Skip to main content
Log in

Efficient room temperature methanol sensors based on polyaniline/graphene micro/nanocomposites

  • Original Research
  • Published:
Iranian Polymer Journal Aims and scope Submit manuscript

A Correction to this article was published on 21 May 2020

This article has been updated

Abstract

The chemically prepared pristine and graphene-doped polyaniline (PANI) samples are utilized for the fabrication of room temperature methanol sensors. For the fabrication of PANI/graphene-based sensing devices, four samples of PANI/graphene composites were prepared with four different concentrations of graphene (2, 4, 6 and 8 wt%). The surface morphology of the prepared composites was analyzed under field emission scanning electron microscopy (FE-SEM), which revealed the agglomerated structures of PANI/graphene composites. X-Ray diffraction studies carried out on these samples revealed the semi-crystalline nature of the samples, whereas, Raman studies confirmed the growth of PANI with the presence of all fundamental bands of PANI in the pristine as well as in its doped state. The prepared PANI/graphene composites devices were tested for alcohol detection at two different concentrations (50 and 100 ppm) of methanol. The change in electric current with the change in environment has been recorded as a sensing parameter and is employed to determine other sensor parameters such as percentage response, response time and recovery time. The sensing response of the prepared samples is found to increase with graphene doping concentration as well as methanol ppm level. The PANI/graphene composite with 8 wt% doping of graphene has shown the highest response (~ 61.5% at 100 ppm) and the lowest response time (55 s). The mechanism of gas sensing has also been discussed in details with the possible theoretical analogy with the adsorption and desorption of gas molecules in accordance with Langmuir kinetic theory.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

Change history

  • 21 May 2020

    The article listed above was initially published with typo error in Eq. (4).

References

  1. Sonmezoglu S, Tas R, Akim S, Can M (2012) Polyaniline micro-rods based heterojunction solar cell: structural and photovoltaic properties. Appl Phys Lett 101:253301

    Article  CAS  Google Scholar 

  2. Wu G, Mack NH, Gao W, Ma S, Zhong R, Han J, Baldwin JK, Zelenay P (2012) Nitrogen-doped graphene-rich catalysts derived from heteroatom polymers for oxygen reduction in nonaqueous lithium-O2 battery cathodes. ACS Nano 6:9764–9776

    Article  CAS  PubMed  Google Scholar 

  3. Pal R, Goyal SL, Gupta V, Rawal I (2019) MnO2-magnetic core-shell structured polyaniline dependent enhanced EMI shielding effectiveness: a study of VRH conduction. Chem Sel 4:9194–9210

    CAS  Google Scholar 

  4. Soleimani E, Aghamiri SF, Molla-Abbasi P, Shabanian M (2020) Tuning the polymer–graphene interfaces by picric acid molecules to improve the sensitivity of a prepared conductive polymer composite gas detector. Iran Polym J 29:341–350

    Article  CAS  Google Scholar 

  5. Arora K, Puri NK (2020) Chemiresistive sensing platform based on PdO-PANI/ITO heterostructure for room temperature hydrogen detection. Mater Chem Phys 247:122850

    Article  CAS  Google Scholar 

  6. Virji S, Huang J, Kaner RB, Weiller BH (2004) Polyaniline nanofibergas sensors: examination of response mechanisms. Nano Lett 4:491–496

    Article  CAS  Google Scholar 

  7. Song E, Choi JW (2013) Conducting polyaniline nanowire and its applications in chemiresistive sensing. Nanomaterials 3:498–523

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Kumar SRS, Oh JS, Kim DW (2006) Polyaniline nanofibres as a cathode material for rechargeable lithium-polymer cells assembled with gel polymer electrolyte. J Power Sour 163:573–577

    Article  CAS  Google Scholar 

  9. Boix PP, Belmonte GG, Munecas U, Neophytou M, Waldauf C, Pacios R (2009) Determination of gap defect states in organic bulk heterojunction solar cells from capacitance measurements. Appl Phys Lett 95:233302

    Article  CAS  Google Scholar 

  10. Li T, Wang X, Liu P, Yang B, Diao S, Gao Y (2020) Synthesis of graphene/polyaniline copolymer for solid-state supercapacitor. J Electroanal Chem 680:113908

    Article  CAS  Google Scholar 

  11. Bundgaard E, Krebs FC (2007) Low band gap polymers for organic photovoltaics. Sol Energy Mater Sol Cells 91:954–985

    Article  CAS  Google Scholar 

  12. Yang Y, Ouyang J, Ma L, Tseng RJH, Chu CW (2006) Electrical switching and bistability in organic/polymeric thin films and memory devices. Adv Funct Mater 16:1001–1014

