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Polyindole Based Nanocomposites and Their Applications: A Review

Rita1, Sameena Mehtab*, M.G.H. Zaidi1, Kavita Singhal1, Bhagwati Arya1 and T.I. Siddiqui2

1Department of Chemistry, G.B. Pant University of Agriculture & Technology, Uttarakhand 263 145, India.

2Department of Chemistry, D.I.T University, Mussoorie Diversion Road, Makkawala, Dehradun, Uttarakhand 248001, India.

Corresponding Author’s Email: smiitr@gmail.com

DOI : http://dx.doi.org/10.13005/msri/160202

Article Publishing History
Article Received on : 01-July-2019
Article Accepted on : 03-Aug-2019
Article Published : 06 Aug 2019
Plagiarism Check: Yes
Reviewed by: Uday Kiran
Second Review by: Bambang Afriadi
Final Approval by: Ramachandra Naik
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ABSTRACT:

Polyindole (PIn) is hetroatomic organic molecule which belongs to the fused-ring family have emerged in the past several decades as promising materials due to their unique physical and electrochemical properties. PIn was successfully synthesized by chemical polymerization of indole. Properties of PIn can be improved by mixing polymer with conducting metals, metal oxide, carbon nanocomposites and other materials. Polyindole nanocomposites (PNCs) were characterized through various spectral, thermal and electrical methods. FT-IR (Fourier transform infrared spectroscopy) spectra confirmed the formation of PNCs and SEM (Scanning electron microscopy) reveal the microstructure of surface of PNCs. Thermal characterization revealed that thermal stability of PNCs increases with addition of metal, metal oxide, carbon nanocomposites and other materials. These studies revealed that PNCs of PIn with other metals have an important influence on supercapacitors electrochemical devices, catalysis, anticorrosion, diodes, sensor and biology related applications. This review provide an overview of the preparation of PIn and their composites, followed by their application in various fields with future perspectives.

KEYWORDS: Metal Composites; Metal Oxides; Nanocomposite; Polyindole

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Rita, Mehtab S, Zaidi M. G. H, Singhal K, Arya B, Siddiqui T. I. Polyindole Based Nanocomposites and Their Applications: A Review. Mat. Sci. Res. India;16 (2).

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Rita, Mehtab S, Zaidi M. G. H, Singhal K, Arya B, Siddiqui T. I. Polyindole Based Nanocomposites and Their Applications: A Review. Mat. Sci. Res. India;16 (2). Available from: http://bit.ly/2GQwXvb

Introduction

The escalating population, industrialization and continuous depletion of traditional fuel reservoirs have been serious issues over natural energy production and its storage since last few decades.1 The demands for production of energy and well regulated system for energy storage is continuously increasing day by day for present and future needs. The source of energy should associate with environmental protection and the prudent replacement of fossil fuels.2 The conjugated conducting polymers (CCPs) and their PNCs have wide applications in the development of research programme and various fields such as communication, pollution, pharmaceuticals, defense and energy storage. The use of CCPs and their PNCs have grown rapidly over past few years. PNCs consist of two components, filler and a polymer matrix. The filler can be an organic material such as carbon, or an inorganic powder of metal. The conductivity, catalytic activity and electrochemical storage depends critically on the characteristics of the filler component.3 Polyindole (PIn), Polypyrrole (PPy), Polythiophene (PTh) and Polyaniline (PANI) are common examples of CCPs which are used for the development of PNCs. The fabrication of electrodes of PIn with other metal composites are described in the literature below.

