Open access peer-reviewed chapter

Gas Sensing Applications of Carbon-Based Nanocomposites

Written By

Arti Rushi and Kunal Datta

Submitted: 30 April 2024 Reviewed: 08 July 2024 Published: 28 August 2024

DOI: 10.5772/intechopen.115296

From the Edited Volume

Nanocomposites - Properties, Preparations and Applications

Edited by Viorica Parvulescu and Elena Maria Anghel

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Abstract

Apart from garnering the dimension effect, it is the synergistic advantage of constituent elements that contributes to enhanced properties in nanocomposites in comparison to pristine counterparts. While in some cases, nanocomposites have been obtained by introducing nanoparticles/nanofibers as fillers to reinforce host materials, plethora of reports employed in situ synthesis of nanocomposites. Novel quantum effects and enhanced surface-to-volume ratio in nanocomposites are reported to contribute towards extraordinary physico-chemical properties. Characteristics of nanocomposites are well reported to be precisely adjusted by modifying nanoparticles/nanofiber size, shape, dispersion and concentration during synthesis. Some of the prominent materials which are used in the synthesis of nanocomposites are carbon nanotubes, graphene, nanoclays, metal nanoparticles, nanostructured ceramics, etc. Their adaptability makes them suitable for use in a variety of industries, such as the biomedical, automotive, aerospace and electronics sectors. Here, exciting opportunities exist for creating innovative materials with improved performance and multifunctionality. This report provides emphasis on the gas sensing properties of carbon-based nanocomposites.

Keywords

  • carbon nanotubes
  • graphene
  • nanocomposites
  • gas sensing
  • sensors

1. Introduction

Pollution is certainly among most ubiquitous and invincible threat to the entire creation. Among the spectrum of pollutions, air pollution is certainly the domain of unfathomable adversities owing to its fundamental contribution for existence, lack of knowledge and absence of adequate purification measures. The constituents of air, when present in a higher than requisite concentration led to severe detrimental effects for both flora and fauna. These materials, sometimes referred to as contaminants, can exist as gases, liquid droplets or solid particles. They can originate from a wide range of natural and man-made sources and have light to long-rooted impacts on the ecosystem, the climate, and human health [1]. Ash, dust, sulphur dioxide and other gases are released during volcanic eruptions, smoke, particle debris, and gases like nitrogen oxides and carbon monoxide that are released during forest fires are some of the natural sources of pollutants [1]. Meanwhile, exhausts from automobiles, industrial emissions, and agricultural activities with high use of pesticides are the anthropogenic sources of pollutant emission. Some prominent air pollutants observed are particulate matter, nitrogen oxides, sulphur oxide, carbon monoxide [2], volatile organic compounds [3], etc., as shown in Figure 1. Prolonged exposure to these pollutants is found to be hazardous to the human body as they create several health problems such as skin issues, lung disorders and pulmonary diseases. Although the effect of pollution on human beings is most studied and reported, the irreparable damage that is being caused to the entire climate and biodiversity is far from being measured to a reliable extent.

Figure 1.

Major air pollutant present in the environment.

The use of green energy sources, regulations by the government on man-made pollution sources, technological solutions, for example, creating greener vehicles and power generation technologies, and awareness and education regarding the negative effects that air pollution has on human health and the environment, could be the necessary steps to curb pollution for coming generations, yet considering current environmental, where human is under eclipse of airborne pollutants, sensitive, selective and detecting technique is required to have real-time monitoring of the air condition [4]. This will assist in implementing proactive safety measures prior to the major hazard. Aplenty of technological interventions have been made, and some of the techniques have gained commercial success.

The following Table 1 shows some of the air pollutant detection techniques along with their working principle [5, 6, 7, 8, 9, 10, 11, 12].

Sr. No.Methods for detecting air pollutionWorking principleApplicationRef.
1Continuous Emission Monitoring Systems (CEMS).These systems track pollutants produced in real time from industrial sources.Particulate matter (PM), nitrogen oxides (NOx), sulphur dioxide (SO2), and other pollutants are measured by these devices.[5]
2Passive Sampling: Over a predetermined time, contaminants are gathered by passive samplers.After pollutants permeate a sorbent, their concentration is measured.Checking the air quality both indoors and outside for different contaminants.[6, 7]
3Active Sampling: The purpose of an active sampler is to actively draw air through a collection medium using a pump.For further analysis, pollutants are gathered on a filter or sorbent material.Good for quantifying particular contaminants, like volatile organic compounds (VOCs).[8]
4Remote Sensing: Lidar or satellite-based sensors are some examples of the devices used in remote sensing techniques.They examine how light interacts with airborne particles to identify contaminants.Wide-ranging, extensive pollution monitoring.[9]
5Electrochemical sensors: Low-cost, portable sensors for pollutant detection on-site.The changes in electrical characteristics caused by the interaction of gases are measured by these sensors.Indoor air quality evaluation and personal exposure monitoring.[10]
6Particle counters: Determines the amount of airborne particles present.Particles’ ability to scatter or block light is utilised to estimate the concentration of those particles.Tracking the amount of particulate matter (PM) in different settings.[11]
7Gas chromatography-mass spectrometry (GC-MS): An extremely precise and sensitive technique for examining intricate gas combinations.Distinguishes and recognises each component of a sample of gas.Determining and measuring other gases and volatile organic compounds (VOCs).[12]

Table 1.

Air pollution detection techniques.

These methods, which are frequently combined, are essential for controlling and keeping an eye on air quality. Applications range from industrial pollutants to urban air pollution, enhancing public health and fostering a healthier environment.

The employment of detection techniques is a major factor that governs the performance of any detection approach. Warrant of ultimate reliability in performance of any detection technique combined with practical demands of ultra-low power consumption and low footprint solution, novel materials are under continuous investigation by scientific and technological community alike. A wide variety of materials, namely carbon nanotubes, conducting polymers [13], graphene [14], porphyrins [15], metal oxides [16], etc., have accepted global recognition as potential gas sensing platforms. In order to alleviate individual shortcomings and to obtain synergistic effects, composites of these materials are relied upon in comparison to individual materials. Finally, the use of nanostructured composites has shown significant potential in real-time monitoring at an extremely low footprint, often resulting in a lab-on-chip realm.

