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polymers

Review
Chemo-Electrical Gas Sensors Based on Conducting
Polymer Hybrids
Seon Joo Park 1 , Chul Soon Park 1,2 and Hyeonseok Yoon 2,3, *
1 Hazards Monitoring Bionano Research Center, Korea Research Institute of Bioscience and
Biotechnology (KRIBB), 125 Gwahak-ro, Yuseong-gu, 34141 Daejeon, Korea;
seonjoopark86@gmail.com (S.J.P.); log71944@gmail.com (C.S.P.)
2 Department of Polymer Engineering, Graduate School, Chonnam National University, 77 Yongbong-ro,
Buk-gu, 61186 Gwangju, Korea
3 School of Polymer Science and Engineering, Chonnam National University, 77 Yongbong-ro,
Buk-gu, 61186 Gwangju, Korea
* Correspondence: hyoon@chonnam.ac.kr; Tel.: +82-62-530-1778

Academic Editor: Po-Chih Yang
Received: 10 March 2017; Accepted: 24 April 2017; Published: 26 April 2017

Abstract: Conducting polymer (CP) hybrids, which combine CPs with heterogeneous species,
have shown strong potential as electrical transducers in chemosensors. The charge transport
properties of CPs are based on chemical redox reactions and provide various chemo-electrical signal
transduction mechanisms. Combining CPs with other functional materials has provided opportunities
to tailor their major morphological and physicochemical properties, often resulting in enhanced
sensing performance. The hybrids can provide an enlarged effective surface area for enhanced
interaction and chemical specificity to target analytes via a new signal transduction mechanism. Here,
we review a selection of important CPs, including polyaniline, polypyrrole, polythiophene and their
derivatives, to fabricate versatile organic and inorganic hybrid materials and their chemo-electrical
sensing performance. We focus on what benefits can be achieved through material hybridization in
the sensing application. Moreover, state-of-the-art trends in technologies of CP hybrid sensors are
discussed, as are limitations and challenges.

Keywords: conducting polymers; composites; sensors; polypyrrole; polyaniline; polythiophene

1. Introduction
Many candidate materials have been explored for chemosensing materials, and, accordingly,
many different transduction mechanisms have been developed [1]. Conducting polymers (CPs) have
been studied extensively since their discovery in 1977 [2]. In 2000, Heeger, MacDiarmid, and Shirakawa
jointly received the Nobel Prize in Chemistry, which reignited considerable interest in CP research.
At the beginning of 2000, so-called nanoscience and nanotechnology were also hot topics in research
worldwide. Many unique and surprising properties of materials were found at the nanoscale. Naturally,
various CP nanomaterials have been developed and have novel and fascinating properties [3]. CPs are
a new class of electronic materials and are completely different from most existing inorganic electronic
materials. Simply, CPs have the advantages of tunable electrical/electronic properties, easy synthesis,
structural diversity, flexibility, and environmental stability (e.g., non-corrosive) [4–6]. These advantages
allow CPs to be explored as alternatives to the inorganic electronic materials that are used in diverse
application fields. Of course, CPs have intrinsic limitations, such as a relatively low conductivity
and a lack of consistency in properties. Therefore, there has been considerable effort to couple CPs
with other heterogeneous species, which has resulted in many remarkable research findings [7–10].
Regarding sensor applications, the hybridization of CPs with other components has been conducted

Polymers 2017, 9, 155; doi:10.3390/polym9050155 www.mdpi.com/journal/polymers

Polymers 2017, 9, x FOR PEER REVIEW 2 of 24

Polymers
with 2017,
other 9, 155
components has been conducted to improve the sensitivity and selectivity [3,4]. 2 of 24
For
example, CPs can achieve sensitive responses to various external stimuli, including chemical species,
at to
relatively
improvelow temperatures,
the sensitivity and which corresponds
selectivity [3,4]. For to one of the
example, CPsgreatest
can achieveadvantages
sensitiveofresponses
using CPs to as
the sensing
various material
external [11,12].
stimuli, However,
including chemical unfortunately, the sensitive
species, at relatively signal transduction
low temperatures, of CPs is
which corresponds
available for all external stimuli, not just a target species. Thus, it is not easy
to one of the greatest advantages of using CPs as the sensing material [11,12]. However, unfortunately, to achieve selective,
specific responses
the sensitive signalto transduction
a target species using
of CPs only purefor
is available CPs.
all To overcome
external thisnot
stimuli, limitation, thespecies.
just a target chemical
structure
Thus, it of is CPs can be
not easy modified
to achieve or functional
selective, specificheterogeneous
responses to amaterials can be
target species coupled
using onlywith
pure CPs.
CPs. A
variety
To overcomeof heterogeneous
this limitation, the materials, including
chemical structure quantum
of CPs dots, two-dimensional
can be modified inorganic
or functional heterogeneous
nanomaterials,
materials can and nanocarbons
be coupled with (e.g.,
CPs. fullerene,
A varietycarbon nanotubes, graphene),
of heterogeneous have beenquantum
materials, including combined
dots,
with CPstwo-dimensional inorganic
to achieve synergistic nanomaterials,
effects [7-10]. and nanocarbons (e.g., fullerene, carbon nanotubes,
graphene),
Figure 1haveshows beenthecombined with CPs
latest research trendto achieve
in CPs.synergistic
CPs have effects
attracted [7–10].
increasing interest over the
Figure 1 shows the latest research trend in CPs. CPs have attracted
last decade, and the proportion of hybrids or composites in CP research has continuously increasing interest over the
increased.
Thelastimproved
decade, and the proportion
properties of hybrids
of the CP hybridsorand composites
compositesin CP
haveresearch
madehas continuously
it possible increased.
to fabricate new,
The improved properties of the CP hybrids and composites have made
high-performance sensors. Many efforts have been devoted to the development of various kinds of it possible to fabricate new,
high-performance
sensors with different sensors. Many efforts
transduction modes have been
using thedevoted
hybridstoand
the composites
development of various
[13,14]. kinds
In this of
review,
wesensors
cover thewithelectrical
differenttransduction
transduction of modes using the
CP hybrids to hybrids and composites
detect gas-phase [13,14].
chemical In this
species, and review,
discuss
we cover the electrical transduction of CP hybrids to detect gas-phase chemical species, and discuss
the transduction mechanisms according to the type of hybrid. Several comprehensive review articles
the transduction mechanisms according to the type of hybrid. Several comprehensive review articles
have been published regarding CP-based sensors [12-14]. Therefore, we focus on what benefits can
have been published regarding CP-based sensors [12–14]. Therefore, we focus on what benefits can
be obtained in using CP hybrids in chemo-electrical sensor applications. In addition, examples are
be obtained in using CP hybrids in chemo-electrical sensor applications. In addition, examples are
introduced to present the recent research trends, most of which have been conducted since 2012.
introduced to present the recent research trends, most of which have been conducted since 2012.

Theproportion
Figure1.1.The
Figure proportionofof articles
articles published on
on hybrids/composites
hybrids/composites in
inthe
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2. 2.
CPCP Chemosensors
Chemosensors
CPs, including
CPs, including polypyrrole
polypyrrole (PPy),
(PPy), polyaniline
polyaniline (PANI),
(PANI), polythiophene
polythiophene (PTh),
(PTh), poly(3,4-
poly(3,4-
ethylenedioxythiophene(PEDOT),
ethylenedioxythiophene (PEDOT), and and their
their derivatives,
derivatives, as as shown
shown ininFigure
Figure2,2,have
havereceived
received
increasing attention because of their easy fabrication and inherent physical properties,
increasing attention because of their easy fabrication and inherent physical properties, biocompatibility,
and optical properties.
biocompatibility, Their main
and optical structures
properties. consist
Their mainof structures
single and double
consistbonds, which
of single andare conjugated
double bonds,
π–electron systems. Although these conjugated polymer chains have conductivity,
which are conjugated π–electron systems. Although these conjugated polymer chains have their values
are very low.their
conductivity, To values
increaseare
their
veryconductivity, a doping
low. To increase theirprocess by redox
conductivity, reaction process
a doping or protonation
by redox
is needed to remove the electrons on the backbone of the CPs. Positive charges in a CP backbone
reaction or protonation is needed to remove the electrons on the backbone of the CPs. Positive charges
are accomplished as a charge carrier, leading to conducting properties (conductivity, ca. 100 to
in a CP backbone are accomplished as a charge carrier, leading to conducting properties 6(conductivity,
105 0S·cm–15) [4,13]. In comparison, copper has a conductivity of approximately 10 S·cm–1 at
ca. 10 to 10 S·cm–1) [4,13]. In comparison, copper has a conductivity of approximately 106 S·cm–1 at
room temperature. The unique electrical properties of doped CPs enable energy and electrical