Figure 1: Applications of Nanoparticles

Figure 1
Click on image to enlarge

 

PIn Based NCs

PIn has received great attention in past several years because of their good electrical properties, environmental stability and ease of synthesis. PIn may have the properties of both poly (para phenylene) and PPy because indole has both benzene and pyrrole rings. PIn has also high redox activity, good thermal stability, high storage ability and slow rate of degradation in comparison with those of PANI and PPy.4

PIn/Metal Composites

Zhou et al. were coated a novel composite catalysts of Pt-PIn on the glassy carbon electrode (GCE) and it used for methanol electrooxidation in 0.5 M H2SO4 acidic solution containing 1.0 M methanol. SEM, XRD and the electrochemical technique were used to characterize the fabricated composite catalysts. CV of Pt-based nanocomposite electrode showed high peak current densities and lower oxidation potential thus efficient catalytic activity.5

The development of PNCs comprising PIn and nanosized Au particle via in-situ polymerization of indole, using metal salt chloro-auric acid as an oxidant. The synthesized polymer composite was monitored by UV-visible spectroscopy. The polymerization mechanism of indole and the interaction between PIn matrix and Au nanoparticles were determined by FT-IR spectroscopy. The XRD confirmed the presence of FCC metallic gold particles in the nanocomposite. The uniform size distribution and spherical structure of Au nanopaticles were reveals by SEM images of nanocomposite. Furthermore, the presence of Au was confirmed by EDX and TGA showed the thermal stability of PNCs with respect to pure polymer at a heating rate of 100°C/min.6

PIn-Metal Oxides

Trung and Huyen prepared the PNCs of PIn and TiO2 by chemical polymerization method. FT-IR and Raman Spectra was studied the chemical structure of conducting polymers in PNCs, whereas SEM and TEM was analyze the morphology of PNCs. TGA analysis was carried out at scan rate of 10°C/min in ambient condition which showed that all CPs in the PNCs were stable at more than 600°C. The electrical conductivity of these PNCs was 1.75 Scm-1. The corrosion of PNCs was studied by using electrochemical impedance spectroscopy.7

The preparation of PIn-ZnO composite polymer electrolyte (CPE) and its conductivity was studied by Rajasudha et al. The PNC was prepared by chemical method using sodium dodecyl sulphate as stabilizer and anhydrous ammonium peroxydisulphate as oxidizing agent. FT-IR spectroscopy used to studied the formation of PNCs or intermolecular interaction between PIn and ZnO. The surface morphology of PNCs was studied by SEM and TEM image showed incorporation of ZnO in PIn matrix. TGA analyzed the thermal stability of nanocomposite that increased with adding amount of filler. The ionic conductivity was increased with concentration of ZnO till 50 (%, w/w) and calculated conductivity was found to be 4.405 × 10-7 at 50°C for the CPE from impedance studies.8 Ganesan et al., synthesized and characterized the CPE of PIn-Fe2O3-LiClO4 from different concentration of indole. The impedance spectroscopy was used to analyze ionic conductivity of CPE, which was dependent on concentration of indole.9

The synthesis of PIn-SnO2 composite and its electrocatalytic applications by chemical oxidative method. The characterization of synthesized PNCs through XRD, FT-IR and TEM which confirmed the formation of a uniform nanocomposite or interaction between polymer matrix and filler. The solution of 0.5 M H2SO4 and 1.0 M HCOOH used as electrolyte for the studies of electrochemical technique.10 Rejani and Beena were synthesize the Mn2O3-PIn hybrid structure and then characterized by XRD, FT-IR, and UV-visible. The prepared Mn2O3 nanomaterial was in crystalline form and the formation of PNC was confirmed by XRD. UV-visible spectrum studied that the band gap of PIn was decreased with hybrid formation from 4.4 eV- 3.3 eV.11 PIn and nano-sized magnetite (Fe3O4) composite was synthesized by Ramesan. The characterization of PNCs through FTIR, UV-visible, SEM, XRD, DSC and σ DC. The peak of PIn of PNCs shifted towards higher wave number in FT-IR spectra. The Fe3O4 nanoparticles were uniformly dispersed in the polymer matrix and their average sizes were studied by SEM where as XRD reveals the crystalline nature of PIn in which incorporation of Fe3O4 nanoparticles but usually PIn is amorphous in nature. The σ DC depends upon the concentration of PIn and the σ DC of PNCs were higher than pure Pin.12

