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Article
A Simple Route to Prepare Polypyrrole Coated Filter papers via
Vapor Phase Polymerization and their Gas Sensing Application
Sibani Majumdar, Kumaresh Sarmah, and Debajyoti Mahanta
ACS Appl. Polym. Mater., Just Accepted Manuscript • DOI: 10.1021/acsapm.0c00147 • Publication Date (Web): 13 Apr 2020
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Page 1 of 35 ACS Applied Polymer Materials

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A Simple Route to Prepare Polypyrrole Coated Filter papers via Vapor Phase
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6 Polymerization and their Gas Sensing Application
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Sibani Majumdara, Kumaresh Sarmahb, Debajyoti Mahantaa*
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a Department of Chemistry
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b Electronics and Communication Technology
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16 Gauhati University
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18 Guwahati, Assam, India, 781014
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36 * To whom correspondence should be addressed
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Dr. Debajyoti Mahanta
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41 Tel: +91-6000682511
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44 Fax: +91-0361-2700311
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46 Email: debam@gauhati.ac.in, debam2@gmail.com
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3 Abstract:
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Vapor phase polymerization has been used for the synthesis of Polypyrrole coated filter paper
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9 (PPy-FP) using a simple experimental setup. Further, we have doped the polymer coated filter
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11 papers with hydrochloric acid (HCl), camphor sulphonic acid (CSA) and p-toluene sulphonic
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13 acid (PTSA) to prepare HCl-PPy-FP, CSA-PPy-FP and PTSA-PPy-FP respectively. These
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16 samples were characterized by scanning electron microscopy (SEM), thermogravimetric analysis
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18 (TGA), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), energy
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20 dispersive X-ray (EDX) analysis and powder X-ray diffraction (PXRD) techniques. The prepared
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23 PPy coated filter papers have been used for ammonia vapor sensing studies at room temperature.
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25 The sensing device of the hybrid filter papers were developed by pasting Cu strips as electrodes.
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27 It has been observed that doping enhances the conductivity from 1.78 x 10-5 S/cm to 3.34 x 10-5
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S/cm. The sensing performance also improved on doping and among the developed sensors,
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32 HCl-PPy-FP shows the best result. The limit of detection (LOD) value for PPy-FP is found to be
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34 13 ppm which has been improved up to 5.2 ppm for HCl-PPy-FP. Doping increases the
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36 delocalization along the PPy chain to generate more active sites. The fabricated devices are
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39 flexible, easy to handle and cost effective.
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51 Keywords: Vapor phase polymerization; Polypyrrole; Filter paper; Paper based sensor;
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Ammonia sensing; Gas Sensing
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3 1. Introduction
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The increasing air pollution in the recent years is a major concern for the global environment
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9 protection. Various organic and inorganic chemicals used in the industries along with the volatile
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11 organic compounds (VOC) are the major sources of air pollution.1,2 Ammonia is a toxic gas
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13 having extensive applications in fertilizers, pesticides, petrochemical, textile and dye industries.
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15 3-5
16 A very low concentration of ammonia can also act as a threat to human eye, skin and
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18 respiratory systems and also affects the animals and the environment.6,7 The exposure limits of
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20 ammonia for 15 min and 8 h exposure time are 35 ppm and 25 ppm respectively, as reported by
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23 American conference of governmental industrial hygienists and national institute for
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25 occupational safety and health.8 Exposure above these limits can cause severe damages to the
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27 human health and a very long-time exposure can cause even human death. Therefore, the
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development of different techniques to detect such pollutants is highly desirable. One of the most
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32 useful approaches in this regard is the applications of gas sensors. So, the development of
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34 effective gas sensing materials has attracted the researchers in recent years. 9-12 The study on
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36 exhaled human breath is another promising field that has got a lot of attention in the recent years
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39 as the exhaled breath consists of VOCs as biomarkers for different diseases and metabolic
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41 disorder. Thus, breath analysis is an invasive and easy way to operate for primary detection of a
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43 diseases or disorder. Ammonia has been used as a biomarker for detection of renal disorders or
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46 ulcers and asthma. So, detection of ammonia from the human breath is helpful for early detection
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48 of renal disease and asthma. It has been reported that a normal health person exhales about 0.05
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50 to 1.5 ppm ammonia concentration, which has been increased above 1.5 ppm to 15 ppm for
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patients with extreme renal disorders.13,14
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3 Conductive polymers are one of the most preferred classes of materials for use in gas sensors
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6 because of their promising electronic properties. Therefore, in the last couple of years numerous
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8 works have been reported on conducting polymer-based biosensors such as Polyaniline/hematite
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10 nanocomposite and composite of polyaniline/multi-walled carbon nanotubes/molybdenum
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disulfide has been developed for sensitive and reproducible ammonia gas sensing.15,16 Several
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15 composites of polythiophene has also been used as an effective gas sensor.17-19 Polypyrrole (PPy)
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17 is another widely studied conductive polymers due to its simple synthesis process, good
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electrical conductivity, low cost and decent chemical and electrochemical stabilities.21,22 Several
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22 studies have been reported on the application of PPy in gas sensors for detection of different
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24 gases. A. Joshi and coworkers have developed PPy thin films by chemical polymerization and
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26 studied their ammonia sensing properties at room temperature.23 Different PPy based hybrid
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29 composites such as PPy-coated SnO2 nanosheets, PPy-reduced GO hybrid composites have been
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31 developed for enhanced ammonia sensing.24,25 J. Liu et al. developed ammonia sensor based on
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33 PPy nanowire arrays.26 Another advanced concept that has been extensively used in the recent
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years is paper based gas sensors. The high abundance, low cost, flexibility, easy to operate and
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38 its versatile properties make cellulose paper one of the potential support materials in this field.
