Preparation and application of catalytic polymeric membranes based on PVDF/cobalt nanoparticles supported on MWCNTs

  • Hossein MahdaviEmail author
  • Maryam Sajedi
  • Taieb Shahalizade
  • Ali Akbar Heidari
Original Paper


In this study, preparation, characterization and application of catalytic polymeric membranes incorporated with cobalt nanoparticles-decorated multi-walled carbon nanotubes (Co/MWCNTs) have been reported as an efficient catalyst for reduction of 4-nitrophenol to 4-minophenol. A facile and green method was used to synthesize Co/MWCNTs by two reducing agents, including sodium borohydride (NaBH4) and l-ascorbic acid, carried out at room temperature. Fourier transform infrared, differential scanning calorimetry, vibrating sample magnetometer, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy analyses were employed to characterize the structure and morphology of the prepared catalyst. Catalytic polymeric membranes were prepared through the phase inversion method by embedding the Co/MWCNTs with three different concentrations (1%, 2% and 3% wt%) in polyvinylidene fluoride matrix. Furthermore, the composition and morphology of the nanocompsite membranes were characterized by energy-dispersive X-ray spectrograph and SEM analyses. To investigate the catalytic activity of the prepared membranes, they were applied in a flow-through reactor, showing good catalytic activity toward the reduction of 4-nitrophenol with NaBH4 aqueous solution. After each run, the solution was analyzed by ultraviolet–visible spectrophotometer, and the conversion of the reactant was calculated. The best result was observed for the catalytic membrane containing 3% of Co/MWCNTs, exhibiting 100% conversion by applying two runs.



  1. 1.
    Marcano JGS, Tsotsis TT (2002) Catalytic membranes and membrane reactors. Wiley, New YorkCrossRefGoogle Scholar
  2. 2.
    Motamedhashemi MY, Egolfopoulos F, Tsotsis T (2011) Application of a flow-through catalytic membrane reactor (FTCMR) for the destruction of a chemical warfare simulant. J Membr Sci 376(1):119–131CrossRefGoogle Scholar
  3. 3.
    Ozdemir SS, Buonomenna MG, Drioli E (2006) Catalytic polymeric membranes: preparation and application. Appl Catal A Gen 307(2):167–183CrossRefGoogle Scholar
  4. 4.
    Vankelecom IF (2002) Polymeric membranes in catalytic reactors. Chem Rev 102(10):3779–3810CrossRefGoogle Scholar
  5. 5.
    Westermann T, Melin T (2009) Flow-through catalytic membrane reactors—principles and applications. Chem Eng Process Intensif 48(1):17–28CrossRefGoogle Scholar
  6. 6.
    Armor J (1989) Catalysis with permselective inorganic membranes. Appl Catal 49(1):1–25CrossRefGoogle Scholar
  7. 7.
    Bottino A, Capannelli G, Comite A, Di Felice R (2002) Polymeric and ceramic membranes in three-phase catalytic membrane reactors for the hydrogenation of methylenecyclohexane. Desalination 144(1):411–416CrossRefGoogle Scholar
  8. 8.
    Miachon S, Dalmon J-A (2004) Catalysis in membrane reactors: What about the catalyst? Top Catal 29(1–2):59–65CrossRefGoogle Scholar
  9. 9.
    Domènech B, Muñoz M, Muraviev D, Macanás J (2012) Catalytic membranes with palladium nanoparticles: from tailored polymer to catalytic applications. Catal Today 193(1):158–164CrossRefGoogle Scholar
  10. 10.
    Fayyazi F, Feijani EA, Mahdavi H (2015) Chemically modified polysulfone membrane containing palladium nanoparticles: preparation, characterization and application as an efficient catalytic membrane for Suzuki reaction. Chem Eng Sci 134:549–554CrossRefGoogle Scholar
  11. 11.
    Zaman J, Chakma A (1994) Inorganic membrane reactors. J Membr Sci 92(1):1–28CrossRefGoogle Scholar
  12. 12.
    Gao H, Xu Y, Liao S, Liu R, Liu J, Li D, Yu D, Zhao Y, Fan Y (1995) Catalytic polymeric hollow–fiber reactors for the selective hydrogenation of conjugated dienes. J Membr Sci 106(3):213–219CrossRefGoogle Scholar
  13. 13.
