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Polymer Bulletin

, Volume 76, Issue 1, pp 119–137 | Cite as

In situ synthesis and characterization of polyaniline/prussian blue/zinc oxide nanocomposite

  • Suganthi MuthusamyEmail author
  • Julie Charles
Original Paper
First Online:
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Abstract

A new ternary nanocomposite of polyaniline (PANI), prussian blue (PB) and zinc oxide (ZnO), i.e., PANI–PB–ZnO was successfully synthesized in one pot process through chemical oxidative polymerization of aniline using ammonium persulfate as oxidizing agent. The morphological studies showed the formation of PB nanocubes and agglomerated quasi-spherical ZnO nanoparticles over PANI matrix, and the elemental composition of PANI–PB–ZnO was analyzed with energy-dispersive X-ray spectroscopy. The XRD measurements reveal the semicrystalline structure of the PANI–PB–ZnO nanocomposite after the polymerization reaction. The various functional groups present in PANI–PB–ZnO were identified using FTIR spectroscopy which confirms the presence of ZnO, PB and PANI in the synthesized ternary nanocomposite. From thermogravimetric analysis, the thermal degradation mechanism of PANI–PB–ZnO nanocomposite was explored and the activation energy (EA) was calculated from Coats–Redfern plot and was found to be 14.33 kJ/mol. 38 wt% of PANI–PB–ZnO nanocomposite was obtained as a residue at 800 °C indicating the high thermal stability. The bulk ionic conductivity value of the synthesized nanocomposite was found to be 8.509 × 10−5 Ω−1 cm−1 at 30 °C and 1.22 × 10−4 Ω−1 cm−1 at 100 °C. The ionic conductivity was found to increase with temperature for the synthesized material which showed an increase in the number of effective charge carriers. The characteristic absorption bands were detected using UV–Vis spectroscopy that confirms the formation of PANI–PB–ZnO nanocomposite. X-ray photoelectron spectroscopy measurements confirmed the valence states of constituent elements in ZnO nanoparticles and ternary PANI–PB–ZnO nanocomposite. I–V studies revealed that hybrid PANI–PB–ZnO nanocomposite has higher conductivity (2.4 × 10−4 S cm−1) than ZnO nanoparticles (3.5 × 10−10 S cm−1).

Keywords

PANI–PB–ZnO Chemical oxidative polymerization Morphology Ionic conductivity Thermal stability Activation energy 
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Notes

Acknowledgements

The authors acknowledge the management of SSN College of Engineering, Kalavakkam, for the financial support provided in the current research work.