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2. Nanocomposites

Nanocomposites are cutting-edge materials obtained by combining nanoparticles with a bulk matrix material to create a material with special qualities and attributes that set it apart from conventional composites and separate components [17]. The concept of nanocomposites looks forward to harnessing attractive properties of contributing constituents with previously unachieved flexibility and physical property improvements. These materials are prospective for a wide range of industrial applications because of their remarkable mechanical, electrical, thermal and barrier capabilities, which have garnered them much attention in recent years. Natural structures such as the structure of the bone and abalone shell contain nanocomposites. Materials rich in nanoparticles have been used for a long time before their physical and chemical properties have been fully understood. Nanoscale organo-clays have been employed since the middle of the 1950s to regulate the composition of gels or the flow of polymer solutions. Although the word “nanocomposites” was not widely used, textbooks on polymer/clay composites were available by the 1970s [18].

Because of the very high aspect ratio and/or surface-to-volume ratio of the reinforcing phase, nanocomposites differ from other common composite materials. The particles (like minerals), sheets (like exfoliated clay stacks), or fibres (like carbon nanotubes or electrospun fibres) can all be components of the reinforcing material. The area of the interface between the matrix and the reinforcing phase(s) is typically orders of magnitude bigger than in conventional composite materials. There is a noticeable influence on the matrix material’s characteristics near the reinforcement. It should be noted that the degree of thermoset cure, the mobility and conformation of the polymer chain, the degree of ordering of the polymer chain, and the crystallinity of polymer nanocomposites can all vary significantly and frequently. Because of the huge surface area of the reinforcement, a relatively modest amount of nanoscale reinforcement can have a noticeable impact on the composite’s macroscale characteristics. Comparing carbon nanotubes to their bulk counterpart, for example, increases both electrical and thermal conductivity.

Some of the most notable properties of nanocomposites are provided in Figure 2. The discussion of the properties of nanocomposites is provided below:

  1. Mechanical Strength: Nanoparticles can significantly increase mechanical properties [19], including hardness, modulus and tensile strength, even at very low concentrations.

  2. Electrical Conductivity: A composite electrical conductivity can be produced by certain nanoparticles, especially those based on carbon, like graphene or carbon nanotubes [20].

  3. Barrier Properties: Due to their remarkable ability to withstand gases, liquids and even electromagnetic interference, nanocomposites find extensive application in packaging and electrical fields.

  4. Lightweight: Despite their enhanced properties, nanocomposites are often lightweight, which makes them attractive for usage in automotive [21] and aerospace [22] applications.

  5. Optical Properties: Nanoparticles can be employed in sensors and optics by modifying the composite’s optical characteristics, such as transparency, colour or opacity.

Figure 2.

Properties of nanocomposites.

This report sheds light on nanocomposites that use carbon nanoforms as their primary constituent. A vast range of charge transport properties is exhibited by the allotropic forms of carbon (amorphous and polycrystalline graphite, carbon black, fullerenes, nanotubes and graphene), which have sparked basic and applied research for the creation of new devices based on micro- and nano-sized electronic systems. Figure 3 gives a pictorial representation of different carbon allotropes. By fusing the characteristics of each separate phase, carbon-based nanomaterials provide the opportunity to enhance device performances and create unique multifunctional material systems [23].

Figure 3.

Carbon allotropes used in the synthesis of carbon-based nanocomposites.

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3. Synthesis of carbon-based nanocomposites

Materials that can effectively get mixed with carbon-based nanoscale materials, including graphene, nanoparticles or nanotubes, contribute to carbon-based nanocomposites. Depending on the particular material utilised, carbon-based nanocomposites can be achieved by a broad spectrum of techniques, among which covalent and non-covalent functionalization can be considered as classic methods.

In order to achieve covalent functionalization of carbon nanotubes, guest material is chemically attached to the sidewall of nanotubes through the formation of covalent adducts [24]. Although such a method offers stronger binding of the guest material, reactive chemical treatment mostly results in an irreversible hybridization shift from sp2 to sp3 and conjugation loss [25]. Covalent functionalization of carbon nanotube sidewalls includes methods, namely oxidative purification, amidation, esterification, thiolation, hydrogenation and electrochemical functionality, which have been adopted for covalent functionalization [26]. On the other hand, non-covalent functionalization is a supramolecular approach. Through π-π interfaces, aromatic compounds like anthracene, phenanthrene, pentacene, porphyrin, pyrene and CNT or graphene interact with each other. The non-covalent functionalization route is a traditional supramolecular method where the surface tailoring of SWNTs is caused by a variety of adsorption forces, including hydrogen bonds, Van der Waals force, electrostatic force, and π-stacking interactions [26, 27, 28, 29, 30, 31, 32]. The interaction of polymers with the CNT surface via wrapping adds up to better dispersion of CNT in water and organic solvents, apart from retaining the attractive surface properties of CNT sidewalls. Polymers and conducting polymers have been abundantly used for non-covalently functionalizing CNT surfaces by simple dip coating method [33] or electrochemical method [34], the latter offering excellent control over the thickness of the polymeric layer on CNT [35]. Enhanced conductivity of polymer/CNT is well accepted for chemical sensing applications [36, 37, 38]. Composites synthesised by in situ chemical polymerisation [39] are reported to have improved the electrical conductivity, electrochemical capacitance or mechanical strength of the polymer. On the other hand, electrochemical polymerisation has been reported to form a donor-acceptor complex with enhanced electroactivity and conductivity of the composite films [40]. Porphyrins and/or metalloporphyrins are among excellent functional materials by dint of their structural aspects and can be attached to CNT sidewalls in an extremely facile manner [41]. As an excellent example of synergy, while the electrical conductivity of porphyrins/metalloporphyrins is not adequate for electrical transduction [42], these fascinating classes of macrocycles are highly prospective functionalizing entities for highly conducting backbones, most popularly, carbon nanotubes. Non-covalent functionalization with porphyrins/metalloporphyrins maintains the graphitic structure of CNTs [43] in an excellent manner, retaining the surface properties of CNTs [44], and this ensures efficient sensing prospects. Van der Waals forces had an impact on the functionalization of SWNTs during the solution phase, as reported by Nakashima et al. [45] in their initial study on the creation of porphyrin-functionalized CNTs. This specific work has really ushered in a new phase of porphyrin(s)-mediated CNT functionalization. With their highly polarizable aromatic porphyrinic cores and strong interaction with π-conjugated graphenic sidewalls, porphyrins are appealing options for the non-covalent functionalization of carbon nanotubes [45, 46, 47]. For non-covalent functionalization of graphene, several nonsolvents for reduced graphene, namely, benzene, hexane, oxylene, and dichloromethane, have been reported [48]. The carboxylate groups facilitate noncovalent functionalization locations to the protonated amine terminals of end-functional polymers after the chemical reduction of graphene oxide [49]. The additional benefit of functionalizing the CNT side wall, graphene, reduced graphene, GO surface, or creating a composite is that it enhances sensor recovery characteristics because the analyte cannot come into direct contact with the CNT surface in this configuration. In fact, the sluggish desorption of analytes due to the honeycomb structure of CNTs and the high binding energy of gas analytes reflects the poor recovery behaviour in pristine CNT-based sensors. As a result, there is a great deal of interest in research on functionalized or composite architectures of CNTs to address the issues of selectivity and recovery of pristine CNT-based sensors.