resulting interaction changes in the the decreased movement charge distribution of theresulting in PPy. including ethanol and by acetonitrile. [35] demonstrated charge behavior transportbetween behaviornanostructured PEDOT and chemical between nanostructured PEDOT gases.15–17]. CP chemo-electrical sensors function by analyzing physical or electrochemical signals such as adsorption of gas and and charge charge transfer transfer between between gas gas molecules molecules and and CPCP backbones. chemosensors offer attractive advantages such as room temperature operation [26–28]. 9. the backbone can interact carboxyl group (−COOH)with phosphoryl of the PPy groups backbone of dimethyl methylphosphonate can interact with phosphoryl(DMMP) groups gas. CP-based attractive advantages such as room temperature operation [26–28]. and the extrinsic factors (e. Recently.g. In this review. and easy fabrication [34].g. synergetic effects we provide and enhanced an overview capacity for gas interaction [1. were used PEDOT for ammonia were membranes gas sensors used because. and acetonitrile. contact resistance) originate from in a single nanoparticle. facile functionalization [29–31]. remain their a challenge.10. The performance nanoparticle–metal of PEDOT electrodes. This (DMMP) gas.33].have improved although suchthe advantages sensing performance of chemosensors. inorganic low sensitivity or organic and selectivitymetal stilloxide/CP remain a hybrid materials challenge. the chemosensors of the can be improved chemosensors can by controllingbythe be improved charge transfer controlling the charge behavior transferbetween behaviorgas molecules between and CPs. However.14]. sensing performance. charge carrier holes along in the decreased the polymer movement chain. Compared to conventional systems owing to their excellent electrochemical properties with target analysis. interactions The resistance of the between PPy and PPy increased withDMMP. 155 3 of 24 Polymers 2017. intrinsic andby extrinsic intrinsicfactors.or in aintra-chains single nanoparticle. mechanisms. Kwonthe preparation method et al. facile structural diversity [32. The unique electrical properties of doped CPs enable energy and electrical 106 S·cm–1 at room temperature. The conductivity the the increasing PEDOT membranethickness of thewith increased PEDOT the membrane. The unique electrical properties of doped CPs enable energy and applications [4. Based on the sensing sensing mechanisms. structural diversity [32. Kwononetthe dependent al. [36] reported of thethe PEDOT membrane preparation method ofby thevapor PEDOT deposition membrane polymerization. backbones. limitations such as Recently.factors The (e. redox reaction with they easily electron-donating underwent a redox molecules such as reaction with NH3 . by vapor depositionThe PEDOT membranesThe polymerization. Chemical structures of of representative representative CPs. which is of dimethyl similar to nerve agent methylphosphonate gases.Yoon and CPs. the effectthe In addition. high the same sensitivity for NH group demonstrated 3 monitoring.. In particular. This in PPy.10.have been applied inorganic in high-performance or organic metal oxide/CP chemosensors hybrid materials owing haveto been their synergetic applied in effects and enhanced high-performance capacity for owing chemosensors gas interaction to their [1. of functional same group groups on the selectivity demonstrated the effect of CP of sensors..Polymers 2017. Figure Figure 2. [35] demonstrated charge transport et al. including and chemical ethanol gases.13.thethe sensing performance.such assuch sensitivity and selectivity. and easy fabrication [34]. In this review. In particular. [36] two reported factors. of the PPy For example. Chemical structures 2.13. sensors they easily because. increasing althoughbetween interactions such advantages PPy and of CP transducers DMMP. for ammonia havinggas a hole carrier. The functional groups can make CPs chemically specific to target functional groups on the selectivity of CP sensors.such interactions the as carboxyl hydrogen group (−COOH) bonding. PEDOT membrane.g. as sensitivity and ofselectivity. CPs. The sensors was highly performance dependent of PEDOT sensorson thehighly was two factors. we provide an overview of the state-of-the-art technologies of CP hybrids for gas chemo-electrical sensors and discuss their limitations and challenges. . The functional groups can make CPs chemically species via intermolecular interactions suchspecies specific to target as hydrogen bonding.33]. oxidation level)with the chargewith are associated transport between the charge the inter- transport or intra-chains between the inter. functionalization [29–31]. interaction changes which is similar the charge to nerve agentdistribution gases. CPs have been used as the active layers in gas-sensing systems electrical applications [4. CPs have been used as the active layers in gas-sensing owing to their excellent electrochemical properties with target analysis. of the Thecarrier charge resistance holesofalong the PPy the increased with increasing polymer chain. 155 3 of 24 room temperature. gas molecules Yoon et al. However. oxidation intrinsic factors level) are associated (e.15–17]. of CP transducers have their limitations improved the such as sensing low sensitivity performance ofand selectivity still chemosensors. leading to In addition.. For via intermolecular example. contact resistance) originate from the interaction between nanoparticle–nanoparticle the interaction or nanoparticle–metal between nanoparticle–nanoparticle orelectrodes. leading toofhigh increasing thickness the sensitivity for NH3 monitoring.g. CP-based chemosensors offer conventional chemical sensors using metal oxides or other inorganic materials [18–25]. and the extrinsic factors (e.. Compared to chemical sensors using metal oxides or other inorganic materials [18–25].14]. The intrinsic and extrinsic factors. 9. The conductivity electron-donating molecules of the suchPEDOT as NHmembrane increasedofwith 3. underwent having a holea carrier.

However. The nanocomposites showed increasing real impedance on exposure to acetone. However. the hybrid was loaded on a polyethylene terephthalate (PET) film to form a flexible sensor. [41] presented a WO3 nanoparticle/water-soluble PANI particle composite doped on dodecylbenzenesulfonic acid at different mass ratios. [40] proposed sensing the trace amounts of toxic NO2 gas at room temperature based on SnO2 /PANI heterostructure nanocomposites. metal oxide semiconducting sensors have a lack of flexibility and selectivity and must be operated at high temperatures (more than 200 ◦ C). the sensing response toward CO gas by the sensor was affected by humidity. The PANI nanofibers were prepared using a template technique. [38] reported a MoO3 /PANI hybrid loaded on a PET film. The WO3 /PANI nanocomposites were deposited onto interdigitated electrodes and characterized using electrochemical impedance spectroscopy in air and in acetone vapor. [42] developed a new route for the synthesis of PANI nanofibers in the presence of various amounts of ZnO. By contrast. Talwar et al.1. However.Polymers 2017. Quan et al. structurally simple.1. in which the ZnO nanoparticles were used as a template. the SnO2 /PANI hybrid sensor has flexible. Inorganic-CP Hybrids 3. and portable characteristics. [37] presented a network structure of a PANI/SnO2 hybrid that was synthesized by chemical oxidative polymerization and utilized ZnO nanorods as a template. cost efficiency and sensing of most toxic gases [18–23]. great selectivity and a linear response at room temperature. Accordingly. single CPs exhibit relatively low sensitivity to chemicals. CP Hybrids 3. The sensor exhibited sensitivity 20 times higher than pure PANI to 10 ppm trimethylamine (TEA). Recently. however. economical. the decreases in film resistance resulted from low WO3 nanoparticle loadings and low acetone concentrations. Sensor #1 exhibited significantly high selectivity toward NO2 (50 ppb) gas. Metal Oxide Hybrids Metal oxide semiconducting sensors have been widely developed and applied for the detection of chemical molecules because of their structural stability. This effect is caused by the balance of charge carriers in the film. causing high power consumption. which were synthesized by the electrochemical deposition of PANI of various thicknesses on nanocrystalline SnO2 prepared by the Langmuir-Blodgett method. which achieves great sensing performance of the novel sensing material over the constituent counterparts.1. a possible strategy is to combine a CP with a metal oxide. Sen et al. In addition. and short lifetimes [24. The sensors can detect 10 ppm acetone vapor at room temperature. safety hazards. 155 4 of 24 of the state-of-the-art technologies of CP hybrids for gas chemo-electrical sensors and discuss their limitations and challenges. A significant decrease (approximately 50%) in response intensity was observed for increased humidity level. with response and successive recovery at room temperature without any carrier gas flow or ultraviolet (UV) irradiation.25]. The Co3 O4 nanoparticles were prepared by an ultrasound-supported coprecipitation technique and then incorporated into the PANI matrix. and the sensing response to ammonia (NH3 ) gas . [39] demonstrated carbon monoxide (CO) gas detection using Co3 O4 /PANI nanocomposites at room temperature. environmental stability. 3. whereas sensor #2 showed a high response and recovery toward SO2 (2 ppm) gas. and sensitive response to chemical molecules at room temperature. Bai et al. The sensor exhibited high selectivity to CO gas at room temperature and obtained a significantly high response to 75 ppm CO gas concentration for 40 s. CP-based sensors have attracted enormous interest because CPs have advantages such as easy synthesis. Hicks et al. and sensor #2 contacted the PANI film (Figure 3). 9. facile integration. Betty et al. The thick PANI films were deposited on an alumina substrate. which was synthesized by an in situ chemical oxidation polymerization method and attained a good linear response to TEA concentrations from 10 to 100 ppm at room temperature. Two types of sensors were prepared with in-plane gold: sensor #1 contacted one each of SnO2 and PANI.