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40 The first paper-based device was demonstrated in 1956 for detection of glucose in urine and after
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that several modifications were carried out. Colorimetric, electrochemical, chemiluminescence,
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45 electrochemiluminescence and electrical conductivity are the major techniques used in paper-
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47 based devices for quantitative analysis. 27-29
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49 Here, we have synthesized PPy coated filter paper (PPy-FP) by a simple and cost-effective vapor
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52 phase polymerization method. Vapor phase polymerization is a very simple, easy and effective
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54 way of deposition of polymer on a substrate. There are several works reported earlier that used
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3 this method of polymerization for deposition of different polymers on various substrates. A
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6 certain pressure was maintained during the process for effective polymerization.30-32 PPy coated
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8 conductive paper, A4 paper and different PPy-composite films were also developed by this
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10 method.33-35 In these works, vacuum reaction chamber or air-tight vapor deposition chamber has
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been used for the vapor deposition process. In the present work, we have synthesized the PPy
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15 coated filter paper in a simple laboratory round bottom flask at atmospheric pressure and room
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17 temperature. We have also modified the properties of PPy-FP by doping it with hydrochloric
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acid, camphor sulphonic acid and para-toluene sulphonic acid. The paper based samples were
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22 characterized by ATR-FTIR, PXRD, TGA, EDX and SEM techniques. The PPy-FP shows a
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24 considerable response for ammonia vapor and that has been improved after doping, where HCl-
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26 PPy-FP shows the maximum response. Although there are certain materials reported that can
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29 detect a very low concentration of ammonia vapor with high percentage response, in most cases
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31 the synthesis procedures are costly and complex. Moreover, most of them require advance device
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33 fabrication processes. In this work, after synthesizing the PPy coated filter papers, the devices
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have been developed by directly pasting the Cu electrodes over the modified filter papers and the
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38 measurements were ready to be carried out. The sensing experiments were also carried out in
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40 simple glass apparatus at ambient atmospheric conditions. Again, as the material and the
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synthesis procedure are easy to handle there is a high scope of modification of the materials to
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45 improve the gas sensing properties by developing hybrid composites with other organic and
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47 inorganic materials by modifying the synthesis procedure.
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50 2. Materials and methods
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53 2.1 Materials
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3 Whatman-40 filter papers, anhydrous ferric chloride (FeCl3), pyrrole, ammonia solution (25%),
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6 hydrochloric acid (HCl), camphorsulphonic acid monohydrate (CSA) and p-toluenesulphonic
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8 acid monohydrate (PTSA) were purchased from Sigma-Aldrich and used as received.
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11 2.2 Preaparation of Polypyrrole coated hybrid filter papers with different dopants
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14 For the preparation of the devices, Whatman-40 filter papers (FP) were cut into small pieces of
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size (3x1) cm2. Each small piece of the filter paper was soaked in 20 ml of 0.1 M FeCl3 solution
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19 for 15 min followed by drying at room temperature. The FeCl3 solution was prepared by
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21 dissolving 1.63 g of anhydrous FeCl3 in 100 ml distilled water. Now these filter papers were
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mounted inside a 250 ml round bottom flask containing 30 ml pyrrole (Py) monomer to get
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26 exposed by the Py vapor.. The polymerization starts immediately after exposure of the FeCl3
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28 contained FP to Py vapor and within a few seconds the blank filter paper turns into black color,
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30 but we continued the exposure for 1 h for complete polymerization on the filter paper. All the
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33 synthesis processes were carried out at a temperature around 32οC. After the selective
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35 polymerization of Py monomers on the surface of filter papers, the uniformly PPy-coated filter
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37 papers were washed with distilled water, dried at room temperature and kept in desiccators. The
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schematic representation of the preparation process of PPy coated filter papers and their
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42 photographs are given in Figure 1(a). The synthesized hybrid filter papers are flexible and very
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44 easy to handle, the flexibility of the PPy coated filter papers can also be seen from the
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photographs in Figure 1(b).