Although the spectrum of synthesis techniques for carbon-based nanocomposite is extremely vast, as could be perceived from the above discussions, a generic pedagogy towards achieving the same is provided in Figure 4.

Figure 4.

Procedure of synthesis of carbon-based nanocomposites.

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4. Gas sensing applications of carbon-based nanocomposites

4.1 Sensing mechanism

Both CNT and graphene, the most prominent members of carbon nanoforms applied for sensing applications, largely rely on changes in resistive properties on exposure to gaseous analytes/noxious vapours through donor-acceptor interactions [50, 51, 52]. CNTs’ circular curvature causes σ-π rehybridization, which causes three σ bonds to be somewhat out of plane. In order to make up for this, the π-orbital is now asymmetrically distributed both inside and outside the nanotube’s cylindrical wall [53]. Because of the deformed electron clouds, a rich π-electron conjugation arises outside the tube, which greatly increases the electrochemical activity of CNTs. Molecules that give or take electrons from the surface of carbon nanotubes (CNTs) include NO2, NH3, O2 and others. These molecules alter the overall conduction behaviour of the CNTs. In essence, the p-hype behaviour of a growing nanotube is caused by the adsorption of O2. Therefore, well-mechanised effects arise from the donation or withdrawal of electrons to the bulk or surface of nanotubes. The overall sensing phenomena are shaped by enhanced molecule adsorption at room temperature and subsequent charge transfer. Gas molecules can be adsorbed at the surface of a single tube, at due interstitial in tube bundles, in a groove above the space between two adjacent tubes, and inside tubes and nanopores [53]. The detection of NO2 and NH3 by a single SWNT FET was initially reported by Kong et al. [54]. This specific endeavour represented a logical progression of a finding from research by Zhou et al. [55], in which the authors had described the FET characteristics of SWNTs integrated in a back-gated configuration. In just one or 2 minutes, Kong et al. [54] saw three orders of shift in the conductance of SWNTs to even 2 ppm concentration of NO2 and 0.1% concentration of NH3. Someya et al. [56] reported using a similar backbone sensing modality with a response time of 5–15 s to detect saturated gaseous content of methanol, ethanol, 1-propanol, 2-propanol and test-butanol. Novak et al. [57] demonstrated the use of a CHEMFET based on an SWNTs network for the detection of dimethyl methylphosphonate (DMMP). In this instance, a sub-ppm level detection was reported. The study’s most important finding was the sensor’s quick recovery through the use of a positive gate bias. Subsequently, the results of Chang et al. [58] further established this recovery strategy. Valentini et al. [59] created a chemiresistor-based sensor using CNT mats that could detect NO2 as low as 10 ppb. The sensor was examined for a high operating temperature, nevertheless. Li et al. created a simple SWNT-based chemiresistor by drop-casting well-dispersed SWNTs onto premade interdigitated Au electrodes [60]. The sensors were effectively used for NO2 and nitrotoluene ppb level measurement. The sensors did not recover quickly unless they were exposed to UV radiation. Suehiro et al. [61] used dielectrophoresis for the first time to construct an ammonia sensor based on the MWNT network. Using CVD, Li et al. [62] have reported the direct synthesis of silicon nanotubes (SWNTS) on interdigitated Pt and Ti electrodes on a Si/SiO2 substrate. The sensors demonstrated the ability to detect concentrations of NH3 and NO2 as low as 1 and 125 ppb, respectively. Goldoni et al. [63] reported on the impact of contaminants created during the synthesis and purification of SWNTs on the sensing characteristics of SWNTs. A CNT film-based H2 sensor with a detection limit of 10 ppm at room temperature has been fabricated, according to Pierton et al.’s publication [64]. According to Matranga and Bockrath’s theory [65], CO may be detected via hydrogen bonding with the hydroxy groups on the CNT.

In a similar fashion, while investigating the effect of ammonia on graphene nanostructures, Freddi et al. have suggested electron transfer to graphene due to the overlapping of ammonia’s highest occupied molecular orbital (HOMO) and graphene orbitals, with a pivotal role of defects and edges in the graphene [66]. In spite of a plethora of reports on pristine CNTs/graphene-based gas sensors, the stiffest hurdle lies in stiff limitations with transduction mechanisms. At this particular point, carbon-based nanocomposites offer wide versatility and additionally restrict the nanotube/graphene surface from coming into direct contact with the analyte, a problem that is well reported to deteriorate the recovery characteristic of sensors.