Lee et al. and were then fabricated through heat treatment. When the gas sensors were exposed to ammonia. [40]. and heat treatment. These nanocomposite films were fabricated by spin-coated assisted deposition in conjunction with a release technique to detach them from the substrate. Shin et al. To decorate FeOOH nanoneedles on the PPy surface. [47] described multidimensional FeOOH nanoneedle-decorated hybrid PPy nanoparticles (PFFs). The core-shell nanohybrids demonstrated an increased recovery toward SO2 (2 ppm) gas. toward NO2 (50 ppb) gas. DMMP. A significant decrease (approximately 50%) in response 9. which were adsorbed on the PPy nanoparticle surface followed by thermal stirring to grow nanorods without aggregation. PANI would change from the nanocomposites. which were synthesized by the electrochemical deposition of PANI of various conducting emeraldine salt form to the insulating emeraldine base form via deprotonation. Schematic of of the the Si/SnO -PANI heterostructure Si/SnO22-PANI heterostructure gas gas sensor sensor with with gold gold contacts contacts [40]. [46] presented a sensor of toxic NO2 gas at room temperature based on multidimensional porous Fe2 O3 nanorod-decorated carbon nanoparticles (MPFCNPs). which were synthesized by a dual nozzle electrospray and heat stirring process. The nanocomposite films could transfer onto substrates due to their high conformability. FeOOH particle-decorated PPys (E-PPy) were fabricated as starting materials. PPy nanoparticles with FeOOH nanorods were synthesized using electrospun Fe3+ ions. Furthermore. [43] described a room-temperature NH3 gas sensor with high response and long-term sensor #2 contacted the PANI film (Figure 3). with response and successive recovery at room temperature without any The core-shell nanocomposites were synthesized by in situ polymerization with different weight carrier gas flow or ultraviolet (UV) irradiation. The to a p−n junction formed by the intimate contact between CeO2 and PANI (Figure 4). The nanocomposites showed accommodate itself and enhance the mechanical strength and chemical stability of the sensors by increasing real impedance on exposure to acetone. which is suitable for asthma monitoring. with the porous structure created in the Fe2 O3 nanorods by hydroxyl group decomposition. The response of the MPFCNP sensor was highly sensitive (1 ppm). Zampetti et al. including CeO2 nanoparticles coated by cross-linked PANI hydrogel (CeO2 @PANI. [44] demonstrated a hybrid sensor consisting of a nanofibrous layer of TiO2 coated with a thin film of PEDOT:polystyrene sulfonate (PEDOT:PSS). An optimal thicknesses on nanocrystalline SnO2 prepared by the Langmuir-Blodgett method. The stoichiometric oxidation of NO into NO2 by CrO3 enabled the conductometric sensor to detect NO2 gas concentrations as low as 1 ppb. The sensor exhibited high selectivity to CO gas at room temperature and obtained a significantly high response to 75 ppm CO gas concentration for 40 s. which would be attributed PANI particle composite doped on dodecylbenzenesulfonic acid at different mass ratios. Schematic Figure 3. Sensor #1 exhibited significantly high selectivity stability. Two types of sensing response was obtained with PANI nanofibers in the presence of 30 wt % ZnO powder. The E-PPy particles were arranged by dual-nozzle electrospray because Fe3+ dispersed on the surface reacted with OH− in the collector solution without the aggregation of each particle. Polymers sensor was affected by humidity. The Co3O4 nanoparticles were prepared by an ultrasound-supported coprecipitation technique and then incorporated into the PANI matrix. which helped the PANI electrochemical impedance spectroscopy in air and in acetone vapor. Their response to humidity was found to increase with increasing nanoparticle concentration (Figure 5). which was investigated as a potential sensing material for NO. Hicks et al. thermal stirring. 155 5 of 24 intensity was observed for increased humidity level. [40] proposed sensing the trace amounts of toxic NO2 gas at room temperature based on SnO2/PANI heterostructure was investigated. Betty et al. thus preserving their functionalities. Furthermore. thickness. which were fabricated using a dual-nozzle electrospray. [45] prepared free-standing nanocomposite ultrathin films based on PEDOT:PSS and embedding iron oxide nanoparticles. PEDOT:PSS and PEDOT:PSS/iron oxide nanoparticle nanofilms were investigated as resistive humidity sensors.Co3O4/PANI nanocomposites at room temperature. resulted from low WO3 nanoparticle loadings and low acetone concentrations. sensors were prepared with in-plane gold: sensor #1 contacted one each of SnO2 and PANI. magnetic and magneto-optical activity. and conductivity characterizations. However. sensitivity improved with decreasing diameters of the MPFCNPs and increasing Fe2 O3 nanorod lengths. the sensing response toward CO gas by the 2017. CPA). The hybrid PPFs detected a nerve gas agent. the decreases in film resistance preventing a “swelling effect” in high relative humidity (Figure 4Aa).5 to 50 ppm at room temperature. [41] presented a WO3 nanoparticle/water-soluble response to NH3 concentration from 6. The effect of the addition of iron oxide nanoparticles on the structural and functional properties of the PEDOT:PSS nanofilms was inspected through topography. Figure 3. whereas sensor #2 showed a high response and ratios of CeO2 nanoparticles and aniline. WO3/PANI nanocomposites were deposited onto interdigitated electrodes and characterized using the stability was examined in the presence of phytic acid working as a gelator. However. at room temperature with high . Taccola et al. and Wang et al.

and 100 to CPA4 ppm of NH 50. 2. 75.5. CPA2.5. and the resulting composites of NH3 . 4. (B) (a) Response curves of CPA0. 75. 6 of 24 FigureFigure 4. 75. and 16 ppm of CeO to aniline was varied as 0. (b) and 3100 fitted ppm of NHcurves (solid lines) 3.5 lines) to CPA6 upon and experimental sequential results (scattered exposure points) of of 50. Reprinted with permission from [43].(b)(b) SEM SEM image of CPA4 shows a well-defined core/shell structure in an optimal CeO2/aniline ratio. weight ratio 4. ratio of CeO2 CPA2. (c) image of CPA4 shows a well-defined core/shell structure in an optimal CeO2 /aniline ratio. The feed weight 2 were denoted as CPA0. CPA4.PANI hydrogel. .5. (c) reversible the 3transient responseand reproducible of sequential responses exposure to 2. sensors.5.(a) (b) Response fitted curves curves (solid of CPA0. and 6. CPA4. were denoted as American Chemical Society. (d) Response concentrations of NH3and response . and CPA6. 4. to aniline wasandvaried CPA6. and Reprinted 6. respectively. The minimum detection level of PFFs was as low as 0. 8. which was higher than that of other hybrid materials Polymers 2017. andof100 NHppm ofisNH 3.1 ppb. . Copyright composites 2014. sequential exposure Thetofeed2. grown75. 8.5 to CPA6 upon sequential exposure of 50. 9.Polymers 2017. CPA0.ofand CPA4 to different 16 ppm of NH3. 9.5. andwith thepermission resulting from [43]. 4. (A)4. as 0.(a) (A) (a) Schematics Schematics of theof fabrication the fabrication of PANI of PANI hydrogel/CeO2core/shell hydrogel/CeO 2 core/shell gas gas sensors. 155 (Figure 6). and 100 ppm of NH (B)3. (c) reversible andand experimental reproducible results responses (scattered of CPA4 points) of to different CPA4 concentrations to 50. Inset is thetime of CPA4 transient to various response ofNH 3 concentrations. (c) SEM SEM image of CPA0. which exhibits a three-dimensional network structure through a homogeneously image of CPA0. 2. 155 6 of 24 sensitivity. respectively.5. American Chemical Society. (d) Response and response time of CPA4 to various NH3 concentrations. Copyright 2014. Inset . which exhibits a three-dimensional network structure through a homogeneously grown PANI hydrogel.

PFF_10) at of gas at temperature.0. picture (h) A and picture(i) the and structure (i) the of structurethe samples of the used samples for used humidity-sensing for humidity-sensing studies. bar paper fiber structure to which the nanofilm conforms (scale bar 50 μm). Reversible and reproducible responses are measured at aa nanoparticles at room Reversible and reproducible responses are measured at at room temperature. Nanofilms Nanofilms collected onto onto collected collected onto (c) Teflon (c) Teflon screw. blue.5. 5).Polymers 2017. 1. from [45]. (e) plastic tube.0. [45]. and 10.5.5. pristine PFF_2. PFF_0. red. and (d) recovery PFF_10) at 10 times 10 ppb ppb of hybrid of DMMP DMMP gasPPy nanoparticles at room room (yellow.PFF_10). and and (f)and tube. temperature. AmericanPFF_2. PFF_2. PFF_0.blue. American Chemical Society.x. E_PPy. which which could could be be attributed attributed to to the the formation formation of of aa p−n p−n junction junction between between TiO TiO22 and and . PEDOT:PSS/iron oxide nanoparticle oxidenanoparticle composite nanoparticlecomposite nanofilms compositenanofilms transferred nanofilmstransferred transferredto to various tovarious substrates: varioussubstrates: substrates: (a) (a) freestanding freestanding PEDOT:PSS/Nanoparticle PEDOT:PSS/Nanoparticle 55 nanofilm nanofilm (2(2 cm cm ×× (a) freestanding PEDOT:PSS/Nanoparticle 5 nanofilm (2 cm × 1 cm) floating in water after 1 1cm) cm) floating floating in in water water after PVA afterPVA PVA dissolution. detection mechanism of hybrid FeOOH nanoneedles on the PPy nanoparticles nanoparticles at room temperature. (a) (a) DMMP DMMP gas gas detection detection mechanism mechanism of of hybrid hybrid FeOOH FeOOH nanoneedles nanoneedles on on thethe PPy PPy Figure 6. Reprinted with permission from [47]. PFF_2. constant valueReversible current value and reproducible −6 A) with (10−6 various amountsresponses amounts and are measured types of FeOOH FeOOH at a constant on the current the PPy PPy value surfaces. of (a) red.0. 2013. American Chemical Society. Copyright 2013. room temperature. The TiO2@PPy-GN nanocomposites demonstrated a good response to NH3 gas at room temperature. 155 7 of 24 Polymers 2017. (yellow). and PFF_10.5. red. Reprinted Reprinted with permission from −1 x mg mL iron concentration of mL (x =nanoparticles 0.5. PEDOT:PSS/iron PEDOT:PSS/ironoxide 5. 155 7 of 24 Polymers 2017. Society.screw. al. 2. and 10. response PFF_5. red. 9.0 wt Reprinted % permission with FeOOH precursors [47]. Chemical and PFF_10. (black). (e) PFF_5. permission 5).0. respectively. green. 10. The samples were referred to as Thesamples samples were were referred referred toto as as PEDOT:PSS/Nanoparticles x. 0. The (c) blue. Figure 5. upon(yellow). 1. with Copyrightfrom permission 2013. The TiO 2@PPy-GN nanocomposites demonstrated a good response to NH3 gas at polymerization. The and PFFs with PFF_10. [48] [48] prepared prepared aa composite composite ofof PPy PPy and and graphene graphene nanoplates nanoplates (GNs) (GNs) decorated decorated with with TiO22 nanoparticles TiO nanoparticles (TiO (TiO22@PPy-GN) @PPy-GN) by by aa sol–gel sol–gel process process combined combined withwith in in situ situ chemical chemical polymerization. (c) Teflon screw.0 wt % FeOOH precursors are denoted as PFF_0. sequential and exposure (b) hybrid toPFF various DMMP concentrations nanoparticles (pink.5.5. structure of the samples used for humidity-sensing studies. and (b) hybrid PFF nanoparticles (pink. μm). PFF_2. blue. PFF_0. Chemical [45]. American Chemical Society.The PFF_10). Chemical American Society. blue. blue. withPFF_2. and green. 1. Figure 6. Society.0. 5. − 6 (10 A) with variouschanges amounts and types ofexposure FeOOH to onvarious the PPy surfaces. 9. (h) A picture and (i) the 50 (h) A µm). and(c)(b) hybridand response PFF(d)nanoparticles recovery (pink. Copyright 2013. PFF_5. (a) DMMP gas temperature. 5. (e) PFFs 0.5. denoting films prepared using PEDOT:PSS/Nanoparticles x. Nanofilms µm). E_PPy. Reprinted with permission from Copyright 2013. PFF_2. red. PFF_10). Normalized resistance Normalized Normalized resistance resistance upon changes upon sequential sequential exposure to DMMP various DMMP concentrations concentrations of (a) of (a) pristine pristine changesE_PPy (black). E_PPy green. green. 0. Reprinted (x 0.(black). dissolution. 9. (g) SEM PDMS. Xiang et Xiang et al. (d) paper. 2. constant current (10 A) with various and types of on surfaces. (e) plastic (d) paper. (g) SEM imageimage (g) image SEM of the of theofedge edge of aa nanofilm the edge of nanofilm of a nanofilm collected on paper collected collected on paper on papershowing the showing showing the paper the fiber paper structure fiber to structure which to the which nanofilm the conforms nanofilm (scale conforms bar (scale 50 μm). green. PFF_5. PFF_2. (e) plastic tube. Copyright American 2013.0.5. PFF_5. denoting films prepared using a colloidal solution with of PEDOT:PSS/Nanoparticles denoting films prepared using a colloidal a colloidal solution with solution a with concentration aa concentration − 1 of oxide xx mg iron oxide mg nanoparticles mL−1 iron oxide nanoparticles (x == with 0. (f) flexible flexible PDMS. (e) The TheE_PPy. times of PFF_0.0 wt % PFF_10) FeOOH at 10 ppb precursors of DMMP are gas denoted at as room temperature. PFF_5. 5). are from [47]. nanoparticles PFF_5. (d) paper. green. PFF_2. The studies. (yellow. hybrid PPy red.(f) flexible PDMS. (b) SEM micrographs showing PEDOT:PSS/Nanoparticles 1 nanofilm collected onto aa dissolution. PFFs with 2. PFF_5. The (c) response and (d) recovery times of hybrid PPy nanoparticles (yellow. 5. PFF_5. E_PPy (yellow). denoted Copyright as PFF_0. respectively. (b) (b) SEM SEM micrographs micrographs showing showing PEDOT:PSS/Nanoparticles PEDOT:PSS/Nanoparticles 1 nanofilm 1 nanofilm collected collected onto onto steel a steel steel mesh meshmesh (scale (scale barbar (scale bar 100100 100 μm). respectively. Figure 6. 155 7 of 24 Figure Figure 5.

