Chemical Papers

, Volume 72, Issue 10, pp 2523–2538 | Cite as

Synthesis and characterization of polyaniline–zirconium dioxide and polyaniline–cerium dioxide composites with enhanced photocatalytic degradation of rhodamine B dye

  • Anwar-ul-Haq Ali Shah
  • Shafaq Akhlaq
  • Murtaza Sayed
  • Salma Bilal
  • Nauman Ali
Original Paper


For the first time, chloroform and 2-butanol were used as solvent systems for the preparation of ZrO2–PANI and CeO2–PANI composites. Solubility of the synthesized composites was studied in chloroform, N-methyl-2-pyrrolidinone (NMP), and in mixture of toluene + 2-propanol (2:1). XRD and cyclic voltammetry data showed that the ZrO2–PANI and CeO2–PANI composites possess both crystalline and amorphous domains indicating some sort of conductivity. TGA results showed that ZrO2–PANI composite have a better thermal stability than pure PANI; however, CeO2–PANI composite has lower thermal stability than pure PANI. The conjugated unsaturated structure of PANI is responsible for the enhanced photocatalytic properties of ZrO2–PANI and CeO2–PANI. Photocatalytic results showed that, at photolysis time of 60 min, rhodamine B (RhB) dye was degraded up to 34 and 35% by ZrO2–PANI and CeO2–PANI, respectively. The degradation products of RhB were quantified by LC–MS and GC–MS, and accordingly, a detailed pathway was proposed.


ZrO2–PANI CeO2–PANI Conjugated unsaturated polymer Inverse polymerization Photocatalysis 

Supplementary material

11696_2018_494_MOESM1_ESM.docx (2.2 mb)
Supplementary material 1 (DOCX 2277 kb)


