 mL/g. Sample B uptakes in be­ Summary of BET surface area plot for the compounds.
tween these two optima, ∼108 mL/g. These findings are in accordance A B C
with the synthetic procedure. Along with decrease in template effect,
there is decrease in the ordered structure which may have caused the Slope 41.631 48.678 74.811
gradual decrease in the total adsorption amount. When we calculated, Intercept 1.578 2.044 3.979
Correlation coefficient (r) 0.999925 0.999774 0.999693
porosity distribution curve from the N2 adsorption curve (Fig. 5b),
C constant 27.375 24.811 19.801
sample B has no definite pore size whereas sample C has the highest Surface area (m2/g) 80.596 68.658 44.200
population of pores with radius of ∼2.10 nm. Interestingly, sample A
has scattered pore sizes with maximum lying between 1.76–2.10 nm.
The specific surface area calculated using the BET theory revealed selectivity to ethanol. Fig. 7(b) also shows a negligible sensor response
(Fig. 5c) that sample C has least surface area (44.200 m2/g) whereas against water vapour as it plotted the response of the sensors against
sample A has the highest surface area (80.596 m2/g). As expected, normal air of 75 % relative humidity (RH). The same is true for VOCs
sample B showed intermediate value of surface area (68.658 m2/g). other than alcohols such as toluene and hexane. Hence, we can safely
Further details on the BET fitting curve are provided in Table 2. conclude that all the synthesized PPY samples exhibit good sensor
performance against alcohol type VOCs and their highest response is
against ethanol. Among the three samples, however, it is evident that
3.5. Sensor performance evaluation
the best performing material is Sample A, i.e. PPY nanoribbons as the
magnitudes of maximum response against ethanol at various con­
The maximum sensing responses of all three PPY samples are
centrations is the highest for this sample.
compared against different concentrations of ethanol vapour at room
Since sample A (PPY nanoribbon) exhibited the best sensing per­
temperature in Fig. 6 (a) whereas the maximum responses against
formance compared to that of other two samples, detailed sensor
100 ppm of different VOCs are compared in Fig. 6 (b). Data in Fig. 6(a)
measurement data are presented for this sample only. The dynamic
and (b) clearly establish the superiority of sample A over other two
sensing response of PPY nanoribbon toward ethanol at concentrations
samples in terms of its sensor performance as it not only shows higher
of 50−150 ppm at room temperature is shown in Fig. 7(a). Upon ex­
response to all concentrations of ethanol but also its response to ethanol
posure to ethanol vapor, the electrical current exhibited by the PPY
is the highest compared to that to other VOCs suggesting its good

Fig. 5. (a). N2 sorption properties of PPY sample A (above CMC), sample B (below CMC) and sample C (no surfactant). (a) Isotherms at 77 K; filled and open symbol
represent adsorption and desorption, respectively, (b) BJH pore size distribution curves and (c) BET plots.

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

Fig. 6. Maximum responses of the three samples measured at room temperature. (a) against different concentration of ethanol, (b) against 100 ppm of different
[Link] A (above CMC), sample B (below CMC) and sample C (no surfactant).

Fig. 7. Room temperature sensing data for PPY nanoribbons (sample A). Dynamic response at varying ethanol concentration (a), Polynomial fit of the response vs.
ethanol concentration (b), Expanded view of the dynamic response at 100 ppm ethanol (c), Response-recovery times at varying ethanol concentrations (d),
Repeatability plot (e), and I-V curve (f).