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We have also determined the amount of PPy coated on blank-FP by gravimetric method. To
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52 carry out this experiment, 1 set of blank filter papers (6 filter papers) of size (3×1) cm2 was taken
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54 and the weight of the blank filter papers was subtracted from the weight of the filter papers after
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3 polymerization. The process was repeated for 3 sets and the average weight was determined. The
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6 average weight of PPy deposited on one filter paper was calculated to be 2.20 mg.
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22 Figure 1: (a) Schematic representation of the synthesis of PPy-FP and the inset shows the
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24 photograph of the Blank-FP and PPy-FP (b) Photographs showing the flexibility of the PPy-FP
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For the synthesis of doped PPy coated filter papers, 0.1 M of HCl, CSA and PTSA were
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29 dissolved in the 0.1 M 100 ml FeCl3 solution keeping the rest of the procedure same as above.
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31 The PPy coated filter paper, HCl, PTSA and CSA doped PPy coated filter papers will be known
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from hereafter as PPy-FP, HCl-PPy-FP, PTSA-PPy-FP and CSA-PPy-FP respectively. The
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36 polymerization reaction of pyrrole with FeCl3 is shown in supporting information (Figure S1). A
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38 video of the synthesis procedure is also given in supporting information (Video S1).
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40 2.3 Characterization of the materials
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43 The synthesized materials were characterized by ATR-FTIR spectroscopy in a BRUKER Alpha
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45 II by using the filter papers directly in the measurement without making KBr pallets. The
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47 morphology of the material was studied in SEM (LEO 1430VP) after gold coating. The
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thermogravimetric characterizations were done by a Mettler Toledo thermogravimetric analyzer.
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52 The crystallinity of hybrid filter papers were investigated from the XRD patterns recorded in a
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54 Rigaku Ultima IV powder diffractometer over the scanning range of 2θ = 5-80° with CuKα (λ =
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3 1.54 Å) radiation. To carry out the XRD, the filter papers were cut into required size and then
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6 placed in the sample holder. To perform the sensing experiment, we have used a Keithley
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10 2.4 Sensor Design and the experimental setup
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13 For preparing the sensing device the coated filter papers were cut in the size of (1.2x1) cm2 and
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16 two copper (Cu) strips were pasted at 0.5 cm apart on the filter paper. Two parallel thin Cu strips
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18 (about 1 mm width and 0.1 mm thickness) act as electrodes to measure the current conduction
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20 through the sensor. Thus, (0.5x1) cm2 of the filter paper device is exposed to interact with the
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23 analyte gas molecules. Uniform series resistance distribution was observed over the surface of
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25 PPy-FP when measured with a digital multimeter (Figure S2). The schematic representation of
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27 the proposed sensor is shown in Figure 2(a).
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52 0.5 cm , (b) Equivalent electronic circuit of the proposed sensor circuit (c) Photographs of both
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55 the sides of PPy-FP sensor device and (d) Schematic representation of the analysis setup
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3 The equivalent circuit model of the proposed sensor is given in Figure 2 (b). As the two
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6 conductors are placed parallel to each other the resistance over the filter paper will be found to
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8 be parallel to each other. Photographs of the developed device with PPy-FP are given in Figure
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10 2(c). After the construction of the sensor, the measurements were carried out in presence and
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absence of the analyte at a temperature in 28οC using a 250 ml conical flask as reported
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15 elsewhere.36 The schematic representation of the analysis setup is given in Figure 2(d). The
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17 required amount of the vapor concentration inside the glass chamber was achieved by injecting
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certain quantity of the respective liquid analyte inside the glass apparatus using a reported
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22 method.37
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24 3. Results and discussions
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26 3.1 Characterizations
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48 Figure 3: Scanning electron micrographs of (a) Blank-FP (b) PPy-FP (c) PTSA-PPy-FP (d)
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50 CSA-PPy-FP (e) HCl-PPy-FP
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53 Figure 3 (a) and (b) show the scanning electron micrographs of blank-FP and PPy-FP,
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55 respectively. The smooth cellulose fibers of the blank-FP as observed in Figure 3(a) are not
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3 visible in the SEM image of PPy-FP, rather the cellulose fibers were coated with uniform
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6 granular particles of PPy as clearly observed in Figure 3(b). It confirms that pyrrole has been
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8 polymerized on the surface of the filter paper and the PPy particles formed get uniformly
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10 distributed. Similar morphologies are observed for the PTSA-PPy-FP, CSA-PPy-FP and HCl-
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PPy-FP are shown in Figure 3 (c), (d) and (e) respectively. Almost spherical shaped particles of
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15 30 to 80 nanometer size have been observed in all PPy coated samples. The uniform distribution
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17 of spherical; PPy particles increases the surface area which favors better interactions with the gas
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molecules that aids during gas sensing. This result is similar to some previously reported studies
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22 .38,39 Moreover, It is observed that the polymer is formed on the surface of cellulose microfibers
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24 in all the dimensions. The coating on the cellulose microfibers results the increase in cellulose
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26 microfiber diameter which causes the blocking of some pores of the paper. This is also
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29 confirmed by the observed electrical connectivity between the two sides of the polymer coated