4.2 Gas-sensing applications

Among earlier studies, Zhang et al. reported electrochemical functionalization of SWNTS with poly (aniline), where the chemiresistive sensor backbone detected ammonia down to 50 ppb concentration [67]. An ultrathin CPPy layer-wrapped carbon nanotube (CNT) hybrid has been obtained through vapour deposition polymerisation by Park et al. [68], which was further decorated with monodispersed Pd nanoparticles on the PPy-CNT hybrid surface that resulted in high-performance field-effect transistor to trace hydrogen at a level of 1 ppm at room temperature. By adding ammonium persulfate to an aniline solution containing carbon nanotubes (CNTs), polyaniline (PANI) nanoparticle-coated CNTs and PANI nanofiber can be created [69]. The resulting PANI thin film exhibits highly sensitive NH3 sensing down to 200 ppb with excellent response/recovery time. It works in the room temperature environment. In order to non-covalently functionalize SWCNTs with poly(N-methyl pyrrole) (P[NMP]) by π−π interaction, Datta et al. [35] used an electrochemical method. The resultant product had a good linear response for ammonia sensing, ranging from 10 ppb to 1 ppm. This study focuses on how the thickness of the polymeric layer in the aligned SWNTs matrix affects the behaviour of the sensors. Using HCl as a dopant and ammonium persulphate (APS) as an oxidant for the detection of NH3, an in situ chemical oxidative polymerisation approach was used to create the nanocomposite of PPy and carboxylated multiwalled carbon nanotubes (MWCNT–COOH). This study focused on how the content of MWNTs affects the sensitivity of the composite backbone [70]. Zhang et al. [71] have documented a change in polyaniline’s sensing behaviour from p-type to n-type by an examination of the interface effect. At the core–shell interface of hierarchical PANI/CNT composites, n-type PANI and p-type CNTs form p–n hetero junctions. The detection limits for NO2 and NH3 by p-type PANI/CNT and n-type PANI/CNT are as low as 16.7 and 6.4 ppb, respectively. In order to monitor health, Hong et al. [72] presented a stretchy array of multifunction sensors that resemble skin and are based on polyurethane foam coated with MWCNT-PANI composite. The sensors can detect skin temperature, wrist pulse and ammonia gas simultaneously. Wu et al. employed tetra-b-carboxyphthalocyanine cobalt(II) to fabricate PANI/multiwalled CNT (MWCNT) nanocomposites for rapid detection of ammonia [73] with a response/recovery time of 5.0/12.0 s to 100 ppm NH3. S. Kumar et al. have functionalized SWNTs with polyethylenimine with significant repetitive behaviour with the assistance of UV irradiance [74]. The investigators achieved 37% higher sensitivity with functionalized structure compared to pristine SWNTs-based sensors.

Among prominent reports of macrocyclic compounds functionalized CNT sensors, Ndiaye et al. employed a simple dispersion technique to non-covalently functionalize SWNTs with pthalocyanines and porphyrin derivatives [75]. Detection of BTX-type gases, especially toluene, was investigated in chemiresistive and Quartz crystal microbalance-based mass sensing modes. Contrary to the generic perception of analyte binding with CNTs, the authors reported slower desorption of analytes functionalized backbone in comparison to pristine SWNTs matrix. The QCM-based sensor could detect target vapour sensitively within a detection window of 60–1200 ppm. Through the interaction of glycyl-substituted porphyrin with non-modified CNTs and PPy/SWCNT-COOH film, Lvova et al. synthesised SWCNT–porphyrin composites [76]. Using the CNT-Porphyrin composite as a QMB coating allowed for the detection of 1-butanol at 46 ppb levels. Shirsat et al. used porphyrins with a variety of functional groups and core metal ions to functionalize aligned SWNTs backbone in an all-encompassing strategy to comprehend the selectivity behaviour of porphyrin/metalloporphyrin functionalized CNT sensor devices [77]. A pattern recognition analysis was employed to analyse the specific behaviour of individuals sensing backbones to saturated vapours of MEK, acetone, methanol and ethanol. This particular study constituted an important step towards specific sensing of volatile organic compounds (VOCs) and the development of e-nose platforms. An electrochemical functionalization route was adopted by Sarkar et al. to functionalize SWNTs with poly(tetraphenyl porphyrin) [78]. The authors applied different charge densities to control functionalization layer and correlated sensing performance with the thickness of poly(tetraphenyl porphyrin) layer. The lowest detection limit of the optimised sensor was recorded to be 9 ppm for oxygen vapour. The sensing was carried out in a field-effect transistor structure, and the electrostatic gating effect was found to be the primary sensor mechanism. This report stressed the stable behaviour of the sensor device for a period of 180 days. A chemiresistive platform that employed iron tetraphenyl porphyrin and tetraphenyl porphyrin for non-covalent functionalization of aligned SWCNTs has been reported by the authors [41]. The functionalization was carried out by the facile solution casting method [41]. The hybrid sensor could detect benzene at a presence of 1 ppm concentration. The better sensing response of iron tetraphenyl porphyrin functionalized SWCNTs sensor was attributed to the vacant d-orbital of the central Fe atom that acted as a point of electron reception. Taking this investigation further, the authors, at a later course, investigated the effect of iron and cobalt as central metal ions in tetraphenyl porphyrin towards functionalization of SWCNTs on selective behaviour of the chemiresistor platform towards benzene, toluene and xylene [79]. A detailed insight into the mechanism was presented in the report, and selective behaviour could be observed with toluene at a lower detection limit of 500 ppb. A chemiresistive sensor array was reported by Liu et al. through non-covalent functionalization of single-walled carbon nanotubes (SWCNTs) with late first-row transition metal complexes of meso-tetraphenyl porphyrin [80]. Vapours of a variety of volatile organic compounds (VOCs) were introduced into the sensor array. A statistical analysis of the results revealed that typical VOCs could be successfully classified into five categories—aliphatic hydrocarbons, alcohols, ketones, aromatic hydrocarbons and amines—with an accuracy rate of 98%.