The preparation of PIn-ZnO nanocomposite was reported by Handore et al., FT-IR spectra confirmed the formation of PNCs at ~3400 cm-1 and 735 cm-1 band. XRD exhibits major diffraction in between 30-40o that indicates partial crystalline nature of PNCs and SEM revealed agglomerated granular particulate nature with ZnO embedded in the PIn matrix. The calculated conductivity PIn-ZnO nanocomposite was 1.68 × 10-6 Scm-1.13 The synthesized nanomaterial composite of PIn-Co3O4 by in-situ cathodic electrodeposition and their structural and morphological changes studied by XRD, SEM, TEM, XPS, FT-IR and Raman spectroscopy. Electrochemical nature of PNCs revealed by CV curves obtained at potential range 0.2-0.5 V in 1.0 M KOH solution. The calculated Cs at a current density of 2 Ag-1 is found to be 1805 Fg-1.14 The nanocomposite of V2O5 and PIn deposited onto the activated carbon cloth for supercapacitors. The electrical conductivity of PNC was increased by doping of PIn. CV curve reveals eminent double layer charge storage performance at different SRs (5-050 mV/s) in 5.0 M LiNO3 solution. The Cs 535.3 Fg-1 was reported and these composite showed good cyclic stability with a high rate of 91.1 % after 5000 cycles.15

Majumder et al., were improved the electrochemical and stability features of PIn by incorporation of rare earth metal oxides (RE2O3 where RE = Nd, Gd and Yb) in PIn matrix. The synthesized PNCs were characterized with the help of FT-IR, XRD, FESEM, TEM and TGA. CV recorded in potential range 0-0.8 V with 1 M H2SO4 as electrolyte at a 0.2 Vs-1 SR. Cs of PIn was calculated 117 whereas Nd2O3 showed higher Cs 401 among the all three rare earth metal oxides.16 Rekha et al. reported a review on rare earth based conduction polymers that addresses the important examples of rare earth metals and conducting polymers with their synthesis, characterization and application. Studies reveal improved thermal and cyclic stability, with low internal resistance of the composites with application as dielectric, semiconductor and energy storage devices.17

Arjomandi et al. synthesized the two novel conducting PIn based Fe2O3 and Al2O3 nanocomposite by in situ electropolymerization. The synthesized PNCs were characterized by FT-IR, SEM, TEM, EDX and TGA. The electrochemical properties of PNCs were studied by CV, σDC and EIS. Optical properties was also investigated by UV-visible spectra. TGA analyzed the thermal stability of PNCs were increased as compared to pure PIn. The conductivity of PNCs was increased with concentration of PIn matrix. The electrochemical properties of PNCs were measured at constant current of 0.5 mA/cm2.18

 PIn-Carbon NCs

The PIn/c-MWCNT nanocomposite was synthesized by using in-situ method or interfacial method was studied by Joshi et al. The synthesized PNCs were investigated through different spectral, thermal and micro analytical methods. Electrochemical behaviour studied by using CV at various SR vs. Ag/AgCl in 0.5 M H2SO4 and I/V curves of synthesized PNCs were almost linear with a low value of current.19 A series of PIn-GO nanocomposite were synthesized through polymerization method, in the presence of different concentration of GO ranging 5-20 (%, w/w) and ferric chloride as an oxidant. The PIn-GO interaction investigated through FT-IR, XRD and SEM. Thermal stability of PNCs were increased with the concentration of GO and CV studied that PNCs of 20% GO showed highest Cs 399.97 in 1.0 M KOH at SR of 0.001 V/s.20 A high capacitance hybrid PNCs based on RGO and PIn was prepared through chemical oxidative polymerization. The electrochemical properties of prepared PNCs were studied at 1.0 M H2SO4 through CV and EIS. The synthesized hybrid nanocomposite showed Cs of 322.8 Fg-1, good stability with a cycling efficiency of 94.5% after 1000 cycles and high power density of 5000 W kg-1.21 Oraon et al. fabricated nanoclay derived mesoporous CNT-PIn electrode by in situ and ex situ method with the help of layered silicate. The microstructure and formation of nanoclay derived EM was observed by FT-IR, UV-visible spectra, SEM, TEM and XRD. The electrochemical properties of electrode was studied through CV measurements which carried out in the potential range of 0-0.8 V at different SR of 0.01- 0.2 V/s.22