respectively. which could be attributed to the formation of a p−n junction between TiO2 and PPy-GN. [56] described a chemiresistive sensor based on PANI nanofibers decorated with Au nanoparticles. [54] reported Pd-decorated nanoporous poly(aniline-co-aniline-2-sunfonic acid):poly(4-styrenesulfonic acid) (P(ANI-co-ASA):PSS) nanostructures fabricated by a novel method and demonstrated the sensing response to hydrogen (H2 ) gas. The TiO2 @PPy-GN nanocomposites demonstrated a good response to NH3 gas at room temperature. The PTh/WO3 hybrids exhibited higher thermal stability than pure PTh and demonstrated a high response and good selectivity for detecting NO2 gas at ppm levels. good response. 155 8 of 24 Xiang et al. and n-propanol. [50] prepared PTh/WO3 organic–inorganic hybrids. The 20 wt % PTh/WO3 hybrid demonstrated high response and good selectivity to NO2 gas at <90 ◦ C. Metal Hybrids Patil et al. which was demonstrated to detect volatile sulfur compounds of human . Liu et al. The urchin-like PPy nanoparticles were tested in various hazardous chemical gas sensors at room temperature.2. Moreover. the nanocomposite films could reversibly detect NH3 concentrations of 1 ppm or less. but the nanocomposite thin films improved the sensor response and response kinetics. which were synthesized by a dual-nozzle electrospray and vapor deposition polymerization method. Huang et al. 3. and the hybrids had higher thermal stability than pure PTh. and they showed a sensing response to NH3 . The SnO2 hollow sphere/PTh hybrids demonstrated a powerful synergistic interaction between the SnO2 hollow sphere and PTh. The nanocomposite thin films and pure PANI exhibited a selective response toward NH3 . higher sensitivity and much faster response than PPy-GN under the same conditions. 9. the TiO2 @PPy-GN thin film exhibited enhanced NH3 sensing properties. showing high selectivity. The response and recovery time of the nanocomposite film were 50 ppm of NH3 and 7 s. The hybrid composite exhibited higher response for NO2 sensing at <90 ◦ C than pure PTh and WO3 sensors. which resulted in enhanced interactions with H2 gas. Cho et al. The porous Pd-decorated P(ANI-co-ASA):PSS nanocomposites achieved a detection limit of 5 ppm for H2 gas at room temperature.Polymers 2017. Xu et al.1. [53] prepared a thin film of Cu nanoparticles intercalated with PANI nanocomposites deposited by in situ oxidative polymerization of aniline in the presence of various concentrations of Cu nanoparticles at room temperature. and the 10 wt % PTh/WO3 hybrid exhibited the highest response at 70 ◦ C. The PANI/Ag nanowire composite surfaces were flexible and optically transparent. and they efficiently exhibited a greater sensitivity for NH3 due to their large surface area and 10 to 100 times higher minimum detectable levels of common analytes. [48] prepared a composite of PPy and graphene nanoplates (GNs) decorated with TiO2 nanoparticles (TiO2 @PPy-GN) by a sol–gel process combined with in situ chemical polymerization. [55] presented PANI/Ag nanowire composites fabricated by chemically polymerizing PANI on top of dispersed Ag nanowires. acetone. These PANI/Ag nanowire composites demonstrated selective sensing of NH3 versus ethanol. The PTh/WO3 hybrids with different mass fractions of PTh were acquired by mechanically mixing the prepared PTh and WO3 . Guo et al. resulting in much higher sensitivity compared to the non-porous counterpart. and a comparatively short recovery time to NO2 gas at 90 ◦ C. Both P(ANI-co-ASA) and PSS supplied sufficient sulfonic acid (–SO3 H) groups to efficiently anchor Pd nanoparticles. Moreover. The pores were 10−30 nm in diameter. Organizing the PANI/Ag nanowire composite surface as chemiresistors led to resistance measurements that could detect 10 ppm of NH3 with an increase in the resistance. [52] prepared PTh/nanosized WO3 organic–inorganic hybrids fabricated by a chemical oxidative polymerization and colloidal chemical method. The enhanced gas performance was due to the high surface area of the hybrids and the p–n heterojunction arranged between p-type PTh and n-type SnO2 hollow spheres. and the enlarged effective surface area enabled interaction with H2 gas. which were synthesized by an in situ chemical oxidative polymerization technique. The response of the PTh/WO3 hybrids was influenced by the PTh mass fraction. Lee et al. [49] presented urchin-like PPy nanoparticles with different diameters. Bai et al. [51] reported SnO2 hollow sphere/PTh hybrid materials that were fabricated by an in situ chemical oxidative polymerization method.

which were fabricated using in situ reduction of [H3 O]2 [PtCl6 ] by the amine group in the pyrrole monomer and oxidation of pyrrole to form PPy. which is 10 to 100 times more sensitive than other nanocomposite-based chemical sensors. The PANI nanofibers horizontally orientated on the insulating gap region of an interdigitated electrode were fabricated by template-free electrochemical polymerization. Three types of ultrathin CPPy skins were fabricated to control the amount of Pd nanoparticles.5 ppm) gases. toluene and hexane. 1:30 (PCCN2). followed by chemical reduction of palladium precursor (PdCl2 ) in the solution. with response and recovery times of 14 and 148 s.Polymers 2017. showing increasing sensor performance compared to pure PPy as a result of the functionalization of Au nanoparticles on PPy. The sensing ability of the fabricated Au/PANI electrode on volatile sulfur compounds contained in human breath was proved by their response upon exposure to the exhaled breath of a healthy volunteer after ingesting raw garlic. Gaikwad et al. Control experiments revealed that lysine plays an important role in the synthesis of homogeneous Au/PPy nanocomposites. were integrated as transducers in a field-effect transistor (FET) system. [31] fabricated porous Pd-coated carboxylated PPy (CPPy) nanoparticles that detected hydrogen gas. [59] reported a facile synthesis of Pt/PPy nanocomposites. The Au/PPy nanocomposites exhibited great potential for detecting NH3 gas at room temperature. The reactions were carried out at various temperatures to alter the degree of reduction of platinum precursor and doping of PPy with a Pt(II) chloro complex. The nanocomposite depended on the size of Pd nanoparticles and the morphology of the nanocomposite film. The fabricated Pt/PPy nanocomposite gas sensors were investigated for their sensing response to liquefied petroleum gas (LPG). 155 9 of 24 breath. in which 4. The Pd-CPPy-CNT hybrids (PCCNs). reversible. The Pd/CPPy nanoparticles showed a detection limit of 0. The composite was utilized for the sensing of a nerve gas simulant DMMP and other vapors. leading to a high-performance H2 gas sensor at low concentration (1 ppm) at room temperature. which effectively exhibited greater selectivity for DMMP than other vapors. Park et al. which is higher than pure PPy. Field-induced sensitivity was observed.2 nm Au nanoparticles were uniformly deposited on PPy. The nanocomposite film demonstrated a sensing response toward NH3 gas of 50–2000 ppm at room temperature. Lee et al. 9. the pyrrole-3-carboxylic acid molar ratios were 1:15 (PCCN1). The population of Pd nanoparticles on the nanohybrid surface increased in the order of PCCN3 < PCCN2 < PCCN1. The decoration of the Au nanoparticles on the PANI nanofibers was made through the redox reaction between chloroauric acid and PANI emeraldine form. benzene. and 1:60 (PCCN3). respectively. Hong et al. [57] presented Cu phthalocyanine-incorporated PPy synthesized by electropolymerization. The Pd/CPPy nanoparticles were developed through alkyl functionalization of CPPy nanoparticles using alkyl amine chain. The fabricated Au/PANI gas sensor electrodes showed excellent sensing response to H2 S (<1 ppm) and CH3 SH (<1. the electrical response was fast. and then mono-disperse Pd nanoparticles were immobilized on the PPy-CNT hybrid surface by a sonochemical method of PdCl2 (Figure 7A). which was fabricated by vapor deposition polymerization. Tiwari et al. which resulted in good sensing at a relatively low temperature. including methanol. Zhang et al. ethanol. The size distribution of the controlled Pd nanoparticles was also proven. enabling the modulation of the H2 gas sensor performance. . and the PCCNs demonstrated excellent reproducible and reversible responses (Figure 7B). [60] reported a one-pot method that was used to fabricate Au/PPy nanocomposites. and reproducible. [58] prepared a Pd/PPy nanocomposite fabricated using a facile method including thermal dynamic refluxing of Pd salt and encapsulation of Pd nanoclusters with PPy by vapor phase polymerization. [61] described a novel method for designing an ultrathin CPPy layer-wrapped carbon nanotube (CNT) hybrid.1 ppm at room temperature. for 1000 ppm NH3 gas. Additionally.