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31 paper samples. The polymer coated paper was cut into two pieces and the cross section appears
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33 uniform black in colour along with both the sides of the sample. The photographs are shown in
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the Supporting Information (Figure S3)
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39 Figure 4(a) shows the thermogravimetric analysis of the blank-FP, PPy-FP and the doped-PPy-
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41 FPs. It is observed that for the Blank-FP after the removal of excess water, the major weight loss
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43 starts at around 320οC due to the degradation of the cellulose chain. Almost 90% weight loss is
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46 observed near 400οC and it almost completely degraded at 700◦C. The important observation
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48 from the TG analysis is that, PPy-FP also follows the similar degradation pattern as that of the
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50 blank-FP, it may be because the amount of PPy coated on the filter paper is less. The major
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weight loss started for PPy-FP at around 280οC is due to the degradation of PPy chain coated on
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55 the cellulose fibres. Almost 60% weight is degraded near 400οC and about 25% weight is left in
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3 the PPy-FP at 700◦C. Similarly, HCl-PPy-FP, PTSA-PPy-FP and CSA-PPy-FP also shows the
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6 similar pattern of thermograms as that of the PPy-FP but the degradation of the PPy chain is
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8 faster for the doped-PPy-FPs than that of the PPy-FP. About 58% weight is degraded at 380οC
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10 for PPy-FP, whereas for the doped PPy-FP the degradation is around 65% at the same
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temperature. The higher thermal stability of the PPy-FP is may be due to the hydrogen bonding
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15 between the N heteroatoms and the pyrrolic H atoms of the PPy chains. But the dopant ions of
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17 the HCl-PPy-FP, CSA-PPy-FP and PTSA-PPy-FP interferes with the N heteroatoms, decreasing
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the extent of hydrogen bonding and thus results in lower thermal stability.40,41
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23 Figure 4(b) shows the XRD pattern of the blank filter paper and the PPy coated filter papers. It is
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25 clear from the plot that for the blank filter paper, a sharp peak at around 22.5ο and two relatively
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27 low intensity peaks at 16.2ο and 14.6ο and a peak at 34ο is observed. These observed peaks are
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characteristic peaks of Whatman filter papers with high crystallinity.42 Peaks are observed for all
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32 the composites in the same position without any characteristic PPy peaks. Generally, PPy is
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34 amorphous in nature and shows a characteristic broad peak at around 25ο but in this case the
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36 sharp peak of the blank-FP is already present in that range hence it may overlap (or overshadow)
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39 the amorphous broad peak of PPy. The important point observed here is that the deposition of
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41 PPy on the filter paper and doping with HCl, CSA and PTSA does not affect the crystallinity of
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32 Figure 4: (a) Thermogravimetric analysis (b) XRD patterns and (c) ATR-FTIIR spectra of the
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34 Blank-FP, PPy-FP, HCl-PPy-FP, CSA-PPy-FP and PTSA-PPy-FP respectively
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37 Figure 4(c) indicates the ATR-FTIR spectra of the blank-FP, PPy-FP and the doped-PPy-FPs. It
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is observed that the spectrum of PPy-FP shows all the characteristics peaks of PPy that are absent
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42 in the blank-FP, thus confirming the formation of PPy on the blank-FP. The characteristic peaks
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44 of cellulose corresponding to C-O and C-O-C stretching vibrations are also present in the
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46 spectrum of blank FP in the range of 1200-900 cm-1.45 But these are not clearly visible in the plot
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49 due to the comparison with PPy peaks of high intensity. To show the characteristic peaks of
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51 cellulose the ATR-FTIR spectrum of blank FP is given in supporting information (Figure S4).
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53 The characteristic peaks due to pyrrole ring vibrations is observed at around 1545 and 1530 cm 1.
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The bands in the range of 1700 cm-1 are due to C=N stretching vibration. The band near 1152
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3 cm-1 is due to C-H in and out of plane deformation. The peak near 1198 cm-1 is attributed to the
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6 C-N stretching vibrations. The bands near 1030 and 1299 cm-1 are observed due to =C-H in plane
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8 vibrations. The peak located at 773 and 912 cm-1 are assigned to C-H stretching vibrations and
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10 the peak due C-H wagging is observed near 683 cm-1. 37,38The FTIR spectra of the HCl-PPy-FP,
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PTSA-PPy-FP and CSA-PPy-FP also show all the characteristic peaks of PPy-FP. But in the
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15 doped-PPy FPs, shifting of some of the peaks are observed which may be due to interaction of
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17 the dopant ions with the PPy chain. The doping of PTSA and CSA is confirmed with the
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appearance of a new peak near 1046 cm-1 which is assigned to the sulphonic group (SO3-) of the
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22 dopant.37,46,47
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24 Elemental analysis was carried out for blank-FP, PPy-FP, PTSA-PPy-FP, CSA-PPy-FP and HCl-
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26 PPy-FP. The EDX plots are given in Figure S5 and the obtained data are shown in Table S1. The
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29 blank-FP contains only C and O and the polymerization of PPy on the blank filter paper is
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31 confirmed by the presence of N in PPy-FP along with C and O. The presence of Cl in PPy-FP
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33 can be explained as, during the chemical oxidative polymerization incorporation of the counter
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ion takes place from the reactive oxidant to help in maintaining the electroneutrality of the PPy
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38 chain. It can also be seen from the structure of PPy chain as shown in Figure S1. In PTSA-PPy-
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40 FP and CSA-PPy-FP, the presence of S along with the other elements confirms the doping of
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PPy-FP with PTSA and CSA. Similarly, in case of HCl-PPy-FP higher amount of Cl is observed
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45 due to the additional Cl- ions present as counter ions.