The electrically conducting PNCs of PIn with CNT were fabricated by an in-situ chemical oxidative polymerization of indole monomer in the presence of APS as oxidizing agent. Surface morphology was revealed by SEM which showed that CNTs were properly distributed and nanoporous structure of PNCs. The measured conductivity of PNC was 0.213 Scm-1, which greater than PIn and I/V characteristic was showed linear graph.23 Mudila et al., synthesized electrochemical energy storage materials at different concentration (w/w) of graphene ranging from 3-9% with PIn matrix in supercritical CO2. FT-IR, XRD and SEM investigated the exfoliation of graphene into the matrix of PIn whereas TGA analyzed the thermal stability of PNCs increased with fraction of graphene. The electrochemical behaviour of PNCs was investigated by CV and EIS. PNCs showed Cs of 289.17 Fg-1 and power density of 511.95 W/kg with good cyclic stability.24 The synthesis of PNCs of PIn-RGO with Au nano-material by green and eco-friendly UV radiation method. Using this method, the nano particles of GO and Au were incorporated on the PIn matrix without using any harmful chemical agents. The fabricated nanomaterial showed a low detection limit (0.26 µM) and a good linear range of 0.8-1000 µM.25

Miscellaneous PIn NCs

The synthesis of electrically conducting PNCs of polyethylene (PE) with varying concentration of PIn and their characterization was confirmed by FT-IR, UV-visible, SEM and TGA. Electrical σ of PIn and PIn-PE composite was measured in the range of 1.2 × 10-3 to 1.96 × 10-6 Scm-1 respectively at 25°C. PIn was found to be 10-3 times more conducting than composite.26 Hassanien et al. prepared the conducting PIn nanowires on DNA templated by chemical oxidation of indole using FeCl3 and their formation was confirmed by FT-IR, UV-visible and XPS. At room temperature, the σ of PIn-DNA composites was found to be 2.5-40 Scm-1. Thermal stability of PIn-DNA nanowires revealed by the temperature dependent conductance during two heating/cooling cycles range of 233 to 373 K. The activation energy of 33.5-0.2 kJmol-1 was also observed.27

PIn and PVC composites were synthesized chemically in the presence of FeCl3 as an initiator. TGA and DSC analyzed the thermal stability where as XRD revealed the amorphous nature of polymer. Conductivity measured the range between 1.0 × 10-5 to 2.1 × 10-4 Scm-1 and the σ DC of composite increased with content of PIn (wt, %) or with increasing temperature.28 PIn-CuS nanocomposite was synthesized for studied the potential effect of CuS nanoparticles, morphology and conductiivity. FT-IR confirmed the formation of nanocomposite and interaction between PIn and CuS. The uniformity and spherical shape of PNCs were showed by SEM images. With increasing the concentration of CuS in PNCs the thermal stability, σ DC and crystallinity were increased.29 The PIn and bacterial cellulose were prepared the biodegradable conductive composite fiber membrane. The microstructure and composition of fiber membrane characterized using SEM and FT-IR. Conductivity of bacterial cellulose increased with incorporation of PIn up to 4.6 × 10-2 Scm-1.30

Conclusion

In this review paper, polyindole based nanocomposites and their application in energy storage system were introduced. PIn is an electrically conducting polymer that obtained by oxidation of indole at the anode in several electrolytes. PNCs were developed by the different composition of electrically conducting polymer PIn with other different types of nanofillers. These fabricated PNCs have variable electrical conductivity due to different properties of nanofillers. PNCs were characterized by various methods such as FT-IR, UV-visible, SEM, EDX, XRD, TGA etc. The use of CPs and their PNCs have grown rapidly over the past few years. These PNCs were utilize in electrochemical energy storage devices.

Acknowledgments and Funding source

Authors are highly thankful to GB Pant University of Agriculture & Technology for providing space and financial support to complete this research work.

Conflicts of interest

The authors have no conflicts of interest to disclose.