The Ag nanoparticle concentration Zhao et al. [63] presented highly conductive PTh films prepared increased and passed usinga specific a facilethreshold aqueous amount. Copyright 2013. where I0 is the initial current. That NH3 gas sensing. the color of PTh films prepared the polymer usingasa main films changed facileabsorption aqueous solution-processing technique with HAuCl 4 as a doping agent. Ag/PEDOT nanotubes Ag nanoparticles. (B) Sensing performance of H2 sensors based on the nanohybrids. concentration the 3small of AgNO size and homogeneous in Ag/PEDOT distribution nanotubes to discover of the Ag the optimal nanoparticles concentration for allowed the Ag/PEDOT nanotubes to be reversible and reproducible. Copyright 2013. above which they aggregated and decreased the gas-sensing performance. Ag/PEDOT PEDOT nanotubes. study estimated the increasing above which concentration they aggregated of AgNO 3 in Ag/PEDOT and decreased nanotubes the gas-sensing to discover the optimal concentration performance. Vds = −50 mV) and (b) on periodic responses of the nanohybrid sensors (a) upon cyclic exposure to H2 (1 to 100 ppm. Therefore. [62] reported reduce Ag ions Ag to Ag nanoparticle-decorated nanoparticles. selectivity and a detection limit <1 ppm. 155 10 of 24 Polymers 2017.Polymers 2017. and I is the instantaneous current). and thiol vapors.48 evaluated [63] presented × 10 highly conductive 21 cm−3. The Au3+ logic-gate ion doped sensing PTh of amine films were easily dedoped when exposed to organic amines and thiol volatile vapors with high selectivity and a detection limit <1 ppm. Therefore. originating from oxidation PEDOT one-pot synthesis because by PEDOT can reduce Ag ions to Ag nanoparticles. Reprinted with permission from [61]. V ds = −50 mV) exposure to 10 ppm H2 (ΔI/I0 = (I − I0)/I0. for NH 3 gas sensing. The density of bands bathochromically shifted from the visible to the near-infrared region. the small size and homogeneous distribution of the Ag nanoparticlesshowed efficient NH 3 gas sensing due allowed the toAg/PEDOT a high surface area andtoimproved nanotubes conductivity. (b) ultrathin CPPy layer-wrapped CNT (inset indicates HR-TEM image of CPPy-CNTs with the skin thickness of 5 nm in diameter). from oxidation PEDOTthe study estimated by Ag nanoparticles. (A) Synthesis process of the PCCNs: (a) Bare CNT (inset indicates HR-TEM image of CNT of 30 nm in diameter). Table 1 lists other notable examples of CP inorganic hybrids-based sensors developed recently and summarizes their main sensing performance. (e) HR-TEM of Pd CPPy-CNTs with the skin thickness of 5 nm in diameter). and (b) on periodic exposure to 10 ppm H2 (∆I/I0 = (I − I0 )/I0 . The colorimetric and chemoresistive Table 1 lists changes during examples other notable the dedoping of CPprocess enabled inorganic dual mode sensors hybrids-based logic-gate sensing of developed amine recently and thiol volatile vapors with high and summarizes their main sensing performance. nanotubes whichefficient showed were fabricated NH3 gas utilizing Ag ion reduction-mediated vapor deposition polymerization via sensing due to a high surface area and improved conductivity. (e) HR-TEM nanoparticles. The colorimetric and bands bathochromically chemoresistive shiftedthe changes during from the visible dedoping to theenabled process near-infrared dual moderegion.4. (b) ultrathin CPPy layer-wrapped CNT (inset indicates HR-TEM image of of 30 nm in diameter). 9. The density of free charge carriers was Zhaotoetbeal. Park et al. where I0 is the initial current. (A) Synthesis process of the PCCNs: (a) Bare CNT (inset indicates HR-TEM image of CNT Figure 7. The Au3+ ion doped PThfree charge carriers was evaluated to be 4. (d) XRD pattern. (d) XRD pattern. (c) PCCNs. . Royal Society of Chemistry. 9. 155 10 of 24 Figure 7.48 × 10 21 cm−3 . be reversible originating That and reproducible. the color of the polymer films changed as main absorption films were easily dedoped when exposed to organic amines and thiol vapors. which were fabricated utilizing Ag ion reduction-mediated vapor deposition polymerization via one-pot synthesis because PEDOT Parkcan et al. Royal Society of Chemistry. (B) Sensing performance of H2 sensors based on the nanohybrids. Real-time the nanohybrid sensors (a) upon cyclic exposure to H2 (1 to 100 ppm. solution-processing technique with HAuCl4 as a doping agent. and I Reprinted with permission from [61]. [62] reported Ag nanoparticle-decorated PEDOT nanotubes. Moreover. increasing Moreover. Real-time responses of of Pd nanoparticles. (c) PCCNs. The Ag nanoparticle concentration increased and passed a specific threshold amount. is the instantaneous current).

5−50 ppm [43] Cu NPs NH3 72 s RT 1−50 ppm [53] Pd NPs H2 <90 s RT 5 ppm [54] Ag NWs NH3 . respectively. Moreover. Organic-CP Hybrids CPs have long been used as sensing materials for detecting vapor-phase molecules due to the change in resistivity/conductivity arising from the interaction between CPs and gas molecules. RT 10 ppm [41] PANI ZnO NPs NH3 50 s RT 25−100 ppm [42] CeO2 NPs NH3 57. Response Sensing CP Hybrid material 1 Analyte Detection limit Ref. Moreover. leading to a change in electronic conductivity or resistance in chemiresistor gas sensors. and reversible adsorption/desorption toward gas molecules limited their application for efficient and reproducible sensing devices. RT [56] CH3 SH: 1. mechanical stability.2. co-polymer hybrids based on the CPs have been explored for the specific interaction in gas sensing systems.1 ppm [31] Pt LPG . which can be readily introduced into CPs during polymerization with a functionalized monomer or post-treatment. RT 5 ppm [55] H2 S: 1 ppm and Au NPs H2 S and CH3 SH . [64] introduced a primary amine-functionalized PANI thin film as a chemiresistor sensor for recognizing formaldehyde. RT–90 ◦ C . it is a challenging task to develop a sensor with high sensitivity.5 s RT 0.Polymers 2017. 1 ppm [63] thiols 1 NP and NW note nanoparticle and nanowire. [52] amines and HAuCl4 . However.5−2.6 s RT 6. 2 RT indicates room temperature. RT 1 ppm [46] FeOOH DMMP 1. high selectivity and good repeatability for rapidly sensing molecules in vapor phase with humidity. using two or more types of polymers could improve mechanical stability and implement a flexible sensor. 155 11 of 24 Table 1.55 ppm [38] Co3 O4 CO 40 s RT 75 ppm [39] SO2 : –. 9. gas molecules act as electron donors or acceptors. CP inorganic hybrid composites used in gas sensors. . selective interaction.0 s RT 0. RT 100 ppm [60] Pd NPs H2 <1 s RT 1 ppm [61] TiO2 nanofiber NO2 5−17 min RT 1 ppb [44] relative humidity PEDOT Fe3 O4 /γ-Fe2 O3 NPs humidity 1s RT [45] 30−70% Ag NPs NH3 2−3 s RT 1 ppm [62] WO3 NO2 .01 ppm [49] PPy Pd NPs H2 4. 90 ◦ C 10−100 ppm [51] PTh WO3 NO2 .5−12. Srinives et al. The chemical functional group of the CPs can enhance the sensitivity and selectivity in electrochemical sensors. To overcome the drawbacks. NO2 : SO2 : 2ppm and SnO2 SO2 and NO2 RT [40] 5 min NO2 : 50ppb WO3 Acetone . 170 ◦C 40 ppm [59] Au NPs NH3 . 3. 40–90 ◦ C 10−100 ppm [50] SnO2 NO2 .1 ppb [47] Graphene-TiO2 NPs NH3 36 s RT 1 ppm [48] FeOOH-Cu2+ NH3 <1 s RT 0. Aldehydes are widely known for reacting with primary and secondary amines and producing Schiff bases and water by nucleophilic addition reaction under . time temperature 2 ZnO TEA 65−130 s RT 10 ppm [37] α-MoO3 TEA 35 s RT 0. In general.5 ppm Fe2 O3 nanorod NO2 .