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47 3.2 Sensing Analysis
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50 One of the most important properties of conducting polymer is electrical conductivity. To
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measure the conductivity, I-V measurements were carried out by sweeping the current from -1 x
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55 10-4 A to + 1 x 10-4 A and the voltage developed through the sensors were recorded. The
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3 resistance of the sensor can be calculated from the slope of the I-V plot using equation (1) and
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6 then from the equation (2) the resistivity is measured. The conductivity is then calculated from
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8 the reciprocal of resistivity in S cm-1.
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11 𝑉
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𝐼
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𝐴
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20 where, “R” is the resistance in ohm (Ω), “V” is voltage in Volt (V), “I” is current in Ampere (A),
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22 “A” is the cross-sectional area in cm2, “l” is the length in cm and “ρ” is the resistivity in ohm cm.
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25 Figure 5(a) shows the I-V plots of PPy-FP, PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP. It is
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27 observed that the plots are continuous, and the voltage increases linearly with increase in the
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29 current. Thus, it confirms that the developed sensors are quite stable and follow the Ohmic
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behavior. As we know that sensing ability of PPy mostly depends on its electrical properties,
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34 thus the enhancement of conductivity is highly appreciable for improving the sensing abilities of
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36 PPy based sensors. Therefore, by expecting the improvement of sensing ability, we have doped
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PPy-FP with PTSA, CSA and HCl. Generally, the conductivity of undoped polymer is in the
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41 range of 10-6 to 10-8 S cm-1, that can be improved by doping to an order of 10 or more magnitude
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43 depending on the types of dopants.48The possible classification of conducting properties and
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45 doping state of CP based on the conductivity range is given in Figure 5(b). Doping generally
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48 increases the conductivity, as on doping the charge carriers in the polymer chain increases.
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50 Doping in conducting polymers like PPy, generates polarons and bipolarons as charge carriers
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52 and movement of these (charge carriers) along the PPy chain develops the conductivity of the
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PPy chain.49As observed in Figure 5(a), the doped PPy-FP shows a decrease in the slope i.e. the
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3 resistance decreases or the conductivity of PPy-FP increases after doping as expected. The
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6 prepared sensors follow the conductivity order HCl-PPy-FP> CSA-PPy-FP> PTSA-PPy-FP>
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8 PPy-FP. The conductivities calculated from the plot are 3.34 x 10-5, 2.49 x 10-5, 2.30 x 10-5 and
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10 1.78 x 10-5 S cm-1 for HCl-PPy-FP, CSA-PPy-FP, PTSA-PPy-FP and PPy-FP respectively. The
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slopes, intercept and standard errors and standard deviations of the measurements are given in
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15 supporting information (Table S2).
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34 Figure 5: (a) I-V plots of PPy-FP, PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP (b) Possible
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conductivity range of insulator to metallic conductor
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The net conductivity of a doped polymer depends on the mobility and concentration of charge
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42 carriers and these two factors depends on the type and structure of dopant and the method of
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44 preparation.50 In this work the method of preparation is same for all the three doped samples, so
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the type and structure of the dopant determines the conductivity. The charge carriers in a doped
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49 conducting polymer particularly depends on the doping level and the mobility is dependent on
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51 the distance barriers between two sites where the charge carriers move. Addition of HCl not only
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53 increases the doping level but also helps in generating some additional bands that improves the
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56 mobility of the charge carriers.51 Moreover, HCl is smaller in size than that of CSA and PTSA.