The different gas-sensing behaviours of virgin graphene, graphene (GO), and reduced graphene (rGO) are caused by their unique structural characteristics. Due to its two-dimensional structure, graphene is extremely sensitive to the adsorption of gas molecules in terms of electron transport [81]. Compared to pristine graphene, reduced graphene oxide (rGO) is more active as a sensor element due to inherent structural defects and residual oxygen groups [82]. Tang et al. [82] have reported a scalable technique to obtain an ultrathin layer of poly(pyrrole) through electro-polymerisation on rGO as support material to obtain room temperature sensors for ammonia. Biswas et al. [83] have developed a Schottky diode electrode based on multi-polymeric layer (PTFE, PVDF and PANI) on top of BiVO4 to obtain a heterojunction where GO has been employed as a filler. On exposure to 1800 ppm of ammonia, the sensor exhibited a sensitivity value of 3654, which was two times higher than the pristine (PTFE, PVDF and PANI), an improvement attributed to the increase in conductivity with added GO (0.04 wt%) nanosheets into polymeric layer. The Nanocomposite of polypyrrole (PPy) and graphene nanoplatelets (GN) was synthesised by a sol–gel process combined with in situ chemical polymerisation and finally decorated with titanium dioxide for the detection of ammonia [84]. The sensors could detect NH3 molecules at room temperature with reproducibility and excellent selectivity. A nanocomposite of graphene-poly(pyrrole)-tungsten oxide [85] could be achieved by oxidative polymerisation of pyrrole in the presence of GO. The nanocomposite could detect ammonia in the 5–15 ppm range at a sensitivity factor of 58% with 50s/120s response and recovery time at an average. Most importantly, the sensor behaviour was unperturbed at 50% relative humidity. Poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] has been employed by Sahu et al. towards the formation of a nanohybrid with GO to fabricate a polymeric thin film transistor [86], that showed a positive shift in threshold voltage ranging from −1 V to +23 V after exposure to 30 ppm concentration of NO2. According to the authors, the adsorption of NO2 molecules in the hybrid PBTTT/GO film causes the hole carrier concentration in the composite film to rise, which in turn causes an increase in drain current. Paramar et al. reported sensing of toluene with graphene/PANI nanocomposite films obtained in the solution phase [87]. The sensors exhibited room temperature detection of 100 ppm toluene with good response recovery behaviour. The authors suggested that the presence of active sites on the graphene in C-PANI and swelling junctions between graphene flakes is responsible for sensing behaviour. Husain et al. reported enhanced electrical conductivity in polythiophene/graphene nanocomposites due to an extended π-conjugated system. The sensor exhibited detection of ethanol with a low detection limit of 400 ppm and complete reversibility within 360 s at room temperature [88].

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5. Challenges and future directions

Although carbon-based nanocomposites have demonstrated potential for sensing a diverse range of gaseous analytes, a few issues remained as a critical constraint towards commercial success

  1. Achieving a homogeneous dispersion of carbon-based nanomaterials throughout the sensor matrix without clustering or aggregation.

  2. Scalable manufacturing process to achieve large-scale production through laboratory synthesis.

  3. Consideration of response and recovery behaviour of sensors as physisorption of gas analyte on sensor surface leads to slow recovery.

  4. Dedicated investigation is needed to achieve a reliant lifetime of sensors under challenging situations, such as humid conditions.

  5. Further study on cross-sensitivity behaviour of nanocomposite sensors to achieve selective behaviour.

  6. Cost-effectiveness for commercial viability.

To sum up, carbon nanocomposites are an exciting and quickly expanding area of materials science that presents a plethora of opportunities for research and development. Because of their special combination of qualities, they can be adapted to address real-life challenges, from enhancing medical treatments to increasing the effectiveness of transportation. The future technologies are anticipated to be significantly shaped by nanocomposites as research and production techniques advance. Continued research and developments in this field are essential for reliable, cost-effective, low-footprint solutions that can be easily interfaced with standard industrial/commodity protocols.