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

nanoribbons (sample A) film increased and reached a maximum. It is dipole-dipole interaction ability, dielectric constant and polarity of the
observed from Fig. 7(a) that at 50 ppm ethanol concentration, the re­ analyte [44,45]. As shown in Scheme 2, the alcohol molecules are
sponse is 23.34, at 75 ppm ethanol concentration it is 66.80,at 100 ppm strongly hydrogen bonded either with the ]N atoms of oxidized units
ethanol concentration it is 87.64, at 125 ppm ethanol concentration it is like pathway (a) and/or –NH atoms of reduced units of PPY like
106.29, and at 150 ppm ethanol concentration the response is 118.56. pathway (b). The current flow should increase throughout the con­
Thus, one can see that the rate of increase of response slows down with jugated chain by the interaction in the pathway (a) due to formation of
increased ethanol concentration. To understand the exact nature of the an ion-dipole like -HN+%……OR by receiving electron cloud of ]N
dependence of the sensor response on ethanol concentration, a separate atoms of oxidized units through strong hydrogen bonding with the H
plot showing only the values of the sensor response against various atoms of alcohol molecules [46]. Whereas, the current flow should
ethanol concentrations is depicted in Fig. 7(b). A polynomial curve was decrease throughout the conjugated chain by the interaction in the
found to give the best fit which was therefore used to join the data pathway (b) due to receiving electron cloud of –O− alcohol molecules
points in Fig. 7(b). It is not surprising given the response of the polymer by the –NH atoms of reducing units [47,48]. Although both pathway (a)
sensor will reach its saturation once sufficient number of ethanol mo­ and (b) are possible but their influence on the electrical conductivity
lecules are already adsorbed using all the available molecules of PPY. does not cancel out because the bond strength of O–H⋯N (pathway (a))
Fig. 7(c) plots an expanded view of the dynamic response of the sensor is much higher than that of N–H⋯O (pathway (b)). As a consequence,
against 100 ppm of ethanol to demonstrate how the response and re­ all three alcohols exhibit an increase in the electrical conductivity in­
covery times were calculated. One can see that the developed PPY dicating the dominant influence of the pathway (a) and this dominance
sensor shows quite fast response time of ∼2 s against 100 ppm ethanol is stronger for smaller/linear molecules than bulky molecules as the
exposure, whereas its recovery time is ∼31 s. A close look at the re­ smaller molecules find it easy to reach the close proximity of N atom of
covery curve reveals that recovery of the response occurs in two steps. the pyrrole ring, whereas the bulky molecules of 2-propanol find it
In the first step, the vapor molecules sitting only on the surface of the difficult to interact via pathway (a) [46]. This explains why 2-propanol
sensor are evaporated almost immediately after the pump is switched has the lowest sensor response compared to methanol and ethanol. In
on resulting in a plateau like region whereas the vapor molecules ad­ general, methanol exhibit higher response than that of ethanol because,
sorbed deep into the porous nanostructured film of PPY are degassed being smaller in size, methanol should diffuse more readily within the
relatively slowly resulting in the second step of recovery graph. This polymeric film compared to ethanol and its polarity and dielectric
behaviour is different from the commonly reported heat-induced re­ constants are both higher than that of ethanol [44,45]. While high
covery of sensors in which case a single step continuous decay curve is polarity ensures strong hydrogen bonding, large dielectric constant
observed due to a gradual and continuous release of the adsorbed improves the crystallinity by stretching conformations of the polymer
molecules since the heating occurs from the bottom of the film. and in turn, increase its current flow. Therefore, the interaction of
It is worth noting that the lowest concentration of ethanol measured methanol with PPY nanoribbon is expected to be not only stronger than
by the PPY nanoribbon sensor was 25 ppm at which the sensor showed that of ethanol but also strong for both the pathways a and b as shown
negligible response of 1.2 which is why we have not shown this data. in Scheme 2. It is not clear why PPY nanoribbons prepared in this work