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3 The bulky size of CSA and PTSA causes adjacent ring distortion in the PPy chain that
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6 consequently decreases the conjugation in the chain. Again, doping with HCl helps in more
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8 compact alignment of PPy chain that creates more localized polaron and bipolaron sites and
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10 improved charge mobility.46
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13 We have studied the sensing response of PPy-FP towards 100 ppm of ammonia, acetone and
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16 ethanol vapor separately by measuring the I-V plots in absence and presence of the respective
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18 analyte at room temperature. I-V measurements are carried out by applying a constant current of
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20 -1 x 10-4 A to + 1 x 10-4 A. Definite amount of the liquid analyte was inserted to obtain the
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23 desired concentration of vapors and kept for 2 min before each measurement to homogeneously
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25 diffuse the vapor in the closed round bottom flask. It is observed from Figure 6(a) that PPy-FP
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27 shows a good response towards ammonia vapor, while the responses towards acetone and
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ethanol are less significant. There is a 43.5 %, 22 % and 14 % increase in resistance has been
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32 observed from the initial value after interaction with 100 ppm of ammonia, acetone and ethanol
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34 vapor, respectively. As, PPy-FP shows better response towards ammonia vapors, we have
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36 continued our study with ammonia vapor. It is observed that after exposing to the ammonia
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39 vapor, the resistance of PPy-FP increases i.e. the conductivity of PPy-FP decreases. As we know
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41 ammonia is a reducing gas and has free lone pair of electrons, thus upon interaction with PPy
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43 chain it donates its electrons and consequently, the PPy chain gets reduced. The practical
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46 application of a sensor is possible only if it shows reversibility. In this work, PPy-FP regains its
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48 original state within a few seconds after removing it from the contact of the analyte as can be
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50 seen from Figure 6(b).
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Figure 6: (a) I-V plots of PPy-FP upon interaction with 100 ppm of ammonia, acetone and
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35 ethanol (b) I-V plot of PPy-FP in air, ammonia and after recovery (c) I-V plots of PPy-FP for
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37 different initial concentration of ammonia vapor (d) Variation of mean of the developed voltage
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39
of PPy-FP with different ammonia concentrations
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We have also studied the effect of different initial concentration on the sensing behavior of PPy-
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45 FP by varying the concentration from 20 to 150 ppm ammonia vapor. The threshold limit for
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47 ammonia vapor is 25 ppm, thus it is more noteworthy for ammonia sensor devices to response
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49
below 25 ppm than in higher concentration. A constant current of 0 to 1 x 10-4 A was applied
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52 throughout the experiment keeping the other factors same as above. It is observed from Figure
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54 6(c) that, with increase in the ammonia vapor concentration the voltage developed through PPy-
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3 FP increases. It is because on increasing the analyte concentration the availability of the analyte
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6 molecules per unit volume for a definite number of sensing sites increases. But after a certain
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8 point, the sensor does not respond to the increasing concentration and the recovery to its original
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10 state also delayed or becomes irreversible. For PPy-FP, after 120 ppm ammonia vapor
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concentration the voltage developed through the sensor remains almost constant as shown in
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15 Figure 6(c) and (d). The standard errors, slopes, intercepts, residual sum of squares, standard
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17 deviations and the R2 values of the measurements are given in supporting information (Table
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19
S3).
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23 We have also carried out the similar experiment for PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-
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25 FP at different initial concentrations. Figure 7 (a), (b) and (c) shows the I-V plots of PTSA-PPy-
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27 FP, CSA-PPy-FP and HCl-PPy-FP in the concentration range of 10 to 100 ppm. It is observed
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that the doped PPy-FP sensors also shows the similar pattern of response as that of PPy-FP i.e.
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32 the resistance increases on exposure to ammonia. On doping, the sensing performance of the
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34 sensors has been found to be improved. Upon interaction with 100 ppm ammonia vapor
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36 concentration, the change in resistance was found to be 43.5% for PPy-FP, which has been
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39 increased up to 62.1%, 70.7% and 84.5% for PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP,
40
41 respectively. The maximum limit of detectable ammonia vapor concentration also increases after
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43 doping. PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP show responses up to 200, 230 and 300
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45
46 ppm ammonia vapor concentration respectively. Figure 7(d) shows the variation of the mean of
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48 the voltage developed through the doped-PPy-FPs with different ammonia vapor concentration.
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50 All the other parameters of the plots are given in supporting information (Table S4).
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34 Figure 7: I-V plots of (a) PTSA-PPy-FP (b) CSA-PPy-FP and (c) HCl PPy-FP for different
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36 initial ammonia vapor concentration (d) Variation of the mean of the voltage developed with
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38
different ammonia concentrations
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The calibration plots (Figure 8) of the sensors have been determined by plotting the mean of the
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44 voltage developed through the sensors with ammonia vapor concentration. The calibration plots
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46 depict the linear increase in voltage with increase in ammonia vapor concentration. The limit of
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detection (LOD) value is one of the important properties of sensors. The LOD value can be
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50
51 calculated from the calibration plots by using equation (3) 36,52,53
52
53
54 𝜎
55 𝐿𝑂𝐷 = 3.3 (3)
𝑆
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3 here, “σ” indicates the standard deviation of the response and S represents the slope of the
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39 Figure 8: LOD values of (a) PPy-FP (b) PTSA-PPy-FP (c) CSA-PPy-FP and (d) HCl-PPy-FP
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42 From the plots (Figure 8), the LOD value for PPy-FP is calculated to be 13 ppm and an
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44
improvement of the LOD values are observed for the doped PPy-FP. The LOD values calculated
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46
47 for PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP are 10, 7.9 and 5.2 ppm, respectively. Thus,
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49 HCl-PPy-FP shows the lowest LOD value and then follows by CSA-PPY-FP and PTSA-PPy-FP.