  1. Ansari MO, Mohammad F (2012) Thermal stability and electrical properties of dodecyl-benzene-sulfonic-acid doped nanocomposites of polyaniline and multi-walled carbon nanotubes. Compos B 43:3541–3548CrossRefGoogle Scholar
  2. Anwer T, Ansari MO, Mohammad F (2013) Dodecylbenzenesulfonic acid micelles assisted in situ preparation and enhanced thermoelectric performance of semiconducting polyaniline–zirconium oxide nanocomposites. J Ind Eng Chem 19:1653–1658CrossRefGoogle Scholar
  3. Aralekallu S, Thimmappa R, Gaikwad P, Devendrachari MC, Kottaichamy AR, Shafi SP, Lokesh KS, Sánchez J, Thotiyl MO (2017) Tuning the interfacial chemistry of redox-active polymer for bifunctional probing. ChemElectroChem 4:692–700CrossRefGoogle Scholar
  4. Armand M, Tarascon J-M (2008) Building better batteries. Nature 451:652–657CrossRefGoogle Scholar
  5. Baker CO, Huang X, Nelson W, Kaner RB (2017) Polyaniline nanofibers: broadening applications for conducting polymers. Chem Soc Rev 46:1510–1525CrossRefPubMedGoogle Scholar
  6. Benlahouès A, Brissault B, Boileau S, Penelle J (2018) Design of optimized reaction conditions for the efficient living anionic polymerization of cyclopropane-1, 1-dicarboxylates. Macromol Chem Phys. CrossRefGoogle Scholar
  7. Bilal S, Gul S, Ali K, Shah A-U-HA (2012) Synthesis and characterization of completely soluble and highly thermally stable PANI-DBSA salts. Synth Met 162:2259–2266CrossRefGoogle Scholar
  8. Bora C, Kalita A, Das D, Dolui SK, Mukhopadhyay PK (2014) Preparation of polyaniline/nickel oxide nanocomposites by liquid/liquid interfacial polymerization and evaluation of their electrical, electrochemical and magnetic properties. Polym Int 63:445–452CrossRefGoogle Scholar
  9. Cao J, Wang Q, Dai H (2003) Electromechanical properties of metallic, quasimetallic, and semiconducting carbon nanotubes under stretching. Phys Rev Lett 90:157601CrossRefPubMedGoogle Scholar
  10. Gök A, Sarı B, Talu M (2004) Synthesis and characterization of conducting substituted polyanilines. Synth Met 142:41–48CrossRefGoogle Scholar
  11. Gumpu MB, Nesakumar N, Sethuraman S, Krishnan UM, Rayappan JBB (2014) Development of electrochemical biosensor with ceria–PANI core–shell nano-interface for the detection of histamine. Sens Actuators B 199:330–338CrossRefGoogle Scholar
  12. Heimel G (2016) The optical signature of charges in conjugated polymers. ACS Cent Sci 2:309–315CrossRefPubMedPubMedCentralGoogle Scholar
  13. Holze R, Wu Y (2014) Intrinsically conducting polymers in electrochemical energy technology: trends and progress. Electrochim Acta 122:93–107CrossRefGoogle Scholar
  14. Huang Z, Huang C, Luo X (2018) Influence of the thermal contact resistance on the thermoelectric property of PANI/Ag nanocomposites. Solid State CommunGoogle Scholar
  15. Hurrle S, Goldmann AS, Gliemann H, Mutlu H, Barner-Kowollik C (2018) Light-induced step-growth polymerization of AB-type photo-monomers at ambient temperature. ACS Macro Lett 7:201–207CrossRefGoogle Scholar
  16. Jaiswal M, Menon R (2006) Polymer electronic materials: a review of charge transport. Polym Int 55:1371–1384CrossRefGoogle Scholar
  17. Khan AM, Mehmood A, Sayed M, Nazar MF, Ismail B, Khan RA, Ullah H, Rehman HMA, Khan AY, Khan AR (2017) Influence of acids, bases and surfactants on the photocatalytic degradation of a model dye rhodamine B. J Mol Liq 236:395–403CrossRefGoogle Scholar
  18. Kosaki M, Nagao M, Mizuno Y, Shimizu N, Horii K (1993) Development of polymer-insulated superconducting power cables. Fusion Eng Des 20:399–407CrossRefGoogle Scholar
  19. Li C, Thostenson ET, Chou T-W (2008) Sensors and actuators based on carbon nanotubes and their composites: a review. Compos Sci Technol 68:1227–1249CrossRefGoogle Scholar
  20. Lienkamp K, Wegner G (2007) Highly conductive polypyrrole copolymers? Macromol Rapid Commun 28:1112–1114CrossRefGoogle Scholar