References

  1. 1. Saxena P, Shukla P. A review on recent developments and advances in environmental gas sensors to monitor toxic gas pollutants, environmental progress and sustainable energy. American Institute of Chemical Engineers. 2023;42(5):e14126
  2. 2. Crippa M, Guizzardi D, Pisoni E, Solazzo E, Guion A, Muntean M, et al. Global anthropogenic emissions in urban areas: Patterns, trends, and challenges. Environmental Research Letters. 2021;16:074033. DOI: 10.1088/1748-9326/ac00e2
  3. 3. Rushi AD, Datta K, Ghosh P, Shirsat MD. Functionalized carbon nanotubes for detection of volatile organic pollutant. In: Saleh HE-D, El-Sheikh SMM, editors. Perspective of Carbon Nanotubes. London, UK: IntechOpen; 2018. DOI: 10.5772/intechopen.85045. ISBN: 978-1-78984-402-3 Print ISBN: 978-1-78984. Available from: http://www.intechopen.com/books/perspective-of-carbon-nanotubes
  4. 4. Idrees Z, Zheng L. Low cost air pollution monitoring systems: A review of protocols and enabling technologies. Journal of Industrial Information Integration. 2020;17:100123. DOI: 10.1016/j.jii.2019.100123
  5. 5. Gupta SK, Singh B. Instruments for monitoring air pollution and air quality. In: Aswal DK, Yadav S, Takatsuji T, Rachakonda P, Kumar H, editors. Handbook of Metrology and Applications. Singapore: Springer; 2023. DOI: 10.1007/978-981-99-2074-7_91
  6. 6. Godlewska K, Stepnowski P, Paszkiewicz M. Pollutant analysis using passive samplers: Principles, sorbents, calibration and applications. A review. Environmental Chemistry Letters. 2021;19:465-520. DOI: 10.1007/s10311-020-01079-6
  7. 7. Huang C, Shan W, Xiao H. Recent advances in passive air sampling of volatile organic compounds. Aerosol and Air Quality Research. 2018;18:602-622. DOI: 10.4209/aaqr.2017.12.0556
  8. 8. Srivastava A, Mazumdar D. Monitoring and reporting VOCs in ambient air, air quality monitoring, assessment and management. In: Air Quality Monitoring, Assessment and Management. London, UK: IntechOpen; 2011. DOI: 10.5772/16774
  9. 9. Engel-Cox JA, Hoff RM, Haymet ADJ. Recommendations on the use of satellite remote-sensing data for urban air quality. Journal of the Air & Waste Management Association. 2004;54(11):1360-1371. DOI: 10.1080/10473289.2004.10471005
  10. 10. Cretescu I, Lutic D, Manea LR. Electrochemical sensors for monitoring of indoor and outdoor air pollution. In: Electrochemical Sensors Technology. London, UK: IntechOpen; 2017. DOI: 10.5772/intechopen.68512
  11. 11. Tittarelli A, Borgini A, Bertoldi M, DeSaeger E, Ruprecht A, Stefanoni R, et al. Estimation of particle mass concentration in ambient air using a particle counter. Atmospheric Environment. 2008;42(36):8543-8548. DOI: 10.1016/j.atmosenv.2008.07.056
  12. 12. Kim YY, Kim MK, Shin HS. Determination of volatile organic compounds (VOCs) levels from various smoking cessation aids by using gas chromatography-mass spectrometry methodology. Journal of Toxicology and Environmental Health, Part A. 2022;85(3):110-120. DOI: 10.1080/15287394.2021.1979436
  13. 13. Ghosh PK, Datta K, Rushi A, Tilekar S, Karle P, Shirsat M. Tailoring of poly (N-methyl pyrrole) thin film surface with Au-nanoparticles for selective sensing of H2S. Journal of Physics: Conference Series. 2023;2426:012046. DOI: 10.1088/1742-6596/2426/1/012046
  14. 14. Wang C, Wang Y, Yang Z, Nantao H. Review of recent progress on graphene-based composite gas sensors. Ceramics International. 2021;47(12):16367-16384. DOI: 10.1016/j.ceramint.2021.02.144
  15. 15. Rushi AD, Datta KP, Ghosh PS, Mulchandani A, Shirsat MD. Functionalized carbon nanotubes for detection of volatile organic pollutant. In: Perspective of Carbon Nanotubes. London, UK: Intech Open; 2019. DOI: 10.5772/intechopen.85045
  16. 16. Yang S, Lei G, Xu H, Lan Z, Wang Z, Gu H. Metal oxide based heterojunctions for gas sensors: A review. Nanomaterials. 2021;11:1026. DOI: 10.3390/nano11041026
  17. 17. Omanović-Mikličanin E, Badnjević A, Kazlagić A, et al. Nanocomposites: A brief review. Health Technology. 2020;10:51-59. DOI: 10.1007/s12553-019-00380-x
  18. 18. Tahir H, Saad M, Shafi N, Muslim F. Chapter 3 - composite. In: Ghaedi M, editor. Interface Science and Technology. Vol. 33. London, UK: Elsevier; 2021. pp. 211-278. DOI: 10.1016/ B978-0-12-818805-7.00004-7
  19. 19. Guo Z, Pereira T, Choi O, Wang Y, Hahn HT. Surface functionalized alumina nanoparticle filled polymeric nanocomposites with enhanced mechanical properties. Journal of Materials Chemistry. 2006;16:2800-2808. DOI: 10.1039/B603020C
  20. 20. Lalire T, Longuet C, Taguet A. Electrical properties of graphene/multiphase polymer nanocomposites: A review. Carbon. 2024;225:119055. DOI: 10.1016/j.carbon.2024.119055
  21. 21. Sakib MN, Iqbal AKMA. Epoxy based nanocomposite material for automotive application - a short review. International Journal of Automotive and Mechanical Engineering (IJAME). 2021;18(3):9127-9140. DOI: 10.15282/ijame.18.3.2021.24.0701. ISSN: 2229-8649 e-ISSN: 2180-1606
  22. 22. Joshi M, Chatterjee U. 8 - polymer nanocomposite: An advanced material for aerospace applications. In: Advanced Composite Materials for Aerospace Engineering, Processing, Properties and Applications. Duxford, UK: Woodhead Publishing; 2016. pp. 241-264. DOI: 10.1016/ B978-0-08-100037-3.00008-0
  23. 23. Datta K, Ghosh PK, Rushi A. In: Ghosh PK, Datta K, Rushi AD, editors. Introduction to Carbon Nanotubes-Redefining the World of Electronics. London, UK: IntechOpen; 2021. DOI: 10.5772/intechopen.87724
  24. 24. Kharlamova MV, Paukov M, Burdanova MG. Nanotube functionalization: Investigation, methods and demonstrated applications. Materials (Basel). 2022;15(15):5386. DOI: 10.3390/ma15155386
  25. 25. Chen RJ, Bangsaruntip S, Drouvalakis KA, et al. Noncovalent functionalization of carbon nanotubes for highly specific electronic biosensors. Proceedings of the National Academy of Sciences. 2003;100(9):4984-4989
  26. 26. Nakayama-Ratchford O, Bangsaruntip S, Sun X, Welsher K, Dai H. Noncovalent functionalization of carbon nanotubes by fluorescein−polyethylene glycol: Supramolecular conjugates with pH-dependent absorbance and fluorescence. Journal of the American Chemical Society. 2007;129(9):2448-2449