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51 From the LOD values it is clear that the developed sensors can detect a lower limit of ammonia
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54 concentration than that of the standard limit for human exposure. The slopes and all the other
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56 parameters of the calibration plots are given in supporting information (Table S5).
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3 The repeatable use of the developed sensors was also checked by performing three consecutive
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6 measurements and almost a constant voltage has been developed during the three readings. The
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8 repeatability of the sensors can also be observed by plotting % response of the respective sensors
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10 with time. To perform this experiment, a two necked conical flask was used where the sensor
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13
was mounted, and the liquid ammonia inserted was vaporized continuously by using a constant
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15 50◦C temperature inside the conical flask with the help of a hot plate as reported elsewhere.54 The
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17 sensing response was calculated by using equation (4).
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19
20 (𝑹𝒈 ― 𝑹𝒂) 𝑿 𝟏𝟎𝟎
21 % 𝑹𝒆𝒔𝒑𝒐𝒏𝒔𝒆 = 𝑹𝒂
(4)
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23
24 where, Ra and Rg are resistances of the material in air and in presence of the analyte respectively.
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26 Figure 9 shows the % Response of PPy-FP, PTSA-PPy-FP, CSA-PPy-FP and HCl-PPy-FP
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28 towards 20 ppm ammonia vapor concentration for three consecutive measurements. For PPy-FP
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31 the response is almost 15%, which has been increased to 33%, 40 % and 75% for PTSA-PPy-FP,
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33 CSA-PPy-FP and HCl-PPy-FP respectively. It is observed that % responses obtained are quite
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35 constant in all the three measurements for all the sensors.The response and recovery time of a
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37
38
sensor is defined as the time to achieve 90% of the total change in resistance during ammonia
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40 adsorption and desorption, respectively.24The average response and recovery time of the three
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42 measurements for PPy-FP is 53 and 79 s respectively. After doping, the response time has been
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44
improved, while the recovery time has been slightly increased. The response time obtained are
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47 24, 23 and 20 s and the recovery time are 88, 90 and 110 s for PTSA-PPy-FP, CSA-PPy-FP and
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49 HCl-PPy-FP respectively. As we have already discussed, doping increases the charge carriers i.e.
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51 more active sites are available for interaction with the ammonia molecule. Thus, the response
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54 time has been improved after doping. Since the interaction is more after doping it takes longer
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3 time to recover. The transient resistance curves of PPy-FP, PTSA-PPy-FP, CSA-PPy-FP and
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6 HCl-PPy-FP towards 20 ppm ammonia vapor is given in the supporting information (Figure S6).
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38 Figure 9: % Response of (a) PPy-FP (b) PTSA-PPy-FP (c) CSA-PPy-FP (d) HCl-PPy-FP
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40 towards 20 ppm ammonia vapor for three consecutive readings
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42
43 There are numerous studies on PPy based sensors in the recent years for ammonia and other
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46
gases. Although the constructed sensors of this study have comparable or more sensing response
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48 or lower LOD values than most of the PPy based sensors but there are certain PPy based sensors
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50 that can detect a lower ammonia concentration up to 0.1 ppm at room temperature. The
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constructions of most of these PPy based hybrid sensors are generally complex as well as costly
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55 and the device fabrication processes are also demanding. But in the present work, the low-cost
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3 synthesis procedure, simple fabrication process and easy to handle sensors make these sensors
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6 potential for practical applications. A table listing the LOD values, synthesis procedure and
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8 device fabrication process of various PPy based sensors towards ammonia vapor is given in
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10 Table S6 to compare our devices.
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13 3.3 Mechanism
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17
In this study, it has been observed that PPy-FP can be used for ammonia sensing and further
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19 doping with PTSA, CSA and HCl has enhanced the sensing responses. PPy is an active material
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21 and its electrical conductivity and swelling nature makes it a good sensing material for different
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23
materials such as humidity.55,56 It has been found from this study that upon exposure to
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26 ammonia, the conductivity of PPy-FP and the doped PPy-FPs decreases and on removing
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28 ammonia, the sensors regain their original state. As we know that PPy chain is consist of
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30 positively charged carriers and exposing it with ammonia, which is a reducing gas, decreases the
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33 density of the charge carriers. As reported in previous studies, two different mechanisms are
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35 possible for the decrease in conductivity of PPy chain.57 One of the mechanisms is based on the
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37 transfer of electrons from electron donating molecules like ammonia to PPy chain and a
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40
reversible redox reaction is possible as depicts in equation (5). Upon removing the contact from
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42 ammonia, the PPy chain regains its original state.
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44
𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛/𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛
45
𝑃𝑃𝑦 + /𝑋 ― + 𝑁𝐻3 𝑃𝑃𝑦0/𝑁𝐻3+ 𝑋 ― (5)
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47
48
49 The other possible mechanism involved is transfer of protons, where the ammonia molecule
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51 attacks the PPy protons and it led to the formation of ammonium ion as shown in equation (6).