On the other hand, for ethanol concentration above 150 ppm, it took show their highest response to ethanol (not methanol), but could be due
long time for us to degas the chamber and hence we avoided doing it. to differences in relative dominance of the two competing pathways a
Also, since the plot of maximum response against different ethanol and b for the two alcohols. The responses of PPY nanoribbon to n-
exposure (Fig. 7b) indicated a gradual decrease of slope of the response hexane and toluene molecules are very small as these do not form hy­
plot, and since the large chamber took long time to recover at high drogen bond with PPY molecule
ethanol exposures, we did not take measurements above 150 ppm as the In order to support the proposed sensing mechanism, the UV–vis
sensor response seemed to soon reach its saturation. and FTIR data are shown in Fig. 8. The characteristic UV–vis absorption
The response and recovery times as a function of ethanol con­ peak (Fig. 8A) of PPYnanoribbon dispersed in water or ethanol ap­
centration extracted from Fig. 7(a) following the method shown in pearing at ∼489 nm is assigned to the polaron-π transition and the
Fig. 7(c) is further plotted in Fig. 7(d). It can be seen that the response peak is slightly blue shifted to a higher wavelength (484 nm) for the
time is slowly decreased with increase in ethanol concentration, PPY nanoribbon dispersed in methanol [49–51]. Therefore, the current
whereas the recovery time is increased with increasing ethanol con­ flow is reduced for methanol exposed PPY due to reducing the polaron-
centration (Fig. 7d). The decrease in the response time with increasing π delocalization for the interaction following the pathway (b) (Scheme
ethanol concentration can be understood by considering that larger 2) and that interaction is absent for the PPY dispersed in water or
number of ethanol molecules interact with the PPY molecules at higher ethanol. In addition, the intensity of polaron and bipolaron band
concentration making the response (change in the resistance) faster. But transitions of PPY dispersed in water is appeared at 667 and 730 nm
while recovery, an opposite trend is observed because unlike most other (Fig. 8A) [45,52,53]. This polaron and bipolaron band transitions of
research groups, in our experiment the removal of ethanol from the PPY PPY are red shifted in methanol or ethanol dispersed sample indicating
sensor occurred only by the action of the pump and not by heat. Ob­ the increase of current flow by increasing the polaron and bipolaron
viously, this means that larger the concentration of ethanol, larger charged centres for the interaction following the pathway (a) (Scheme
would be the recovery time due to ethanol’s vapour pressure. To verify 2) [54,55]. As shown in Fig. 8B, the same inference can be drawn from
the reproducibility of the sensor, the dynamic response curves of the the FTIR spectra of the PPY nanoribbon dispersion in water, methanol
PPY nanoribbon sensor against 75 ppm of ethanol recorded for five and ethanol. In FTIR spectra the stretching band of C]N and CeNH is
consecutive cycles are shown in Fig. 7(e). From the figure, it is clear respectively red shifted to 1650 and 1410 cm−1 for PPY dispersed in
that the sensor response curves are highly reproducible as only minor ethanol while 1644 and 1410 cm−1 for PPY dispersed in methanol from
fluctuations are observed in the maximum value of some curves, but the its original value [45,54,55]. This is because of the interaction between
curves showed identical shape (Fig. 7e). The ohmic contacts at the the PPY and ethanol or methanol molecule [45,54,55]. The C]N/CeN
junction between the polymer film and the metallic electrical leads, peak ratio denoting the ratio of oxidized and reduced ring is almost 1:1
were ascertained, at least in the lower region of the applied voltage, by in ethanol due to strong interaction with methanol with both the rings
the I–V characteristic as shown in Fig. 7(f). where as it is higher than 1:1 due to the strong interaction of ethanol
In order to understand the sensing mechanism and explain the se­ with the oxidizing ring [54,55]. In addition, there is more red shift of
lectivity of the PPY nanoribbon towards ethanol following mechanism the oxidizing peak at 1650 cm−1 for PPY dispersed in ethanol than that
has been proposed (Scheme 2). The response of PPY nanoribbon layer of the PPY dispersed in methanol at 1644 cm−1 [54,55]. It is impossible
upon exposure of VOCs mostly depend on the hydrogen bonding ability, to analyze the FTIR spectrum for PPY dispersed in water due to a very