  21. MacDiarmid AG (2001) Synthetic metals: a novel role for organic polymers. Synth Met 125:11–22CrossRefGoogle Scholar
  22. McAllister BT, Schon TB, DiCarmine PM, Seferos DS (2017) A study of fused-ring thieno [3, 4-e] pyrazine polymers as n-type materials for organic supercapacitors. Polym Chem 8:5194–5202CrossRefGoogle Scholar
  23. Migdalski J, Błaż T, Lewenstam A (2013) Conducting polymers-mechanisms of cationic sensitivity and the methods of inducing thereof. Electrochim Acta 133:316–324CrossRefGoogle Scholar
  24. Ogurtsov NA, Bliznyuk VN, Mamykin AV, Kukla OL, Piryatinski YP, Pud AA (2018) Poly (vinylidene fluoride)/poly (3-methylthiophene) core–shell nanocomposites with improved structural and electronic properties of the conducting polymer component. Phys Chem Chem Phys 20:6450–6461CrossRefPubMedGoogle Scholar
  25. Pant P, Bansal R, Gulati S, Kumar S, Kodwani R (2016) Porous and chelated nanostructured multifunctional materials: recoverable and reusable sorbents for extraction of metal ions and catalysts for diverse organic reactions. J Nanostructure Chem 6:145–157CrossRefGoogle Scholar
  26. Parvatikar N, Jain S, Bhoraskar S, Ambika Prasad M (2006) Spectroscopic and electrical properties of polyaniline/CeO2 composites and their application as humidity sensor. J Appl Polym Sci 102:5533–5537CrossRefGoogle Scholar
  27. Ramanavičius A, Ramanavičienė A, Malinauskas A (2006) Electrochemical sensors based on conducting polymer—polypyrrole. Electrochim Acta 51:6025–6037CrossRefGoogle Scholar
  28. Ramu S, Lingaiah N, Devi BP, Prasad R, Suryanarayana I, Prasad PS (2004) Esterification of palmitic acid with methanol over tungsten oxide supported on zirconia solid acid catalysts: effect of method of preparation of the catalyst on its structural stability and reactivity. Appl Catal A 276:163–168CrossRefGoogle Scholar
  29. Rohani N, Bamoharram FF, Marjani A, Heravi MM (2017) Gold nanoparticles Wells-Dawson heteropolyacid nanocomposite film as an effective nanocatalyst in photocatalytic removal of azo dyes from wastewaters. J Nanostructure Chem 7:171–178CrossRefGoogle Scholar
  30. Sadegh H, Ali GA, Gupta VK, Makhlouf ASH, Shahryari-ghoshekandi R, Nadagouda MN, Sillanpää M, Megiel E (2017) The role of nanomaterials as effective adsorbents and their applications in wastewater treatment. J Nanostructure Chem 7:1–14CrossRefGoogle Scholar
  31. Sayed M, Pingfeng F, Khan HM, Zhang P (2014) Effect of isopropanol on microstructure and activity of TiO2 films with dominant {001} facets for photocatalytic degradation of bezafibrate. Int J PhotoenergyGoogle Scholar
  32. Sayed M, Fu P, Shah LA, Khan HM, Nisar J, Ismail M, Zhang P (2015) VUV-photocatalytic degradation of bezafibrate by hydrothermally synthesized enhanced 001 facets TiO2/Ti film. J Phys Chem A 120:118–127CrossRefPubMedGoogle Scholar
  33. Sayed M, Khan JA, Shah LA, Shah NS, Khan HM, Rehman F, Khan AR, Khan AM (2016a) Degradation of quinolone antibiotic, norfloxacin, in aqueous solution using gamma-ray irradiation. Environ Sci Pollut Res 23:13155–13168CrossRefGoogle Scholar
  34. Sayed M, Shah LA, Khan JA, Shah NS, Nisar J, Khan HM, Zhang P, Khan AR (2016b) Efficient photocatalytic degradation of norfloxacin in aqueous media by hydrothermally synthesized immobilized TiO2/Ti films with exposed 001 facets. J Phys Chem A 120:9916–9931CrossRefPubMedGoogle Scholar
  35. Sayed M, Khan JA, Shah LA, Shah NS, Shah F, Khan HM, Zhang P, Arandiyan H (2017) Solar light responsive poly (vinyl alcohol)-assisted hydrothermal synthesis of immobilized TiO2/Ti film with the addition of peroxymonosulfate for photocatalytic degradation of ciprofloxacin in aqueous media: a mechanistic approach. J Phys Chem C 122:406–421CrossRefGoogle Scholar
  36. Shirakawa H, Louis EJ, MacDiarmid AG, Chiang CK, Heeger AJ (1977) Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x. J Chem Soc Chem Commun 16:578–580CrossRefGoogle Scholar