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53 This process also reduces the charge carriers along the PPy chain and consequently decreases the
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56 conductivity of the PPy chain. Generally, on removing from the ammonia exposure, the
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3 ammonium ion again decomposes to ammonia and the PPy chain also regains its original state by
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6 taking a proton. In this process, the reversibility of the PPy chain to its original state depends on
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8 the bonding of the ammonium ion with the counter ion. A strong bonding will result in
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10 irreversibility of the process i.e. PPy will be not able to regain its original state.58,59
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13 𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛/𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛
14 𝑃𝑃𝑦 + /𝑋 ― + 𝑁𝐻3 𝑃𝑃𝑦0 + 𝑁𝐻4+ 𝑋 ― (6)
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16
17 Thus, the mechanism involved in the sensing process may be electron transfer or proton transfer
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19
or the combination of both. Since, in this work the sensors show a good reversibility so electron
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21
22 transfer is supposed to be the most favorable mechanism involved between the two. The
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24 schematic representation of the two processes is shown in Scheme 1. From the obtained results,
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26 we have found that among the doped PPy-FPs, HCl-PPy-FP shows the best result. Thus,
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29 conductivity plays the major role in determining the sensing performance of the reported
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31 sensors.60-62Moreover, the ease of approachability of the ammonia molecules towards the active
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33 sites of the PPy chain is favored by the smaller size of the HCl dopant as we have discussed
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35
36
earlier. While the bulky dopants like CSA and PTSA hinders the accessibility of the active sites
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38 for the analytes.46 Therefore, the formation of well distributed and ordered PPy particles, smaller
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40 size of the dopant and the higher conductivity are responsible for lower LOD value and higher
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42
sensitivity of HCl-PPy-FP.
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22 Scheme 1: Schematic representation of possible mechanism involved in NH3 gas sensing (a)
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24 electron transfer and (b) Proton transfer
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27 4. Conclusion
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30 In this work, cost effective and flexible PPy coated filter papers have been synthesized by a
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32
simple vapor phase polymerization method and further their conductivity and morphology have
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34
35 been improved by doping with PTSA, CSA and HCl. By vapor phase polymerization, it is
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37 possible to deposit PPy on a porous substrate selectively on the substrate surface without any
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39 material lost. Moreover, by this simple deposition technique, there is a possibility to control the
40
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42 amount of deposited material by simply controlling the concentration of adsorbed oxidizing
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44 agent in the blank filter paper. The synthesized hybrid filter papers have been used as ammonia
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46 sensors at room temperature and the sensing devices were developed by pasting Cu strips as
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48
49
electrodes. The PPy-FP sensor shows conductivity in the range of 1.78 x 10-5 S cm-1, whereas
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51 after doping the conductivity has been increased and HCl-PPy-FP shows the highest conductivity
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53 of 3.34 x 10-5 S cm-1. Among the sensors, HCl-PPy-FP shows the lowest LOD value of 5.2 ppm,
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which is lower than that of the human threshold limit, followed by CSA-PPy-FP > PTSA-PPy-
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3 FP > PPy-PPy-FP. The high conductivity on doping may help to enhance the sensing
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6 performance of the doped-PPy-FPs. Again, smaller dopant in HCl-PPy-FP favors good
7
8 interaction of the PPy active sites with the analyte molecules. Since the prepared sensors are easy
9
10 to handle, stable and of low cost, there is high possibility of preparing different hybrid paper
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12
13
based composite materials with improved sensing performance. Thus, this method may have a
14
15 potential future to construct low cost flexible gas sensors with different conducting polymer
16
17 based hybrid composite materials.
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19
20 Supporting Information Summary
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22
23 The readers can get the video of synthesis procedure and some other experimental details in the
24
25 supporting information. The supporting information also includes the ATR-FTIR spectrum of
26
27 blank FP, EDX plots, tables containing EDX data and a comparison list of various sensors. The
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29
30
various slopes and other parameters of the plots are also given in the supporting information.
31
32
33
34 Acknowledgement
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36
37 Sibani Majumdar thanks Council of Scientific and Industrial Research (CSIR), Government of
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India, for financial support in the form of Senior Research Fellowship. Moreover, we thank
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42 DST-SERB for financial support through EMR project (EMR/2016/005747).
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3 References:
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17 10. Zhang, D.; Li, Q.; Li, P.; Pang, M.; Luo, Y. Fabrication of Pd-Decorated Mose2
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24 11. Zhang, D.; Jiang, C.; Li, P.; Sun, Y. e. Layer-by-Layer Self-Assembly of Co3o4
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10 16. Zhang, D.; Wu, Z.; Li, P.; Zong, X.; Dong, G.; Zhang, Y. Facile Fabrication of
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3 62. Jain, S.; Karmakar, N.; Shah, A.; Kothari, D. C.; Mishra, S.; Shimpi, N. G. Ammonia
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