References

  1. Choi, H.J., Jung, S.M., Seo, J.M., Chang, D.W., Dai, L. and Baek, J.B. 2012. Graphene for energy conversion and storage in fuel cells and supercapacitors. Nano Energy, 1(4): 534-551.
    CrossRef
  2. Ghosh, A. and Lee, Y.H. 2012. Carbon‐based electrochemical capacitors. Sustainabile Chemistry, 5(3): 480-499.
    CrossRef
  3. Stru Mpler, R. and Glatz-Reichenbach, J. Feature article conducting polymer composites. Journal of Electroceramics, 1999; 3(4): 329-346.
    CrossRef
  4. Ramesan, M.T. Synthesis and characterization of magnetoelectric nanomaterial composed of Fe3O4 and polyindole. Advances in Polymer Technology, 2013; 32(3): 1-7.
    CrossRef
  5. Zhou, W., Du, Y., Ren, F., Wang, C., Xu, J. and Yang, P. High efficient electrocatalytic oxidation of methanol on Pt/polyindoles composite catalysts. International Journal of Hydrogen Energy, 2010; 35(8): 3270-3279.
    CrossRef
  6. Joshi, L. and Prakash, R. One pot synthesis of Polyindole-Au nanocomposite and its nanoscale electrical properties. Materials Letters, 2011; 65(19-20): 3016-3019.
    CrossRef
  7. Trung, V.Q. and Huyen, D.N. Synthesis, properties and application of polyindole/TiO2 nanocomposites. In Journal of Physics: Conference Series 2009; 187(1): 12058-12063.
    CrossRef
  8. Rajasudha, G., Shankar, H., Thangadurai, P., Boukos, N., Narayanan, V. and Stephen, A. Preparation and characterization of polyindole-ZnO composite polymer electrolyte with LiClO4. Ionics, 2010; 16(9): 839-848.
    CrossRef
  9. Ganesan, R., Dhinasekaran, D., Paramasivam, T., Boukos, N., Vengidusamy, N. and Arumainathan, S. Preparation and characterization of polyindole-iron oxide composite polymer electrolyte containing LiClO4. Polymer Plastics Technology and Engineering, 2012; 51(3): 225-230.
    CrossRef
  10. Kumar, A., Pandey, A.C. and Prakash, R. Electro-oxidation of formic acid using polyindole-SnO2 nanocomposite. Catalysis Science and Technology, 2012; 2(12): 2533-2538.
    CrossRef
  11. Rejani, P. and Beena, B. Structural and optical properties of polyindole-manganese oxide nanocomposite. Indian Journal of Advances in Chemical Science, 2013; 2(3): 244-248.
    CrossRef
  12. Ramesan, M.T. Synthesis and characterization of magnetoelectric nanomaterial composed of Fe3O4 and polyindole. Advances in Polymer Technology, 2013; 32(3): 1-7.
    CrossRef
  13. Handore, K.N., Bhavsar, S.V., Pande, N., Chhattise, P.K., Sharma, S.B., Dallavalle, S. and Chabukswar, V.V. Polyindole-ZnO nanocomposite: Synthesis, characterization and heterogeneous catalyst for the 3, 4-dihydropyrimidinone synthesis under solvent-free conditions. Polymer Plastics Technology and Engineering, 2014; 53(7): 734-741.
    CrossRef
  14. Raj, R.P., Ragupathy, P. and Mohan, S. Remarkable capacitive behavior of a Co3O4-polyindole composite as electrode material for supercapacitor applications. Journal of Materials Chemistry A, 2015; 3(48): 24338-24348.
    CrossRef
  15. Zhou, X., Chen, Q., Wang, A., Xu, J., Wu, S. and Shen, J. Bamboo-like composites of V2O5/polyindole and activated carbon cloth as electrodes for all-solid-state flexible asymmetric supercapacitors. ACS Applied Materials and Interfaces, 2016; 8(6): 3776-3783.
    CrossRef
  16. Majumder, M., Choudhary, R.B., Thakur, A.K., Rout, C.S. and Gupta, G. Rare earth metal oxide incorporated polyindole composites: gravimetric and volumetric capacitive performance for supercapacitor applications. New Journal of Chemistry, 2018; 42(7): 5295-5308.