The phosphoryl group of DMMP provides great strength in hydrogen-bond basicity. Figure 8 shows the dynamic response profiles of a HPEDOT sensor toward DMMP gas. The HPEDOT nanotubes had rapid response times (less than 1 s) and recovery times (3−25 s). Moreover. They displayed enhanced sensitivity (detection limit. In particular. L-lysine (LYS) having a diamine with alkyl backbone and poly-L-lysine (PLY) at room temperature. investigated the sensing responses with different functionalization degrees for DMMP gas sensors [6]. the sensor showed low sensitivity because it had only secondary amine and a low surface-to-volume ratio due to the smooth compact thin film. C-PPy_2. However.1 ppm) as the ratio of carboxylic functional groups increased. promoting the nucleophilic addition reaction. As a result. providing a larger surface area. and 15:1 (C-PPy_3) were prepared. indicating that hydroxyl groups improve the sensing performance. Remarkably. In 2012. the CP was functionalized with strongly nucleophilic primary amine. These results indicate that the carboxyl group plays a pivotal role in producing chemiresistive responses toward DMMP. 0.Polymers 2017. as a control. thus DMMP acts as a strong hydrogen bond base that accepts protons from the HPEDOT. Ammonia sensors based on C-PPy_1. The resistance of the sensors gradually increased after exposure to ammonia. 9. and C-PPy_3 were measured in real time. this sensor exhibited a limit of detection of 10 ppt on exposure to DMMP vapors. The sensing performance clearly depended on the amount of the functional group introduced. 155 12 of 24 ambient conditions [65. the LYS-treated PANI film displayed the best sensor activity. pure PEDOT nanotubes with no functionalized hydroxyl groups did not show a notable response at the same concentration. Kwon et al. To improve sensing performance. [72] also reported the effect of introduced functional groups of co-polymers in chemical sensing performance. with a lower detection limit of 400 ppb for aldehyde gas due to the nucleophilicity of amine. PPy and PANI are candidates as sensing materials for formaldehyde because of their amine-rich chemical structures. Monodispersed CPPy nanoparticles containing different amounts of carboxyl groups were successfully fabricated. and carboxylic functional groups were confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) measurements. The result of LYS-treated PANI film presented far better sensing performance than PPy thin film and previous other sensors [67–70].66]. Jun et al. DMMP is one of the nerve gas simulant organophosphate molecules that can induce serious damage in the nervous system. Many technical methods have been developed to detect nerve agents at low concentrations because they are odorless and colorless. Moreover. By contrast. Kwon et al. demonstrating the effect of carboxyl groups in the ammonia sensor. CPPy nanoparticles were prepared via copolymerization with two types of monomers. In addition. In 2005. pyrrole and pyrrole-3-carboxylic acid. . The devices were modified with three kinds of primary amine: phenylenediamine (PDA) having a diamine with aromatic ring. This result is because the carboxylic groups on the surface of the PPy work as supplementary active sites toward ammonia gas by hydrogen bonding. Because PEDOT is a p-type semiconductor. in an aqueous solution with polymer to prevent aggregation and metal cation complexes as the initiator [73]. the morphology of the surface became more uneven after treatment. [71] demonstrated a high-performance DMMP gas sensor based on hydroxylated PEDOT (HPEDOT) nanotubes. 30:1 (C-PPy_2). In related work also published in 2016. the sensitivity increased as the amount of carboxyl group increased. PPy nanotubes with no carboxyl groups showed measurable resistance changes only at high concentrations of more than 10 ppm. The treated PANI film with primary amines showed significantly enhanced sensitivity and selectivity compared to a pristine PANI film. a PPy thin film was reported to be a chemiresistor sensor for detecting formaldehyde [33]. Three types of C-PPy NPs with pyrrole monomer-topyrrole-3-carboxylic acid monomer weight ratios of 45:1 (C-PPy_1). the amount of carboxyl groups was controlled with pyrrole monomer-to-pyrrole-3-carboxylic acid monomer weight ratios. this phenomenon is accompanied by a decrease in PEDOT conductivity via intermolecular hydrogen bonding.

Unfortunately. American Chemical Society. Copyright 2012. (c) periodic responses to 5 ppb DMMP. .15–0. Moreover. SEM images of prepared nanotubes with diverse morphologies in real time. American Chemical Society. (a) Sequential exposure to images of prepared nanotubes with diverse morphologies in real time. it was itreported has limitations that itfor various could be applications because it is not soluble by itself. were then Twodrawnelectrodes connecting with silver paste. short time because Moreover. (e) principal component analysis plots of the 16 vapors at 4 ppm.5–500 storageppm) was stability. SEM Figure 8. L-aspartic acid (ASP) and p-toluenesulfonic acid (PTSA) were used as aciddoping the (CSA). Unfortunately. agent L -aspartic during acidthe(ASP) and p-toluenesulfonic synthesis of PANI. 9. 155 13 of 24 Polymers 2017.15–0. theand temperature sensor was tested stored every fewindays ambient air at for one room month. The chlorine chlorine sensor based on the PEDOT/PSS channel was constructed without a professional technique. (c) periodic responses to 5 ppb DMMP. TCP. Reprinted with permission from [71]. although PEDOT is a highly conductive free-chlorine sensor based on paper polymer. in theelectrodes cartridge pen and usedthe connecting when drawing the PEDOT/PSS sensing channel channel. trimethyl phosphate. Dynamic sensing performance of HPEDOT nanotubes toward DMMP gas (inset. a wide sensing To investigate range reusability and (0. with it has PEDOT/PSS limitations for (Figure various9). [75]alcohols reportedinan200 ppm of methanol electrochemical vapor. Copyright 2012. it was reported embedded in PSS via the so-called Baytron-P process. methyl dichlorophosphate. organophosphorus molecules at 1 ppb (trichlorophosphate. (d) selective response to similar without hydroxyl groups. (d) selective response to similar organophosphorus molecules at 1 ppb (trichlorophosphate. the sensorTo wasinvestigate stored inreusability ambient airand storage at room stability. TMP). (a) Sequential exposure to different DMMP gas concentrations (10 ppt to 50 ppb) in real time. applications although because it isPEDOT is a highly not soluble by conductive itself. Manmatha PANI/poly(vinyl alcohol) et (PVA) al. manuallyThe applied to the silver electrodes to minimize the noise. First. [74]composite reported a membrane. Dynamic sensing performance of HPEDOT nanotubes toward DMMP gas (inset. [74] reported a mechanically stable freestanding doped In 2016. DMMP. TCP. 155 13 of 24 Figure 8. Membranes acid with (PTSA) were used thicknesses ofas the doping 0. aPEDOT was oxidized wide sensing by free-chlorine range (0. sulfoxide the blended Thesolution doped with thesemembrane polymer doped CPsshowed and PVAgood in dimethyl sensing sulfoxide performance(DMSO). (b) pristine PEDOT nanotube without hydroxyl groups. sensor based on paper with PEDOT/PSS free-chlorine Qin et al. In 2016.5–500 ppm) was quickly. of the response towards Qin aliphatic et al. Membranes with thicknesses of 0. (b) pristine PEDOT nanotube different DMMP gas concentrations (10 ppt to 50 ppb) in real time. Baytron-Pprocess The fabrication process. 9. indicating excellent stability and reusability.sensor based on the PEDOT/PSS channel The sensorwasresponses constructed without toward a professional different free-chlorine technique.isproviding very easya and water-soluble simple withoutPEDOT/PSS complex. MDCP. and camphorsulfonic camphorsulfonic acid (CSA). methyl dichlorophosphate. Manmatha et al. MDCP. obtained. the silver and a petroleum electrodes to minimize jelly the wasnoise. The any instruments fabrication or equipment. process First. Reprinted with permission from [71]. mechanically It stable freestanding was prepared doped PANI/poly(vinyl by oxidative polymerization alcohol) of aniline(PVA) in thecomposite presence of membrane. Thus. ppm.Polymers 2017.18 mmagentwere during the synthesis of PANI. The degradation of the sensor performance was less than 15% in 30 days.18 obtained by a casting method of the blended solution with these doped CPs and PVA in dimethyl mm were obtained by a casting method of(DMSO). the PEDOT/PSS and a petroleum channel jelly waswere then drawn manually applied with to silver paste. [75] reported an electrochemical (Figure 9). PEDOT/PSS sensing was filledTwo channel. obtained.and The doped polymer repeatability membrane of the response showed towards good sensing aliphatic alcohols performance in 200 ppm and repeatability of methanol vapor. TMP). the presence of sodium dodecyl sulfate (SDS) at 0 ◦ C under nitrogen atmosphere.polymer. (e) principal component analysis plots of the 16 vapors at 4 DMMP. It was prepared sodium dodecyl sulfate (SDS)by oxidative polymerization at 0 °C under of aniline inand nitrogen atmosphere. The sensor concentrations wereresponses represented toward different accurately at free-chlorine low concentrations concentrations in a shortwere timerepresented because PEDOT accurately at low concentrations was oxidized by free-chlorinein a quickly. PEDOT/PSS solution was filled in the cartridge pen and used when drawing the solution is very easy and simple without any instruments or equipment. Thus. providing a water-soluble PEDOT/PSS that it could be embedded in PSS via the so-called complex. trimethyl phosphate.

providing the identification of four volatile organic Weisolvents.6-pentafluorophenyl) [78].15-({3. doped with free-base In this paper.3. toluene. 155 14 of 24 Figure 9. and ethyl acetate. et al. meso-tetra(2.. By contrast. In addition.and NH3 serially into the test chamber at ambient temperature for practical application.electrodes and ethyl by spin-coating acetate.8 (Figure 10b). introduced a new kind of poly(2-phenyl-1. Schematic diagram of fabrication methods for paper-based free chlorine sensor strip based on on PEDOT/PSS. of the propanone. SPEEK was used as polymeric 3 at a very low concentration of NH3 (20 ppb). In this paper. the polyacrylonitrile (PAN)/PPy material responded to NH3 at the limit of detection (over 5 ppm). Copyright 2016. toluene. (e) sensing responses sensing responses with different free-chlorine concentrations. meso-tetra(2. the at a polyacrylonitrile very low concentration(PAN)/PPyof NH 3 (20 ppb). C2 H2 .chemiresistive Among the several gas sensors importbased on multi-electrode factors. affecting providing the electrical the identification of conductivity. Schematic diagram of fabrication methods for paper-based free chlorine sensor strip based Figure 9. between The results the sensing of the resistance materials change and each solvent were directly influenced by the interaction between the sensing materials and because distinct organic vapor led to different degrees of rotation of the polymeric chain. was used as polymeric nanofiber for an ultrasensitive and flexible providing stable and distinct responses NH sensor (Figure 10).e. (d) photograph of manually prepared sensor kit. CH4.5. the authors introduced a new kind of poly(2-phenyl-1. which was as adsorbent. methanol. Moreover.5-bis(isopentyloxy)benzene}porphyrin were deposited [79])onto as a selective sensing material instead of organic Lewis acids. drawing of film as sensing active layer by using a pen filled with PEDOT/PSS. multi-electrode array was analyzed via a three-dimensional scatter plot composed by the relative The response of the multi-electrode array was analyzed via a three-dimensional scatter plot resistance change of the three sensors toward four kinds of gases. [76] illustrated chemiresistive gas sensors based on multi-electrode arrays modified with Esteves differentetporphyrin al.6-pentafluorophenyl) doped with free-base porphyrins (H2TPFP) porphyrin (meso-tetra(phenyl)porphyrin (H2TPP) [77]. under 61% relative humidity. composites were deposited onto metallic propanone. 9. 5. under 61%andrelative exposedhumidity. Prepared composites(H2BTBOP) porphyrin (H2TPFP) [78]. (c) protecting the Ag electrodes from electrodes from water with petroleum jelly.e.8stable and10b). drawing of electrodes with silver paste. The SPEEKmechanicalwas prepared by electrospinning as a template and core.5. plot showed a unique pattern. American Chemical Society. (a) First. excellent anti-interference performance was obtained by injecting 100 ppm of mechanical flexibility. interdigitated toluene. [80] presented for an ultrasensitive and flexiblesulfonated poly(ether NH3 sensor (Figureether 10). (b) second.5-bis(isopentyloxy)benzene}porphyrin (H2BTBOP) [79]) as a selective sensing material instead of organic Lewis acids. methanol. providing high as 3. the SPEEK/PPy (toward In 10 addition. for practical application. Copyright 2016. a highly sensitive and theselective authors response toward specific analytes in several mixture gases is most important. ethanol. Polymers than 15% in 30 days. to four organic solvents.15-({3.response The SPEEK intensity was of PAN/PPy prepared by was less than 1/12 electrospinning as ofa that of theand template SPEEK/PPy core.4. affecting each solvent because distinct the organic electrical vapor led toThe conductivity. Esteves et al. The scatter four volatile organic solvents. (f) Storage stability. 155 14 of 24 temperature and tested every few days for one month. ethanol. indicating excellent stability and reusability. 2. a unique polymeric chain. the response intensity nanofibers as reference material of PAN/PPy responded was less to than NH3 1/12at theoflimit thatofofdetection (over 5 ppm). (b) second.3. (a) First. (c) protecting the Ag solution. . drawing of electrodes with silver paste. permission from [75]. response toward specific analytes in several mixture gases is most important. Reprinted with permission from [75].aswhich nanofibers was reference as high as 3. The response i. [76] illustrated species. The results of the resistance composed by the relative resistance change werechange of the directly three sensors influenced by thetoward four kinds interaction of gases. and NH3 serially into the test chamber2 at ambient CH4 . (e) water with petroleum jelly. Moreover. temperature ethanol. CO. porphyrins (meso-tetra(phenyl)porphyrin (H2TPP) [77]. a highly sensitive arrays and modified selective with different porphyrin species. Prepared metallic interdigitated electrodes by spin-coating and exposed to four organic solvents. ethanol. 5. CO. toluene. (f) Storage stability.4. different scatterdegrees of rotation plot showed of thepattern. (d) photograph of manually prepared sensor kit.4-xylylene) (PPPX) composite. ppm NH the3).4-xylylene) (PPPX) composite. C2H2. Among the several import factors. 9. which produced outstanding flexibility. (Figure distinctBy responses contrast. Reprinted with with different free-chlorine concentrations. i. [80] presented sulfonated poly(ether ether ketone) (SPEEK)/PPy core/shell nanofiber Wei et al.. which (toward 10 ppmoutstanding produced NH3 ).ketone) SPEEK (SPEEK)/PPy core/shelladsorbent. The degradation of the sensor performance was less2017. H excellent anti-interference performance was obtained by injecting 100 ppm of H .Polymers 2017. American Chemical Society. drawing of film as sensing active layer by using a pen filled with PEDOT/PSS PEDOT/PSS solution.