References

  1. 1.
    Reddy KR, Karthik KV, Prasad SB, Soni SK, Jeong HM, Raghu AV (2016) Enhanced photocatalytic activity of nanostructured titanium dioxide/polyaniline hybrid photocatalysts. Polyhedron 120:169–174Google Scholar
  2. 2.
    Reddy KR, Lee KP, Lee Y, Gopalan AI (2008) Facile synthesis of conducting polymer–metal hybrid nanocomposite by in situ chemical oxidative polymerization with negatively charged metal nanoparticles. Mater Lett 62:1815–1818Google Scholar
  3. 3.
    Hu C, Li Y, Zhang N, Ding Y (2017) Synthesis and characterization of a poly(o-anisidine)–SiC composite and its application for corrosion protection of steel. RSC Adv 7:11732–11742Google Scholar
  4. 4.
    Reddy KR, Lee KP, Gopalan AI (2007) Self-assembly directed synthesis of poly(ortho-toluidine)-metal (gold and palladium) composite nanospheres. J Nanosci Nanotechnol 7:3117–3125Google Scholar
  5. 5.
    Ameen S, Akhtar MS, Ansari SG, Yang OB, Shin HS (2009) Electrophoretically deposited polyaniline/ZnO nanoparticles for p–n heterostructure diodes. Superlattices Microstruct 46:872–880Google Scholar
  6. 6.
    Sathiyanarayanan S, Azim SS, Venkatachari G (2007) Preparation of polyaniline–TiO2 composite and its comparative corrosion protection performance with polyaniline. Synth Met 157:205–213Google Scholar
  7. 7.
    Stejskal J, Sapurina I, Trchová M (2010) Polyaniline nanostructures and the role of aniline oligomers in their formation. Prog Polym Sci 35:1420–1481Google Scholar
  8. 8.
    Zhang YP, Lee SH, Reddy KR, Gopalan AI, Lee KP (2007) Synthesis and characterization of core-shell SiO2 nanoparticles/poly(3-aminophenylboronic acid) composites. J Appl Polym Sci 104:2743–2750Google Scholar
  9. 9.
    Reddy KR, Lee KP, Gopalan AI (2007) Novel electrically conductive and ferromagnetic composites of poly(aniline-co-aminonaphthalenesulfonic acid) with iron oxide nanoparticles: synthesis and characterization. J Appl Polym Sci 106:1181–1191Google Scholar
  10. 10.
    Reddy KR, Lee KP, Gopalan AI, Showkat AM (2006) Facile synthesis of hollow spheres of sulfonated polyanilines. Polym J 38:349–354Google Scholar
  11. 11.
    Hassan M, Reddy KR, Haque E, Faisal SN, Ghasemi S, Minett AI, Gomes VG (2014) Hierarchical assembly of graphene/polyaniline nanostructures to synthesize free-standing supercapacitor electrode. Compos Sci Technol 98:1–8Google Scholar
  12. 12.
    Rodrigues R, Ferreira Q, Mendonça AL, Morgado J (2014) Template role of polyhexylthiophene nanowires on efficient bilayer photovoltaic cells. Synth Met 190:72–78Google Scholar
  13. 13.
    Chiang JC, MacDiarmid AG (1986) ‘Polyaniline’: protonic acid doping of the emeraldine form to the metallic regime. Synth Met 13:193–205Google Scholar
  14. 14.
    Reddy KR, Park W, Sin BC, Noh J, Lee Y (2009) Synthesis of electrically conductive and superparamagnetic monodispersed iron oxide-conjugated polymer composite nanoparticles by in situ chemical oxidative polymerization. J Colloid Interface Sci 335:34–39Google Scholar
  15. 15.
    Le Goff A, Holzinger M, Cosnier S (2011) Enzymatic biosensors based on SWCNT-conducting polymer electrodes. Analyst 136:1279–1287Google Scholar
  16. 16.
    Ohyama M, Kouzuka H, Yoko T (1997) Sol-gel preparation of ZnO films with extremely preferred orientation along (002) plane from zinc acetate solution. Thin Solid Films 306:78–85Google Scholar
  17. 17.
    Jin ZC, Hamberg I, Granqvist CG, Sernelius BE, Berggren KF (1988) Reactively sputtered ZnO:Al films for energy-efficient windows. Thin Solid Films 164:381–386Google Scholar
  18. 18.
    Spanhel L, Anderson MA (1991) Semiconductor clusters in the sol–gel process: quantized aggregation, gelation, and crystal growth in concentrated zinc oxide colloids. J Am Chem Soc 113:2826–2833Google Scholar
  19. 19.
    Chu SY, Yan TM, Chen SL (2000) Characteristics of sol–gel synthesis of ZnO-based powders. J Mater Sci Lett 19:349–352Google Scholar
  20. 20.
    Tokumoto MS, Briois V, Santilli CV, Pulcinelli SH (2003) Preparation of ZnO nanoparticles: structural study of the molecular precursor. J Sol-Gel Sci Technol 26:547–551Google Scholar
  21. 21.