7
A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

Scheme 2. Proposed mechanism of alcohol sensing through the hydrogen bonding interaction either (a) with the ]N atoms of oxidized units or (b) eNH atoms of
reduced units of PPY nanoribbon.

Fig. 8. (a) UV–vis and (b) FTIR absorption spectra of PPY nanoribbon dispersion in water, methanol and ethanol.

Table 3
List of performance parameters of polymer based ethanol sensors.
Sr. no. Sensor material Ethanol conc. (ppm) Response Response/Recovery times (s) Referencess

1 PVA wrapped MWCNTs 100 1.56 24/29 [56]

2 PPY in PVA matrix 100 1.70 42/200 [57]
3 m-CNTs/NaClO4/Ppy 30,000 1.19 20/20 [58]
4 Poly m-aminophenol 126 1.24 180/225 [24]
5 PPY nanoribbons 100 87.64 2/31 This work

broad and strong peak of−OH groups of water. Table 3, the main performance parameters of polymer based room
Thus, we have shown that the PPY nanoribbons synthesized in this temperature ethanol sensors reported previously by other research
work exhibits good sensing properties against ethanol. However, one groups. The values listed in the table clearly establish the superiority of
may ask how this sensor compares with ethanol sensors made by pre­ the PPY nanoribbons synthesized in this work as it not only outsmarts
vious researchers. To answer this question, we have compared, in previous sensors in terms of its sensitivity (response) but also its

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A. Adhikari, et al. Journal of Environmental Chemical Engineering 8 (2020) 104249

Fig. 9. (a) Plots of Cytotoxicity (cell viability) against concentration of the three PPY samples and (b) SEM micrographs of fibroblast cells: control, Sample A, Sample
B, Sample C treated cells.

response and recovery times are the fastest compared to others. CRediT authorship contribution statement

Arpita Adhikari: Conceptualization, Methodology, Validation,

3.6. Cytotoxicity study Investigation, Writing - original draft. Punam Tiwary: Methodology,
Validation, Formal analysis, Investigation. Dipak Rana: Visualization,
The cytotoxicity study was conducted to test whether the sensor can Supervision, Project administration. Arijit Halder: Validation.
be integrated in human bodies if required. In particular, polymer based Jyotisko Nath: Validation. Arijita Basu: Validation. Debojyoti
sensors are preferred over metal oxide counter parts for their flexible Ghoshal: Visualization, Supervision. Pradip Kar: Validation,
nature which allows them for easy integration with irregular shaped Investigation, Visualization, Supervision. Amit Kumar Chakraborty:
objects. We have studied the cell viability of our synthesized PPY na­ Resources, Writing - review & editing, Visualization, Supervision,
nostructures on normal mouse fibroblast cell line, L929. The L929 cells Funding acquisition. Dipankar Chattopadhyay: Resources, Writing -
incubated with varying concentrations of the different PPY nanos­ review & editing, Visualization, Supervision, Project administration,
tructures were subjected to MTT assay, the results of which have been Funding acquisition.
plotted in Fig. 9A. It is apparent from Fig. 9A that the cytotoxicity in­
creased with increasing dosage. It has also been observed from Fig. 9A Declaration of Competing Interest
that synthesized PPY samples exhibited very less cytotoxicity which is
indicative of the biocompatible nature of the samples. Sample A shows The authors declare no competing financial interest.
minimum cytotoxicity among all the PPY samples probably due to its
ribbonlike morphology. Additionally, SEM images presented in Fig. 9B Acknowledgements
reflected the cytomorphological architecture of the fibroblast cell lines.
PPY treated cells showed no specific alteration in cellular morphology The first author, A. Adhikari likes to thank the Department of
with respect to the untreated control cells. Thus, all the above data Science & Technology (DST), New Delhi, Govt. of India, for her fel­
indicated the non-cytotoxic nature of the synthesized PPY. lowship under Women Scientist Scheme WOS-B (SoRF) [Internship
mode]. P. Tiwary acknowledges the University Grants Commission
(UGC), Govt. of India (GoI) for her fellowship as a JRF. AKC ac­
4. Conclusions knowledges the Ministry of Human Resource Development (MHRD),
GoI for the generous grant under TEQIP-III (Centre of Excellence), May
Ribbonlike PPY nanostructure was synthesized through single-step 2018 provided to NIT Durgapur. We also acknowledge the Center for
polymerization of pyrrole monomer using sodium cholate biosurfactant Research in Nanoscience and Nanotechnology (CRNN), University of
as a soft template in the presence of APS oxidant. The nanoribbon Calcutta, for instrumental facilities.
morphology showed large surface area which was exploited to observe
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