  27. 27. Maser W, Benito AM, Munoz E, Martinez MT. Carbon nanotubes: From fundamental nanoscale objects towards functional nanocomposites and applications. In: Vaseastha A, Mihailescu IN, editors. Functionalized Nanoscale Materials, Devices and Systems. Dordrecht, The Netherlands: Springer; 2008. pp. 101-120
  28. 28. Vogel SR, Muller K, Plutowski U, Kappes MM, Richert C. DNA–carbon nanotube interactions and nanostructuring based on DNA. Physica Status Solid B. 2007;244:4026-4029
  29. 29. Shin SR, Lee CK, So IS, Jeon JH, Kang TM, Kee CW, et al. DNA-wrapped single-walled carbon nanotube hybrid fibers for supercapacitors and artificial muscles. Advanced Materials. 2008;20:466-470
  30. 30. Mu Q , Liu W, Xing Y, Zhou H, Li Z, Zhang Y, et al. Protein binding by functionalized multiwalled carbon nanotubes is governed by the surface chemistry of both parties and the nanotube diameter. Journal of Physical Chemistry C. 2008;112:3300-3307
  31. 31. Yu JG, Huang KL, Liu SQ , Tang JC. Preparation and characterization of polycarbonate modified multiple-walled carbon nanotubes. Chinese Journal of Chemistry. 2008;26:560-563
  32. 32. Zhang D, Shi L, Fang J, Li X, Dai K. Preparation and modification of carbon nanotubes’. Materials Letters. 2005;59:4044-4047
  33. 33. Holzinger M, Baur J, Haddad R, Wang X, Cosnier S. Multiple functionalization of single-walled carbon nanotubes by dip coating. Chemical Communications. 2011;47:2450-2452
  34. 34. Peng C, Zhang S, Jewell D, Chen GZ. Carbon nanotube and conducting polymer composites for supercapacitors. Progress in Natural Science. 2008;18(7):777-788
  35. 35. Datta K, Ghosh P, More MA, Shirsat MD, Mulchandani A. Controlled functionalization of single-walled carbon nanotubes for enhanced ammonia sensing: A comparative study. Journal of Physics D: Applied Physics. 2012;45:355305
  36. 36. Chai H, Xu Y, He PG, Fang YZ. Indicator free DNA hybridization detection by impedance measurement based on the DNA-doped conducting polymer film formed on the carbon nanotube modified electrode. Electroanalysis. 2003;15:1864-1870
  37. 37. Tsai YC, Li SC, Liao SW. Electrodeposition of polypyrrole-multiwalled carbon nanotube–glucose oxidase nanobiocomposite film for the detection of glucose. Biosensors & Bioelectronics. 2006;22:495-500
  38. 38. Luo X, Killard AJ, Morrin A, Smyth MR. Enhancement of a conducting polymer-based biosensor using carbon nanotube-doped polyaniline. Analytica Chimica Acta. 2006;575:39-44
  39. 39. Zhou Y-K. Electrochemical capacitance of well-coated single-walled carbon nanotubes with polyaniline composite. Electrochimica Acta. 2004;49:257-262
  40. 40. Huang J-E, Li X-H, Xu J-C, Li H-L. Well dispersed single-walled carbon nanotube/polyaniline composite films. Carbon. 2003;41:2731-2736
  41. 41. Rushi A, Datta K, Ghosh P, Mulchandani A, Shirsat MD. Iron tetraphenyl porphyrin functionalized single wall carbon nanotubes for the detection of benzene. Materials Letters. 2013;96:38-41
  42. 42. Natale CD, Brunink J, Bungaro F, Davide F, Amico AD, Paolesse R, et al. Metalloporphyrin coated quartz micro balance sensor for amine detection. In: Proceedings of the 2nd East Asia Conference on Chemical Sensors, Xian China October 1995. Beijing: International Academic; 1995
  43. 43. Cognet L, Tsyboulski DA, Rocha JR, Doyle CD, Tour JM, Weisman RB. Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions. Science. 2007;316:1465-1468
  44. 44. Meng L, Fu C, Lu Q. Advanced technology for functionalization of carbon nanotubes. Progress in Natural Science. 2009;19:801-810
  45. 45. Lefrant S, Buisson JP, Schreiber J, Chauvet O, Baibarac M, Baltog I. Raman studies of carbon nanotubes and polymer nanotube composites. Molecular Crystals and Liquid Crystals. 2004;415:125-132
  46. 46. Murakami H, Nomura T, Nakashima N. Noncovalent porphyrin-functionalized single-walled carbon nanotubes in solution and the formation of porphyrin–nanotube nanocomposites. Chemical Physics Letters. 2003;378:481-485
  47. 47. Zhong Q , Diev VV, Roberts ST, Antunez PD, Brutchey RL, Bradforth SE, et al. Fused porphyrin-single-walled carbon nanotubes hybrids: Efficient formation and photophysical characterization. ACS Nano. 2013;7:3466-3475
  48. 48. Zhou X, Dai Z, Bao J, Guo Y-G. Wet milled synthesis of an Sb/MWCNT nanocomposite for improved sodium storage. Journal of Materials Chemistry A. 2013;1(44):13727-13731
  49. 49. Zein SHS, Yeoh L-C, Chai S-P, Mohamed AR, Mahayuddin MEM. Synthesis of manganese oxide/carbon nanotube nanocomposites using wet chemical method. Journal of Materials Processing Technology. 2007;190(1-3):402-405
  50. 50. Dariyal P, Sharma S, Chauhan GS, Singh BP, Dhakate SR. Recent trends in gas sensing via carbon nanomaterials: Outlook and challenges. Nanoscale Advances. 2021;3:6514-6544
  51. 51. Xu K, Fu C, Gao Z, Wei F, Ying Y, Xu C, et al. Nanomaterial-based gas sensors: A review. Instrumentation Science & Technology. 2018;46(2):115-145. DOI: 10.1080/10739149.2017.1340896
  52. 52. Recum P, Hirsch T. Graphene-based chemiresistive gas sensors. Nanoscale Advances. 2024;6:11-31
  53. 53. Meyappan M, editor. Carbon Nanotubes: Properties and Applications. Boca Raton: Taylor and Francis; 2005
  54. 54. Kong J, Franklin N, Zhou C, Chapline M, Peng S, Cho K, et al. Nanotube molecular wires as chemical sensors. Science. 2000;287:622
  55. 55. Zhou C, Kong J, Dai H. Gating individual nanotubes and crosses with scanning probes. Applied Physics Letters. 2000;76:1597-1599
  56. 56. Someya T, Small J, Kim P, Nuckolls C, Yardley JT. Alcohol vapor sensors based on single-walled carbon nanotube field effect transistors. Nano Letters. 2003;3:877
  57. 57. Novak JP, Snow ES, Houser EJ, Park D, Stepnowski JL, Mc Gill RA. Nerve agent detection using networks of single-walled carbon nanotubes. Applied Physics Letters. 2003;83:4026
  58. 58. Chang YW, Oh JS, Yoo SH, Choi HH, Yoo KH. Electrically refreshable carbon-nanotube-based gas sensors. Nanotechnology. 2007;18:435504