    Gu Y, Favier I, Pradel C, Gin DL, Lahitte J-F, Noble RD, Gómez M, Remigy J-C (2015) High catalytic efficiency of palladium nanoparticles immobilized in a polymer membrane containing poly(ionic liquid) in Suzuki–Miyaura cross-coupling reaction. J Membr Sci 492:331–339CrossRefGoogle Scholar
  14. 14.
    Malik T, Razzaq H, Razzaque S, Nawaz H, Siddiqa A, Siddiq M, Qaisar S (2019) Design and synthesis of polymeric membranes using water-soluble pore formers: an overview. Polym Bull. CrossRefGoogle Scholar
  15. 15.
    Macanas J, Ouyang L, Bruening ML, Muñoz M, Remigy J-C, Lahitte J-F (2010) Development of polymeric hollow fiber membranes containing catalytic metal nanoparticles. Catal Today 156(3):181–186CrossRefGoogle Scholar
  16. 16.
    Alpatova A, Meshref M, McPhedran KN, El-Din MG (2015) Composite polyvinylidene fluoride (PVDF) membrane impregnated with Fe2O3 nanoparticles and multiwalled carbon nanotubes for catalytic degradation of organic contaminants. J Membr Sci 490:227–235CrossRefGoogle Scholar
  17. 17.
    Molinari R, Poerio T (2009) Preparation, characterisation and testing of catalytic polymeric membranes in the oxidation of benzene to phenol. Appl Catal A Gen 358(2):119–128CrossRefGoogle Scholar
  18. 18.
    Wang X, Chen C, Liu H, Ma J (2008) Preparation and characterization of PAA/PVDF membrane-immobilized Pd/Fe nanoparticles for dechlorination of trichloroacetic acid. Water Res 42(18):4656–4664CrossRefGoogle Scholar
  19. 19.
    Wang Z, Chen X, Li K, Bi S, Wu C, Chen L (2015) Preparation and catalytic property of PVDF composite membrane with polymeric spheres decorated by Pd nanoparticles in membrane pores. J Membr Sci 496:95–107CrossRefGoogle Scholar
  20. 20.
    Yan L, Li YS, Xiang CB (2005) Preparation of poly(vinylidene fluoride)(pvdf) ultrafiltration membrane modified by nano-sized alumina (Al2O3) and its antifouling research. Polymer 46(18):7701–7706CrossRefGoogle Scholar
  21. 21.
    Bhatt AS, Bhat DK (2012) Influence of nanoscale NiO on magnetic and electrochemical behavior of PVDF-based polymer nanocomposites. Polym Bull 68(1):253–261CrossRefGoogle Scholar
  22. 22.
    Chen X, Wang Z, Bi S, Li K, Du R, Wu C, Chen L (2016) Combining catalysis and separation on a PVDF/Ag composite membrane allows timely separation of products during reaction process. Chem Eng J 295:518–529CrossRefGoogle Scholar
  23. 23.
    Mahdavi H, Panahi MKS, Shahalizade T (2018) Preparation and application of hyperbranched polymer-modified polyethersulfone membrane containing Ni–Pd–Sn-coated MWCNT for catalytic aryl halide coupling reactions. Polym Bull 75(12):5677–5694CrossRefGoogle Scholar
  24. 24.
    White RJ, Luque R, Budarin VL, Clark JH, Macquarrie DJ (2009) Supported metal nanoparticles on porous materials. Methods and applications. Chem Soc Rev 38(2):481–494CrossRefGoogle Scholar
  25. 25.
    Mahdavi H, Rahimi A, Alam LA (2017) Preparation, characterization and performance study of modified PVDF-based membranes containing palladium nanoparticle-modified graphene hierarchical nanostructures: as a new catalytic nanocomposite membrane. Polym Bull 74(9):3557–3577CrossRefGoogle Scholar
  26. 26.
    Safari J, Gandomi-Ravandi S (2013) Environmentally friendly synthesis of 2-aryl-2, 3-dihydroquinazolin-4 (1H)-ones by novel Co-CNTs as recoverable catalysts. C R Chim 16(12):1158–1164CrossRefGoogle Scholar
  27. 27.