    Article  CAS  Google Scholar 

  13. Paul EW, Ricco AJ, Wrighton MS (1985) Resistance of polyaniline films as a function of electrochemical potential and the fabrication of polyaniline-based microelectronic devices. J Phys Chem 89:1441–1447

    Article  CAS  Google Scholar 

  14. Nadagouda MN, Varma RS (2007) Preparation of novel metallic and bimetallic cross-linked poly(vinyl alcohol) nanocomposites under microwave irradiation. Macromol Rapid Commun 28:465–472

    Article  CAS  Google Scholar 

  15. Karim MR, Yeum JH, Lee MY, Lee MS, Lim KT (2008) UV-curing synthesis of sulfonatedpolyaniline/silver nanocomposites by an in situ reduction method. Polym Adv Technol 20:639–663

    Article  CAS  Google Scholar 

  16. Pramod NG, Pandey SN, Sahay PP (2012) Structural, optical and methanol sensing properties of sprayed In2O3 nanoparticle thin films. Ceram Int 38:4151–4158

    Article  CAS  Google Scholar 

  17. Péres LO, Li RWC, Yamauchi EY, Lippi R, Gruber J (2012) Conductive polymer gas sensor for quantitative detection of methanol in Brazilian sugar-cane spirit. Food Chem 130:1105–1107

    Article  CAS  Google Scholar 

  18. Lee JH (2009) Gas sensors using hierarchical and hollow oxide nanostructures: overview. Sens Actuators B Chem 140:319–336

    Article  CAS  Google Scholar 

  19. Lange U, Roznyatovskaya NV, Mirsky VM (2008) Conducting polymers in chemical sensors and arrays. Anal Chim Acta 614:1–26

    Article  CAS  PubMed  Google Scholar 

  20. Pal R, Goyal SL, Sharma S (2019) Facial synthesis of polyaniline and its nanocomposites for room temperature methanol sensors. AIP Conf Proc 2115:030217

    Article  CAS  Google Scholar 

  21. Jumali MHH, Ramli N, Izzuddin MMSI, Yahaya M (2011) Influence of PANI additions on methanol sensing properties of ZnO thin films. Sains Malays 40:203–210

    Google Scholar 

  22. Crowley K, Morrin A, Shepherd RL, Panhuis M, Wallace GG, Smyth MR, Killard AJ (2010) Fabrication of polyaniline-based gas sensors using piezoelectric inkjet and screen printing for the detection of hydrogen sulfide. IEEE Sens J 10:1419–1426

    Article  CAS  Google Scholar 

  23. Banerjee N, Roy S, Sarkar CK, Bhattacharyya P (2013) High dynamic range methanol sensor based on aligned ZnO nanorods. IEEE Sens J 13:1669–1676

    Article  CAS  Google Scholar 

  24. Prasad GK, Krishnan TPR, Kumar DS, Krishna MG (2005) Ammonia sensing characteristics of thin film based on polyelectrolyte templated polyaniline. Sens Actuator B Chem 106:626–631

    Article  CAS  Google Scholar 

  25. Eising M, Cava CE, Salvatierr RV, Zarbin AJG, Roman LS (2017) Doping effect on self-assembled films of polyaniline and carbon nanotube applied as ammonia gas sensor. Sens Actuator B Chem 245:25–33

    Article  CAS  Google Scholar 

  26. Ridhi R, Gawri R, Abbas SJ, Saini GSS, Tripathi SK (2015) Chemical sensing of copper phthalocyanine sol-gel glass through organic vapors. AIP Conf Proc 1661:110015

    Article  CAS  Google Scholar 

  27. Dong B, He BL, Xu CL, Li HL (2007) Preparation and electrochemical characterization of polyaniline/multi-walled carbon nanotubes composites for supercapacitor. Mater Sci Eng B 143:7–13

    Article  CAS  Google Scholar 

  28. Chaudhari HK, Kelkar DS (1997) Investigation of structure and electrical conductivity in doped polyaniline. Polym Intern 42:380–384

    Article  CAS  Google Scholar 

  29. Reddy KR, Sin BC, Ryu KS, Noh J, Lee Y (2009) In situ self-organization of carbon black-polyaniline composites from nanospheres to nanorods: synthesis, morphology, structure and electrical conductivity. Synth Methods 159:1934–1939

    Article  CAS  Google Scholar 

  30. Pouget JP, Hsu CH, MacDiarmid AG, Epstein AJ (1995) Structural investigation of metallic PAN-CSA and some of its derivatives. Synth Methods 69:119–120

    Article  CAS  Google Scholar 

  31. Lee DS, Riedl C, Krauss B, Klitzing KV, Starke U, Smet JH (2008) Raman spectra of epitaxial graphene on SiC and of epitaxial graphene transferred to SiO2. Nano Lett 8:4320–4325