  59. 59. Valentini L, Cantalini C, Armentano I, Kenny JM, Lozzi L, Santucci S. Investigation of the sensitivity properties of multiwalled carbon nanotubes prepared by plasma enhanced chemical vapor deposition. Journal Vaccum Science and Technology B. 1996;2003:21
  60. 60. Li J, Lu JY, Ye Q , Cinke M, Han J, Meyappan M. Carbon nanotube sensors for gas and organic vapor detection. Nano Letters. 2003;3:929-933
  61. 61. Suehiro J, Zhou GB, Hara M. Fabrication of a carbon nanotube-based gas sensor using dielectrophoresis and its application for ammonia detection by impedance spectroscopy. Journal of Physics D: Applied Physics. 2003;36:109
  62. 62. Li J, Lu Y, Ye Q , Delzeit L, Meyyapan M. Gas sensor array using carbon nanotubes and microfabrication technology. Electronics Solid – State Letters. 2005;8:H100
  63. 63. Goldoni A, Larciprete R, Petaccia L, Lazzit S. Single-wall carbon nanotube interaction with gases: Sample contaminants and environmental monitoring. Journal of American Chemical Society. 2003;125:11329
  64. 64. Sippel-Oakley AJ, Wang HT, Kang BS, Wu Z, Ren F, Rinzler AG, et al. Carbon nanotube films for room temperature hydrogen sensing. Nanotechnology. 2005;16:2218
  65. 65. Matranga BC, Bockrath B. Hydrogen-bonded and physisorbed CO in single-walled carbon nanotube bundles. Journal of Physical Chemistry B. 2005;109:4853
  66. 66. Freddi S, Michele Vergari G, Sangaletti PL. A chemiresistor sensor array based on graphene nanostructures: From the detection of ammonia and possible interfering VOCs to chemometric analysis. Sensors. 2023;23(2):882
  67. 67. Zhang T, Nix MB, Yoo B-Y, Deshusses MA, Myung NV. Electrochemically functionalized single-walled carbon nanotube gas sensor. Electroanalysis. 2006;18(12):1153-1158
  68. 68. Park SJ, Kwon OS, Jang J. A high-performance hydrogen gas sensor using ultrathin polypyrrole-coated CNT nanohybrids. Chemical Communications. 2013;49:4673-4675
  69. 69. Xue L, Wang W, Guo Y, Liu G, Wan P. Flexible polyaniline/carbon nanotube nanocomposite film-based electronic gas sensors. Sensors and Actuators B: Chemical. 2017;244:47-53
  70. 70. Bachhav SG, Patil DR. Study of polypyrrole-coated MWCNT nanocomposites for ammonia sensing at room temperature. Journal of Materials Science and Chemical Engineering. 2015;3:30
  71. 71. Zhang W, Cao S, Wu Z, Zhang M, Cao Y, Guo J, et al. High-performance gas sensor of polyaniline/carbon nanotube composites promoted by interface engineering. Sensors. 2020;20:149
  72. 72. Hong S, Oh J, Park H, et al. Polyurethane foam coated with a multi-walled carbon nanotube/polyaniline nanocomposite for a skin-like stretchable array of multi-functional sensors. NPG Asia Materials. 2017;9:e448
  73. 73. Wu H, Chen Z, Zhang J, et al. Phthalocyanine-mediated non-covalent coupling of carbon nanotubes with polyaniline for ultrafast NH3 gas sensors. Journal of Materials Chemistry A. 2017;5:24493-24501
  74. 74. Kumar S, Pavelyev V, Mishra P, et al. Thin film chemiresistive gas sensor on single-walled carbon nanotubes-functionalized with polyethylenimine (PEI) for gas sensing. Bulletin of Materials Science. 2020;43:61
  75. 75. Ndiaye A, Bonnet P, Pauly A, Dubois M, Brunet J, Varenne C, et al. Noncovalent functionalization of single-wall carbon nanotubes for the elaboration of gas sensor dedicated to BTX type gases: The case of toluene. Journal of Physical Chemistry C. 2013;117:20217-20228
  76. 76. Lvova L, Mastroianna M, Pomarico G, Santonico M, Pennazza G, Natale CD, et al. Carbon nanotubes modified with porphyrin units for gaseous phase chemical sensing. Sensors and Actuators B. 2012;170:163-171
  77. 77. Shirsat MD, Sarkar T, Kakoullis J Jr, Myung NV, Konnanath B, Spanias A, et al. Porphyrins-functionalized single-walled carbon nanotubes chemiresistive sensor arrays for VOCs. Journal of Physical Chemistry C. 2012;116:3845-3850
  78. 78. Sarkar T, Srinives S, Sarkar S, Haddon RC, Mulchandani A. Single-walled carbon nanotube−poly(porphyrin) hybrid for volatile organic compounds detection. Journal of Physical Chemistry C. 2014;118:1602-1610
  79. 79. Rushi AD, Datta KP, Ghosh PS, Mulchandani A, Shirsat MD. Selective discrimination among benzene, toluene, and xylene: Probing metalloporphyrin-functionalized single-walled carbon nanotube-based field effect transistors. Journal of Physical Chemistry C. 2014;118:24034-24041
  80. 80. Liu SF, Moh LCH, Swager TM. Single-walled carbon nanotube-metalloporphyrin composites in chemiresistive gas sensor arrays for volatile organic compounds. Chemistry of Materials. 2015;27:3560-3563
  81. 81. Tian W, Liu X, Yu W. Research progress of gas sensor based on graphene and its derivatives: A review. Applied Sciences. 2018;8(7):1-21
  82. 82. Tang X, Raskin J-P, Kryvutsa N, Hermans S, Slobodian O, Nazarov AN, et al. An ammonia sensor composed of polypyrrole synthesized on reduced graphene oxide by electropolymerization. Sensors and Actuators B: Chemical. 2020;305:127423
  83. 83. Md Rokon U, Biswas D, Oh W-C. Comparative study on gas sensing by a Schottky diode electrode prepared with graphene–semiconductor–polymer nanocomposites. RSC Advances. 2019;9:11484-11492
  84. 84. Xiang C, Jiang D, Zou Y, Chu H, Qiu S, Zhang H, et al. Ammonia sensor based on polypyrrole–graphene nanocomposite decorated with titania nanoparticles. Ceramics International. 2015;41:6432-6438
  85. 85. Albaris H, Karuppasamy G. Investigation of NH3 gas sensing behavior of intercalated PPy–GO–WO3 hybrid nanocomposite at room temperature. Materials Science and Engineering: B. 2020;257:114558
  86. 86. Sahu PK, Pandey RK, Dwivedi R, et al. Polymer/graphene oxide nanocomposite thin film for NO2 sensor: An in situ investigation of electronic, morphological, structural, and spectroscopic properties. Scientific Reports. 2020;10:2981
  87. 87. Parmar M, Balamurugan C, Lee D-W. PANI and graphene/PANI nanocomposite films — comparative toluene gas sensing behavior. Sensors. 2013;13:16611-16624
  88. 88. Husain A, Ahmad S, Mohammad F. Synthesis, characterisation and ethanol sensing application of polythiophene/graphene nanocomposite. Materials Chemistry and Physics. 1 Jan 2020;239:122324

Written By

Arti Rushi and Kunal Datta

Submitted: 30 April 2024 Reviewed: 08 July 2024 Published: 28 August 2024