    Kim JH, Choi WC, Kim HY, Kang Y, Park YK (2005) Preparation of mono-dispersed mixed metal oxide micro hollow spheres by homogeneous precipitation in a micro precipitator. Powder Technol 153:166–175Google Scholar
  22. 22.
    Damonte LC, Zélis LM, Soucase BM, Fenollosa MH (2004) Nanoparticles of ZnO obtained by mechanical milling. Powder Technol 148:15–19Google Scholar
  23. 23.
    Kahn ML, Monge M, Collière V, Senocq F, Maisonnat A, Chaudret B (2005) Size-and shape-control of crystalline zinc oxide nanoparticles: a new organometallic synthetic method. Adv Funct Mater 15:458–468Google Scholar
  24. 24.
    Komarneni S, Bruno M, Mariani E (2000) Synthesis of ZnO with and without microwaves. Mater Res Bull 35:1843–1847Google Scholar
  25. 25.
    Zhao X, Zheng B, Li C, Gu H (1998) Acetate-derived ZnO ultrafine particles synthesized by spray pyrolysis. Powder Technol 100:20–23Google Scholar
  26. 26.
    Tani T, Mädler L, Pratsinis SE (2002) Homogeneous ZnO nanoparticles by flame spray pyrolysis. J Nanopart Res 4:337–343Google Scholar
  27. 27.
    Dai ZR, Pan ZW, Wang ZL (2003) Novel nanostructures of functional oxides synthesized by thermal evaporation. Adv Funct Mater 13:9–24Google Scholar
  28. 28.
    Ao W, Li J, Yang H, Zeng X, Ma X (2006) Mechanochemical synthesis of zinc oxide nanocrystalline. Powder Technol 168:148–151Google Scholar
  29. 29.
    Kovtyukhova NI, Gorchinskiy AD, Waraksa C (2000) Self-assembly of nanostructured composite ZnO/polyaniline films. Mater Sci Eng B 69:424–430Google Scholar
  30. 30.
    He Y (2005) A novel emulsion route to sub-micrometer polyaniline/nano-ZnO composite fibers. Appl Surf Sci 249:1–6Google Scholar
  31. 31.
    Siddheswaran R, Sankar R, Ramesh Babu M, Rathnakumari M, Jayavel R, Murugakoothan P, Sureshkumar P (2006) Preparation and characterization of ZnO nanofibers by electrospinning. Cryst Res Technol 41:446–449Google Scholar
  32. 32.
    Mitra S, Patra P, Chandra S, Pramanik P, Goswami A (2012) Efficacy of highly water-dispersed fabricated nano ZnO against clinically isolated bacterial strains. Appl Nanosci 2:231–238Google Scholar
  33. 33.
    Lai Y, Meng MYuY, Wang X, Ding T (2011) Photoluminescence and photocatalysis of the flower-like nano-ZnO photocatalysts prepared by a facile hydrothermal method with or without ultrasonic assistance. Appl Catal B 105:335–345Google Scholar
  34. 34.
    Hussein MZB, Yun-Hin TY, Bin Tawang MM, Shahadan R (2002) Thermal degradation of (zinc–aluminium-layered double hydroxide-dioctyl sulphosuccinate) nanocomposite. Mater Chem Phys 74:265–271Google Scholar
  35. 35.
    Ghule K, Ghule AV, Chen BJ, Ling YC (2006) Preparation and characterization of ZnO nanoparticles coated paper and its antibacterial activity study. Green Chem 8:1034–1041Google Scholar
  36. 36.
    Wang Y, Wang RXuS, Liu Q, Wang J (2015) Polypyrrole/polyaniline composites with enhanced performance for capacitive deionization. Desalination Water Treat 54:3248–3256Google Scholar
  37. 37.
    Planche MF, Thieblemont JC, Mazars N, Bidan G (1994) Kinetic study of pyrrole polymerization with iron(III) chloride in water. J Appl Polym Sci 52:1867–1877Google Scholar
  38. 38.
    Wu C, Qiao X, Chen J, Wang H, Tan F, Li S (2006) A novel chemical route to prepare ZnO nanoparticles. Mater Lett 60:1828–1832Google Scholar
  39. 39.
    Wahab R, Kim YS, Lee K, Shin HS (2010) Fabrication and growth mechanism of hexagonal zinc oxide nanorods via solution process. J Mater Sci 45:2967–2973Google Scholar
  40. 40.
    Zhao QX, Klason P, Willander M (2007) Growth of ZnO nanostructures by vapor–liquid–solid method. Appl Phys A Mater Sci Process 88:27–30Google Scholar
  41. 41.
    Babaei-Dehkordi A, Moghaddam J, Mostafaei A (2013) An optimization study on the leaching of zinc cathode melting furnace slag in ammonium chloride by Taguchi design and synthesis of ZnO nanorods via precipitation methods. Mater Res Bull 48:4235–4247Google Scholar
  42. 42.
    Cullity BD, Stock SR (2001) Elements of X-ray diffraction. Prentice-Hall, Englewood CliffsGoogle Scholar
  43. 43.
    Pant HC, Patra MK, Negi SC, Bhatia A, Vadera SR, Kumar N (2006) Studies on conductivity and dielectric properties of polyaniline–zinc sulphide composites. Bull Mater Sci 29:379–384Google Scholar