American Chemical Society. Thus. because gas Moreover. The first is hopping are not connected by a single polymer chain or graphene sheet in the hybrid system. investigated carbon and have nanofibers. and capacity. Reprinted with permission from [80]. have been widely investigated performance [82]. and thermal high carrier mobility stability. carbon CP hybrids nanofoams.3. electric CNT transduced sensorprovide and graphene systems. [88] presented a sensitive ammonia gas sensor based on reduced graphene oxide (RGO)/PANI nanoparticles hybrids. graphene couldchannels. sensing materials Moreover.Polymers 2017. the electrodes are not There are three possible means of charge transport because the electrodes connected by a single polymer chain or graphene sheet in the hybrid system. chains. including CNTs [81]. modulus. 9. (c) the sensor response as a function of the NH3 concentration (inset: the response curve in the range of sensor response as a function of the NH3 concentration (inset: the response curve in the range of 20−1000 ppb). resulting in decreased time in theelectrical influence sensor system. they enhance were intrinsic charge transport due to high carrier mobility [87]. quality They have of their shown crystal a high lattices andsignal-to-noise ratio due chemical structure. a large surface area. The morphology of the RGO/PANI hybrid was .performance gas-sensing Recently. theymolecules enhance can penetrate hybrids rapidly and allow more opportunities for reaction. sensor system.The last is hopping Graphene between plays important the graphene-connected roles in improving the charge polymer chains. Based on these introduced intoadvantages. they high haveYoung’s modulus. Based on these advantages. the addition of graphene transportin the polymer between matrix even electrodes. based on nanocarbons. Reprinted with permission from [80].02−500 ppm (inset: the concentration range of 20−500 ppb). and the charge transport occurred in the electric transduced materials were connected between two electrodes. Another possibility is suggested in terms of tunneling tunneling the charge carrier between the graphene as a highly conducting region and CP as a the charge carrier between the graphene slightly as a highly insulating medium. fullerenes. CNTs and graphene have been widely screen charge fluctuations. (a) Illustration of the SPEEK/PPy core-shell nanofibers for NH3 sensor. Remarkably. (c) the responses to NH3 in the range of 0. Copyright 2012. American Chemical Society. resulting in decreased time in the sensor system.conducting The graphene regionprovides and CP as a slightly insulating a dominant medium. Generally. and Thethelastsecond is hopping is hopping between between polymer chains and graphene the graphene-connected polymer sheets. sensing carbon nanofoams. Huang et al. and the second is hopping between polymer chains and graphene sheets. Thus. CNTs and graphene physical and electrical properties. Last. and graphene/RGO. They have shown a highconsidered promising candidates for electrical gas-sensing signal-to-noise ratio due tomaterials the high[84–86]. There areand the possible three charge transport means ofoccurred in the electric charge transport transduced because sensor system. Generally. between polymer chains. 155 15 of 24 Polymers 2017.3. charge transport possibility between electrodes. 3. We discuss hybrids based on CNT and graphene for chemical sensors and have exhibited excellent in this sensing performance [82]. path for efficient The graphene carrier migration provides a dominant path for efficient carrier migration through the through the channels. CP channelsCNTs and graphene in electric transduced have been sensor widely introduced into CP channels in systems. and graphene/RGO. (b) real-time Figure 10. CNT/Graphene-CP Hybrids CP hybrids based on nanocarbons. CNT or graphene/CP composites have shown dramatic improvements in and graphene for chemical sensors in this section. (a) Illustration of the SPEEK/PPy core-shell nanofibers for NH3 sensor.because transport Graphene plays important graphene has extremely roles in improving high the charge mobility compared to transport because graphene has extremely high mobility compared to the CPs. leading tofor opportunities better signals reaction. graphene signal transmission could influence electrical signal transmission geometrically. CNT/Graphene-CP Hybrids 3. providing screen charge fluctuations. carbon nanofibers. exhibited excellentfullerenes. and thermal stability. Copyright 2012. such as extremely transparency.02−500 ppm (inset: the concentration range of 20−500 ppb). We discuss hybrids based on CNT section. have been widely including CNTs [81]. such as extremely high carrier mobility and capacity. geometrically. they have been promising candidates for electrical gas-sensing materials [84–86]. high [83] have excellent physical and electrical Young′s properties. 20−1000 ppb). RGO sheets allowed the nanoparticles to form uniformly without aggregation during polymerization. the addition of graphene in the polymer matrix created an easier path for chargethe CPs. Last. leading to better signals because gas molecules CNT and graphene provide can penetrate hybrids rapidly and a large allow surface more area. CNTs haveandshown dramatic graphene [83]improvements have excellent in gas-sensing performance under ambient conditions. The first is hopping between polymer chains. 9. been considered transparency. intrinsic charge transport due to high carrier mobility [87]. 155 15 of 24 Figure 10. Remarkably. sensing connected between two electrodes. (b) real-time responses to NH3 in the range of 0. created in an easier small path forAnother amounts. Recently. is suggested even in in terms of small amounts. to the providing high quality of their crystal lattices and chemical structure. CNT or graphene/CP under composites ambient conditions.

Kim et al. which were affected by the attached PANI nanoparticles directly. no gas sensor transduced electrically based on it has been reported because the PPr is usually prepared as a powder. Moreover. a longer recovery period was needed. Furthermore. i. [90] introduced graphene oxide/polypyrene (GO/PPr) composite films for sensors of volatile organic compounds (VOCs). a parallel type. and it had a significantly rapid response/recovery time. Although the response time was also improved. the circuit networks completely depended on the RGO sheets.4 and 10. the VOC sensor based on GO/PPr showed high performance and a rapid. similar to PANI. 155 16 of 24 Huang et al. which provides much better sensing performance because of the advantage in the adsorption of NH3 gas molecules. an approximately 30% change in resistance can be observed for this device. [89] demonstrated the effect of a geometrical configuration with graphene/PANI (G-t-PANI) film in an electrical NH3 sensing system. Alternating layers of graphene and PANI were obtained. In this experiment. as shown in SEM images and analysis of elemental mapping. As a result. The G-t-PANI architectures were prepared by ultrasonication after synthesizing PANI with a ternary dopant such as camphorsulfonic acid (CSA). and D-sorbitol (SBT).4 compared to those of the sensors based on bare PANI nanofibers and bare RGO sheets toward NH3 gas at 50 ppm. the RGO/PANI hybrid sensor showed enhanced sensing performance by factors of approximately 3. reversible response. and lower toxicity. and the resistance could not return to its initial state.Polymers 2017. Finally. In general. and X-ray diffraction (XRD). Moreover. This result reveals that positive synergetic effects have probably occurred between PANI nanoparticles and RGO sheets in terms of the intrinsic electronic properties and large surface area. four types of samples. respectively. as controls were constructed for an electrical NH3 gas sensor. thermal stability. Despite its outstanding properties. As a result. The morphology of the RGO/PANI hybrid was confirmed by TEM images. GO/PPr composite film was fabricated via electrochemical co-deposition and characterized by SEM. resulting in increased resistance. [88] presented a sensitive ammonia gas sensor based on reduced graphene oxide (RGO)/PANI nanoparticles hybrids. Because NH3 is an electron donor. dodecylbenzenesulfonic acid (DBSA). As a result. RGO also showed p-type behavior having hole-like charge carriers under ambient conditions owing to absorbed humidity or oxygen. it can lead to decreases in the number of charge carriers. 9. and the interaction between RGO and PANI nanoparticles was analyzed by the peak of polaron–π* transition with UV-visible spectroscopy. As a result. the surface area values of 32 and 22 m2 g−1 for RGO/PANI hybrids and PANI nanoparticles. it showed thermal stability owing to the strong interfacial interaction. . only PPr was impossible to apply to the active layers toward vapor sensors. and the response intensity as sensitivity and response/recovery time were profiled. the graphene was considered to preserve excellent electrical properties because no D peak was observed in Raman spectroscopy. Finally. which is better than those of the devices based on bare RGO and PANI nanoparticles.. As a result.e. PPr was successfully grown on GO sheets easily during polymerization due to the π−π stacking interaction between the GO sheet and the aromatic rings of PPr. the charge carrier was reduced. the G-t-PANI exhibited markedly improved sensing performance compared to a bulk-PANI film. a combination type connected with two series films of half-thickness and a bulk PANI film. improving the junctions. RGO sheets allowed the nanoparticles to form uniformly without aggregation during polymerization. FT-IR. the GO/PPr composite exhibited enhanced the mechanical properties and conductivity compared to powdery PPr film due to continuous structures. TGA. high electrochemical conductivity. suggest that a larger surface area of RGO/PANI hybrids can be obtained. In this article. When the PANI was de-doped due to NH3 gas. a series type. PPr has potential as sensing material due to its strong fluorescence. the PANI was densely intercalated into the graphene sheets. As a result. Li et al. To observe the effect of the alternating configuration. Interestingly. a voltage was applied in perpendicular and parallel to the samples. The G-t-PANI film was integrated into the sensor device as a sensing channel (Figure 11). and the chains of PPr layers played important roles in the interaction between GO sheets. the series type showed a signal more than 10 times higher than the parallel type.