    Article  CAS  PubMed  Google Scholar 

  32. Kumar P, Lahiri I, Mitra A (2019) Nickel mediated few-layer graphene growth on glass substrates by pulsed laser deposition. Results Phys 14:102350

    Article  Google Scholar 

  33. Wang K, Tai G, Wong KH, Lau SP, Guo W (2011) Ni induced few-layer graphene growth at low temperature by pulsed laser deposition. AIP Adv 1:022141

    Article  CAS  Google Scholar 

  34. Cancado LG, Takai K, Enoki T, Endo M, Kim YA, Mizusaki H, Jorio A, Coelho LN, Magalhães-Paniago R, Pimenta MA (2006) General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy. Appl Phys Lett 88:163106

    Article  CAS  Google Scholar 

  35. Gautam M, Jayatissa AH (2012) Detection of organic vapors by graphene films functionalized with metallic nanoparticles. J Appl Phys 112:114326

    Article  CAS  Google Scholar 

  36. Gemeay AH, Mansour IA, El-Sharkawy RG, Zaki AB (2015) Preparation and characterization of polyaniline/manganese dioxide composites via oxidative polymerization: effect of acids. Euro Pol J 41:2575–2583

    Article  CAS  Google Scholar 

  37. Paulraj R, Mani GK, Nallathambi L, Rayappan JBB (2016) Aroom temperature methanol vapour sensor based on polyaniline nanoparticles. J Nanosci Nanotechnol 16:8315–8321

    Article  CAS  Google Scholar 

  38. Kumar L, Rawal I, Kaur A, Annapoorni S (2017) Flexible room temperature ammonia sensor based on polyaniline. Sens Actuator B Chem 240:408–416

    Article  CAS  Google Scholar 

  39. Saaedi A, Shabani P, Yousefi R (2019) High performance of methanol gas sensing of ZnO/PAni nanocomposites synthesized under different magnetic field. J Alloys Compd 802:335–344

    Article  CAS  Google Scholar 

  40. Saaedi A, Shabani P, Yousefi R (2019) Study on the effects of the magneto assisted deposition on ammonia gas sensing properties of polyaniline. J Mater Sci Mater Electro 30:10765–10775

    Article  CAS  Google Scholar 

  41. Navazania S, Shokuhfara A, Hassanisadi M, Carlo AD, Shahcheraghi N (2018) Fabrication and characterization of a sensitive, room temperature methane sensor based on SnO2@reduced graphene oxide-polyaniline ternary nanohybrid. Mater Sci Semicond Proc 88:139–147

    Article  CAS  Google Scholar 

  42. Tabr FA, Salehiravesh F, Adelnia H, Gavgani JN, Mahyari M (2019) High sensitivity ammonia detection using metal nanoparticles decorated on graphene macroporous frameworks/polyaniline hybrid. Talanta 197:457–464

    Article  CAS  Google Scholar 

  43. Lee CT, Wang YS (2019) High-performance room temperature NH3 gas sensors based on polyaniline-reduced graphene oxide nanocomposite sensitive membrane. J Alloys Compd 789:693–696

    Article  CAS  Google Scholar 

  44. Zhang LS, Wang WD, Liang XQ, Chu WS, Song WG, Wang W, Wu ZY (2011) Characterization of partially reduced graphene oxide as room temperature sensor for H2. Nanoscale 3:2458–2460

    Article  CAS  PubMed  Google Scholar 

  45. Hu H, Trejo M, Nicho ME, Saniger JM, Valenzuela AG (2002) Adsorption kinetics of optochemical NH3 gas sensing with semiconductor polyaniline films. Sens Actuator B Chem 82:14–23

    Article  CAS  Google Scholar 

  46. Tan CK, Blackwood DJ (2000) Interactions between polyaniline and methanol vapour. Sens Actuator B Chem 71:184–191

    Article  CAS  Google Scholar 

  47. Babaei M, Alizadeh N (2013) Methanol selective gas sensor based on nano-structured conducting polypyrrole prepared by electrochemically on interdigital electrodes for biodiesel analysis. Sens Actuator B Chem 183:617–626

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Authors are thankful for financial assistance from DST-FIST for providing XRD facility. Authors are also grateful to UGC-DAE CSR, Indore for providing the FESEM and Raman facilities for the present work.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Sneh Lata Goyal.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pal, R., Goyal, S.L., Rawal, I. et al. Efficient room temperature methanol sensors based on polyaniline/graphene micro/nanocomposites. Iran Polym J 29, 591–603 (2020). https://doi.org/10.1007/s13726-020-00822-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13726-020-00822-8

Keywords

Navigation