  44. 44.
    Vinayak GK, Chakradhar SB, Hussain J, Prasad MA (2015) Synthesis, characterization and DC conductivity studies on polyaniline/ZnO composites. Ferroelectrics 486:106–113Google Scholar
  45. 45.
    El-hadi AM, Al-Jabri FY, Altaf WJ (2017) Higher dielectric properties of semiconducting biopolymer composites of poly(3-hydroxy butyrate) (PHB) with polyaniline (PANI), carbon black, and plasticizer. Polym Bull.  https://doi.org/10.1007/s00289-017-2118-8 Google Scholar
  46. 46.
    Hao J, Zhao W, Zhang H, Wang D, Yang Q, Tang N, Wang X (2017) Controlled synthesis of PANI nanostructures using phenol and hydroquinone as morphology-control agent. Polym Bull.  https://doi.org/10.1007/s00289-017-2159-z Google Scholar
  47. 47.
    Souquet JL, Levy M, Duclot M (1994) A single microscopic approach for ionic transport in glassy and polymer electrolytes. Solid State Ion 70:337–345Google Scholar
  48. 48.
    Wang JG, Yang Y, Huang ZH, Kang F (2012) Interfacial synthesis of mesoporous MnO2/polyaniline hollow spheres and their application in electrochemical capacitors. J Power Sources 204:236–243Google Scholar
  49. 49.
    Ma RENZHI, Bando Y, Zhang LIANQI, Sasaki T (2004) Layered MnO2 nanobelts: hydrothermal synthesis and electrochemical measurements. Adv Mater 16:918–922Google Scholar
  50. 50.
    Chang MY, Wu CS, Chen YF, Hsieh BZ, Huang WY, Ho KS, Hsieh TH, Han YK (2008) Polymer solar cells incorporating one-dimensional polyaniline nanotubes. Org Electron 9:1136–1139Google Scholar
  51. 51.
    Wang X, Li Y, Zhao Y, Liu J, Tang S, Feng W (2010) Synthesis of PANI nanostructures with various morphologies from fibers to micromats to disks doped with salicylic acid. Synth Met 160:2008–2014Google Scholar
  52. 52.
    Šeděnková I, Trchová M, Stejskal J (2008) Thermal degradation of polyaniline films prepared in solutions of strong and weak acids and in water–FTIR and Raman spectroscopic studies. Polym Degrad Stab 93:2147–2157Google Scholar
  53. 53.
    Zheng JH, Jiang Q, Lian JS (2011) Synthesis and optical properties of flower-like ZnO nanorods by thermal evaporation method. Appl Surf Sci 257:5083–5087Google Scholar
  54. 54.
    Moulder JF, Stickle WF, Sobol PE, Bomben KD (1992) Standard spectra for identification and interpretation of XPS data. Perkin Elmer Eden Prairie MN 89Google Scholar
  55. 55.
    Das J, Pradhan SK, Sahu DR, Mishra DK, Sarangi SN, Nayak BB, Verma S, Roul BK (2010) Micro-Raman and XPS studies of pure ZnO ceramics. Phys B Condens Matter 405:2492–2497Google Scholar
  56. 56.
    Qiu Z, Gong H, Yang X, Zhang Z, Han J, Cao B, Nakamura D, Okada T (2015) Phosphorus concentration dependent microstructure and optical property of ZnO nanowires grown by high-pressure pulsed laser deposition. J Phys Chem C 119:4371–4378Google Scholar
  57. 57.
    Moulder JF, Stickle WF, Sobol PE, Bomben KD (1992) Handbook of X-ray photoelectron spectroscopy. Perkin-Elmer Eden Prairie MN 52Google Scholar
  58. 58.
    Zhou H, Li Z (2005) Synthesis of nanowires, nanorods and nanoparticles of ZnO through modulating the ratio of water to methanol by using a mild and simple solution method. Mater Chem Phys 89:326–331Google Scholar
  59. 59.
    Zhang J, Gao J, Song Q, Guo Z, Chen A, Chen G, Zhou S (2016) N-substituted carboxyl polyaniline covalent grafting reduced graphene oxide nanocomposites and its application in supercapacitor. Electrochim Acta 199:70–79Google Scholar
  60. 60.
    Zou Y, Wang Q, Xiang C, She Z, Chu H, Qiu S, Xu F, Liu S, Tang C, Sun L (2016) One-pot synthesis of ternary polypyrrole–Prussian-blue–graphene-oxide hybrid composite as electrode material for high-performance supercapacitors. Electrochim Acta 188:126–134Google Scholar
  61. 61.
    Yu H, Jang K, Chung I, Ahn H (2016) Fabrication and electrochemical characterization of polyaniline/titanium oxide nanoweb composite electrode for supercapacitor application. J Nanosci Nanotechnol 16:2937–2943Google Scholar

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© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of PhysicsSSN College of EngineeringKalavakkam, ChennaiIndia

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