respectively. Prepared materials (C-MWCNTs and PANI-MWCNTs) were characterized UV-visible spectroscopy. FT-IR spectroscopy. conductivity by the strong interaction between PANI and C-MWCNT via π−π stacking.58%).American CopyrightChemical 2016. American Society. Aldalbahi et al. Interestingly. The response of the sensor based on PANI-MWCNTs (15. composite showed more richness in quinoid units than PANI in FT-IR spectra. [91] presented an excellent ammonia gas sensor based on PANI-functionalized Abdulla et al. Raman spectroscopy. A band at approximately 425−430 nm explained the doping electronic by interactions between the imine sites of PANI and carboxyl groups in C-MWCNTs. (c) sensing performance of a G-t-PANI film with various stacked orientation toward 1 ppm orientation toward NH 1 ppm NH3 gas. Excellent sensing performance was observed at room temperature.336 and 33. The electrical conductivities of this effect was also observed in a previous study [92]. The UV-visible spectra of PANI-MWCNTs displayed very broad tailing-shaped band at approximately 700 nm. Copyright [89]. of half-thickness. 155 17 of 24 Figure11. 9. the effect of the functional group of MWCNTs was studied with PANI/polymer/MWCNTs and PANI/polymer/MWCNTs-COOH nanocomposites in a CH4 gas sensor system. XPS. [93].Schematic Schematic illustration illustration of G-t-PANI of (a) (a) G-t-PANI film. The UV-visible spectra of PANI-MWCNTs displayed a transmission electron microscopy (HR-TEM). resistometric sensor. 155 17 of 24 Polymers 2017.58%). [93]. XPS. indicating enhanced the composite showed more richness in quinoid units than PANI in FT-IR spectra. (d) initial (R0 )(d) andinitial change(R0)(∆R) and of change (∆R) in resistance of resistance in resistometric sensor. Prepared materials (C-MWCNTs and PANI-MWCNTs) were characterized by CNTs (C-MWCNTs). attributed to the were observed with PANI-MWCNTs compared to C-MWCNTs.374 S cm−1 . (e) signal-to-noise ratio under the same conditions. film. this effect was also observed in a previous study [92]. (ii) a parallel type. Abdulla et al. (iii) a combination type connected with two series two series films films of half-thickness. inducing electron delocalization.5%) exhibited of NH3 gas. Interestingly. from permission from2016. Interestingly. Reprinted with permission Reprinted with [89]. (iii) a combination type connected with 3 gas. attributed to the enhanced charge enhanced charge transfer. The comparative sensing unit of PANI to the MWCNT. (ii) a parallel type. 9.t-PANI film). The sensor . which was synthesized by a simple and low-cost in situ chemical oxidative polymerization of aniline monomer on the surface of carboxylated multiwalled chemical oxidative polymerization of aniline monomer on the surface of carboxylated multiwalled CNTs (C-MWCNTs).336 and 33.Chemical Society.Polymers 2017. Figure 11. The comparative sensing performance performance based on the C-MWCNTs and PANI-MWCNTs were carried out in the range of a trace based on the C-MWCNTs and PANI-MWCNTs were carried out in the range of a trace level (2−10 ppm) level (2−10 ppm) of NH3 gas. ((i) a series type. and high-resolution transmission electron microscopy (HR-TEM). Fast response and result several times higher than that of C-MWCNTs (2. Moreover. Fast response and good reversibility good reversibility were observed with PANI-MWCNTs compared to C-MWCNTs. Both composites showed high sensitivity and selectivity toward CH4 gas.5%) exhibited a more enhanced a more enhanced result several times higher than that of C-MWCNTs (2. Excellent sensing performance was observed at room temperature. indicating enhanced conductivity by the strong interaction between PANI and C-MWCNT via π−π stacking. The reason The reason for improved conductivity was suggested to be the dopant effect or charge transfer from for improved conductivity was suggested to be the dopant effect or charge transfer from the quinoid the quinoid unit of PANI to the MWCNT. and (iv) a bulkandt-PANI (iv) a bulk film). PANI-MWCNT composite was also introduced as a highly efficient CH4 gas sensor by gas sensor by Aldalbahi et al. The response of the sensor based on PANI-MWCNTs (15. (b) (b) gas gasand flow flow and electrical electrical setup forsetup for the the chemical chemical gas sensor. Moreover. the state by interactions between the imine sites of PANI and carboxyl groups in C-MWCNTs. ((i) a series type. which revealed the highly doped form of a very broad tailing-shaped band at approximately 700 nm. (c) sensing performance of a G-t-PANI film with various stacked gas sensor. PANI-MWCNT composite was also introduced as a highly efficient CH4 transfer. and high-resolution by UV-visible spectroscopy. The electrical conductivities−1of PANI and PANI and PANI-MWCNT were measured and calculated to be 3. respectively. FT-IR spectroscopy. PANI-MWCNT were measured and calculated to be 3.374 S cm . Interestingly. Raman spectroscopy. which revealed the highly doped form PANI in the composite. [91] presented an excellent ammonia gas sensor based on PANI-functionalized multiwalled CNTs (PANI-MWCNTs). inducing electron delocalization. (e) signal-to-noise ratio under the same conditions. A band at approximately 425−430 nm explained the doping electronic state of PANI in the composite. which was synthesized by a simple and low-cost in situ multiwalled CNTs (PANI-MWCNTs).

the thermal stability of the MWCNT/PEDOT:PSS composite appeared to be much better than that of the MWCNT/PANI composite and showed excellent repeatability of standard resistance in the optimized recovery condition. which were compared for their ammonia gas-sensing performance at room temperature.5 s RT 0. PAA H2 O2 . organic molecules. 155 18 of 24 the effect of the functional group of MWCNTs was studied with PANI/polymer/MWCNTs and PANI/polymer/MWCNTs-COOH nanocomposites in a CH4 gas sensor system. which can induce electrical sensing responses toward chemical gases. the MWCNT/PEDOT:PSS composite was revealed to be considerably more sensitive (~16% better sensitivity) with a shorter response time (~15 min). RT 250 ppb [100] PCDTBT PCDTBT NO 300 s RT 5 ppm [101] 1 NP and NT note nanoparticle and nanotube. and the DC electric field and heating-cooling profile were controlled to optimize fast and complete recovery.Polymers 2017.5 mM [96] PANI PDA Formaldehyde .92 mM Graphene sugar 4 min RT [97] and D-glucose: 3.3%.1 ppm [72] PSS Chlorine 15−300 s RT 0. selectivity. The sensor of PANI/polymer/MWCNTs exhibited a clear signal. 2 RT indicates room temperature. Both composites showed high sensitivity and selectivity toward CH4 gas. RT 10 ppt [71] MWCNT NH3 <15 min RT 1 ppm [94] PT Graphene NH3 . and summarizes their main sensing performance. In terms of sensitivity. RT 750 ppb [64] polymer/MWCNT CH4 <5 s RT−60 ◦ C 5–15 ppm [93] MWCNT NH3 <6s RT 2–10 ppm [91] D-fructose: 2.46 mM Graphene NH3 <40 s RT 1 ppm [89] Phthalocyanine NH3 4−10 min RT 25–90 ppm [98] PPy PPy-COOH NTs DMMP . and nanocarbons as heterogeneous functional species. RT 5−50 ppm [88] Aliphatic PVA 4.6−7. upon comparison.8 s RT . time temperature 2 RGO NH3 . Both sensors exhibited excellent sensitivity. CP organic hybrid composites used in gas sensors. Sharma et al.5 ppb [6] PPy-COOH NPs NH3 2. SWCNT VOCs .0−3. RT Ethanol: 5. RT 0. [74] alcohols Poly-3-hydroxybutirrate NH3 100 s RT 834 ppb [95] HEC. and they exhibited better sensing performance .1%) than those of the PANI/polymer/MWCNTs-COOH. Several studies have demonstrated that versatile organic/inorganic CP hybrids can be fabricated using a metal/metal oxide. CP-based sensors still have room for improvement [13]. which was attributed to the nonconductive property of the functional element. Table 2. Furthermore. 4. Table 2 lists other notable examples of CP organic hybrid-based sensors developed recently. and higher sensitivity (3. RT 0. [94] reported on PEDOT:PSS and PANI on MWCNTs. quicker response time (<1 s). However.95%. [99] PEDOT methylethylketone: 3% PEDOT-OH NTs DMMP . respectively. Response Sensing CP Hybrid material 1 Analyte Detection limit Ref. to aid in the understanding of recent trends in CP sensors.5 ppm [75] Methanol: 1. 9. Conclusions This review has introduced prominent findings for CP hybrids as chemo-electrical transducers. and environmental stability.

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