    CrossRef
  17. Rekha, Bisht, A., Joshi, I., Sharma, S., Mehtab, S., Sand, N.K. and Zaidi, M.G.H. Rare earth based conducting polymers: A review. International Journal of Chemical Studies 7 (3), 1246-1250.
  18. Arjomandi, J., Soleimani, H., Parvin, M.H. and Azizi, E. Synthesis and characterization of novel polyindole/metal oxide nanocomposites and its evaluation for lithium ion rechargeable battery applications. Polymer Composites, 2019; 40(2): 496-505.
    CrossRef
  19. Joshi, L., Singh, A.K. and Prakash, R. Polyindole/carboxylated-multiwall carbon nanotube composites produced by in-situ and interfacial polymerization. Materials Chemistry and Physics, 2012; 135(1): 80-87.
    CrossRef
  20. Mudila, H., Rana, S., Zaidi, M.G.H. and Alam, S. Polyindole/graphene oxide nanocomposites: the novel material for electrochemical energy storage. Fullerenes, Nanotubes and Carbon Nanostructures, 2015; 23(1): 20-26.
    CrossRef
  21. Zhou, X., Chen, Q., Wang, A., Xu, J., Wu, S. and Shen, J. Bamboo-like composites of V2O5/polyindole and activated carbon cloth as electrodes for all-solid-state flexible asymmetric supercapacitors. ACS Applied Materials and Interfaces, 2016; 8(6): 3776-3783.
    CrossRef
  22. Oraon, R., De Adhikari, A., Tiwari, S.K., Bhattacharyya, S. and Nayak, G.C. Hierarchical self-assembled nanoclay derived mesoporous CNT/polyindole electrode for supercapacitors. RSC Advances, 2016; 6(69): 64271-64284.
    CrossRef
  23. Cai, Z.J., Zhang, Q. and Song, X.Y. Improved electrochemical performance of polyindole/carbon nanotubes composite as electrode material for supercapacitors. Electronic Materials Letters, 2016; 12(6): 830-840.
    CrossRef
  24. Mudila, H., Rana, S. and Zaidi, M.G.H. Supercritical CO2 aided polyindole-graphene nanocomposites for high power density electrode. Advanced Materials Letters, 2017; 8(3): 269-75.
    CrossRef
  25. Li, R., Yao, L., Wang, Z., Lv, W., Wang, W., Kong, F. and Wang, W. Facile Synthesis Gold-Polyindole-Reduced Graphene Oxide Ternary Nanocomposites with Enhanced Electrocatalytic Activity for the Electrochemical Sensing of Caffeine. Journal of the Electrochemical Society, 2019; 166(4): 212-218.
    CrossRef
  26. Sari, B., Yavas, N., Makulogullari, M., Erol, O. and Unal, H.I. Synthesis, electrorheology and creep behavior of polyindole/polyethylene composites. Reactive and Functional Polymers, 2009; 69(11): 808-815.
    CrossRef
  27. Hassanien, R., Al-Hinai, M., Farha Al-Said, S.A., Little, R., Šiller, L., Wright, N.G. and Horrocks, B.R. Preparation and characterization of conductive and photoluminescent DNA-templated polyindole nanowires. ACS nano, 2010; 4(4): 2149-2159.
    CrossRef
  28. Taylan, N.B., Sari, B. and Unal, H.I. Preparation of conducting poly (vinyl chloride)/polyindole composites and freestanding films via chemical polymerization. Journal of Polymer Science Part B: Polymer Physics, 2010; 48(12): 1290-1298.
    CrossRef
  29. Ramesan, M.T. Fabrication and characterization of conducting nanomaterials composed of copper sulfide and polyindole. Polymer Composites, 2012; 33(12): 2169-2176.
    CrossRef
  30. Zhijiang, C., Cong, Z., Ping, X. and Yunming, Q. Preparation, characterization and antibacterial activity of biodegradable polyindole/bacterial cellulose conductive nanocomposite fiber membrane. Materials Letters,2018; 222: 146-149.
    CrossRef
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