  37. Singh M, Nesakumar N, Sethuraman S, Krishnan UM, Rayappan JBB (2014) Electrochemical biosensor with ceria–polyaniline core shell nano-interface for the detection of carbonic acid in blood. J Colloid Interface Sci 425:52–58CrossRefPubMedGoogle Scholar
  38. Smirnova N, Surovtseva N, Fesenko T, Demianenko E, Grebenyuk A, Eremenko A (2015) Photodegradation of dye acridine yellow on the surface of mesoporous TiO2, SiO2/TiO2 and SiO2 films: spectroscopic and theoretical studies. J Nanostructure Chem 5:333–346CrossRefGoogle Scholar
  39. Smith R, Moule MG, Sule P, Smith T, Cirillo J, Grunlan JC (2017) Polyelectrolyte multilayer nanocoating dramatically reduces bacterial adhesion to polyester fabric. ACS Biomater Sci Eng 3(8):1845–1852CrossRefPubMedPubMedCentralGoogle Scholar
  40. Stejskal J, Exnerovã M, Morãvkovã Z, Trchovã M, Hromãdkovã JI, Prokeå J (2012) Oxidative stability of polyaniline. Polym Degrad Stab 97:1026–1033CrossRefGoogle Scholar
  41. Vohra S, Kumar M, Mittal SK, Singla M (2013) Thermal and electrical behavior of silver chloride/polyaniline nanocomposite synthesized in aqueous medium using hydrogen peroxide. J Mater Sci 24:1354–1360Google Scholar
  42. Wang S, Tan Z, Li Y, Sun L, Zhang T (2006) Synthesis, characterization and thermal analysis of polyaniline/ZrO 2 composites. Thermochim Acta 441:191–194CrossRefGoogle Scholar
  43. Wang J, Wang J, Zhang X, Wang Z (2007) Assembly of polyaniline nanostructures. Macromol Rapid Commun 28:84–87CrossRefGoogle Scholar
  44. Wang L, Huang H, Xiao S, Cai D, Liu Y, Liu B, Wang D, Wang C, Li H, Wang Y (2014) Enhanced sensitivity and stability of room-temperature NH3 sensors using core-shell CeO2 Nanoparticles@ cross-linked PANI with p–n heterojunctions. ACS Appl Mater Interfaces 6:14131–14140CrossRefPubMedGoogle Scholar
  45. Wang H, Yuan X, Wu Y, Zeng G, Chen X, Leng L, Li H (2015) Synthesis and applications of novel graphitic carbon nitride/metal-organic frameworks mesoporous photocatalyst for dyes removal. Appl Catal B 174:445–454CrossRefGoogle Scholar
  46. Wang H, Yuan X, Wu Y, Zeng G, Tu W, Sheng C, Deng Y, Chen F, Chew JW (2017) Plasmonic Bi nanoparticles and BiOCl sheets as cocatalyst deposited on perovskite-type ZnSn (OH) 6 microparticle with facet-oriented polyhedron for improved visible-light-driven photocatalysis. Appl Catal B 209:543–553CrossRefGoogle Scholar
  47. Yang S, Ishikawa Y, Itoh H, Feng Q (2011) Fabrication and characterization of core/shell structured TiO2/polyaniline nanocomposite. J Colloid Interface Sci 356:734–740CrossRefPubMedGoogle Scholar
  48. Yin P, Tan Y, Fang H, Hegde M, Radovanovic PV (2018) Plasmon-induced carrier polarization in semiconductor nanocrystals. Nat Nanotechnol. CrossRefPubMedGoogle Scholar
  49. Yuan X, Wang H, Wu Y, Zeng G, Chen X, Leng L, Wu Z, Li H (2016) One-pot self-assembly and photoreduction synthesis of silver nanoparticle-decorated reduced graphene oxide/MIL-125 (Ti) photocatalyst with improved visible light photocatalytic activity. Appl Organomet Chem 30:289–296CrossRefGoogle Scholar
  50. Zare K, Gupta VK, Moradi O, Makhlouf ASH, Sillanpää M, Nadagouda MN, Sadegh H, Shahryari-Ghoshekandi R, Pal A, Wang Z-J (2015) A comparative study on the basis of adsorption capacity between CNTs and activated carbon as adsorbents for removal of noxious synthetic dyes: a review. J Nanostructure Chem 5:227–236CrossRefGoogle Scholar
  51. Zhang M, Wang J, Jin Z (2018) Supramolecular hydrogel formation between chitosan and hydroxypropyl β-cyclodextrin via Diels-Alder reaction and its drug delivery. Int J Biol Macromol 114:381–391CrossRefPubMedGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  1. 1.Institute of Chemical SciencesUniversity of PeshawarPeshawarPakistan
  2. 2.National Centre of Excellence in Physical ChemistryUniversity of PeshawarPeshawarPakistan

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