    Serp P, Corrias M, Kalck P (2003) Carbon nanotubes and nanofibers in catalysis. Appl Catal A Gen 253(2):337–358CrossRefGoogle Scholar
  28. 28.
    Zhao L, Wang Z-B, Sui X-L, Yin G-P (2014) Effect of multiwalled carbon nanotubes with different specific surface areas on the stability of supported Pt catalysts. J Power Sources 245:637–643CrossRefGoogle Scholar
  29. 29.
    Zhang Y (2015) Carbon nanotubes/polyacrylic acid coating materials prepared by in situ polymerization technique. Polym Bull 72(10):2519–2526CrossRefGoogle Scholar
  30. 30.
    Maron G, Noremberg B, Alano J, Pereira F, Deon V, Santos R, Freire V, Valentini A, Carreno NLV (2018) Carbon fiber/epoxy composites: effect of zinc sulphide coated carbon nanotube on thermal and mechanical properties. Polym Bull 75(4):1619–1633CrossRefGoogle Scholar
  31. 31.
    Mahdavi H, Rahimi A, Shahalizade T (2016) Catalytic polymeric membranes with palladium nanoparticle/multi-wall carbon nanotubes as hierarchical nanofillers: preparation, characterization and application. J Polym Res 23(3):1–12CrossRefGoogle Scholar
  32. 32.
    Wu C, Chen X, He Z (2018) Polymer/silica hybrid hollow nanoparticles with channels and thermo-responsive gatekeepers for drug storage and release. Colloid Polym Sci 296(12):1961–1969CrossRefGoogle Scholar
  33. 33.
    Pandey S, Mishra SB (2014) Catalytic reduction of p-nitrophenol by using platinum nanoparticles stabilised by guar gum. Carbohydr Polym 113:525–531CrossRefGoogle Scholar
  34. 34.
    Krishna R, Fernandes DM, Dias C, Ventura J, Ramana EV, Freire C, Titus E (2015) Novel synthesis of Ag@ Co/RGO nanocomposite and its high catalytic activity towards hydrogenation of 4-nitrophenol to 4-aminophenol. Int J Hydrog Energy 40(14):4996–5005CrossRefGoogle Scholar
  35. 35.
    Mahdavi H, Heidari AA (2018) Chelated palladium nanoparticles on the surface of plasma-treated polyethersulfone membrane for an efficient catalytic reduction of p-nitrophenol. Polym Adv Technol 29(2):989–1001CrossRefGoogle Scholar
  36. 36.
    Chen R, Jiang Y, Xing W, Jin W (2011) Fabrication and catalytic properties of palladium nanoparticles deposited on a silanized asymmetric ceramic support. Ind Eng Chem Res 50(8):4405–4411CrossRefGoogle Scholar
  37. 37.
    Mohl M, Kónya Z, Kukovecz Á, Kiricsi I (2008) Functionalization of multi-walled carbon nanotubes (MWCNTS). In: Vaseashta A., Mihailescu IN (eds) Functionalized nanoscale materials, devices and systems. NATO science for peace and security series B: physics and biophysics. Springer, Dordrecht, pp 365–368. CrossRefGoogle Scholar
  38. 38.
    Mahdavi H, Rahimi A, Shahalizade T (2016) Catalytic polymeric membranes with palladium nanoparticle/multi-wall carbon nanotubes as hierarchical nanofillers: preparation, characterization and application. J Polym Res 23(3):39CrossRefGoogle Scholar
  39. 39.
    Vollath D (2008) An introduction to synthesis, properties and application. Management 7(6):865–870Google Scholar
  40. 40.
    Bhatt AS, Bhat DK, Santosh M (2011) Crystallinity, conductivity, and magnetic properties of PVDF-Fe3O4 composite films. J Appl Polym Sci 119(2):968–972CrossRefGoogle Scholar
  41. 41.
    Wang Y-J, Kim D (2007) Crystallinity, morphology, mechanical properties and conductivity study of in situ formed PVdF/LiClO4/TiO2 nanocomposite polymer electrolytes. Electrochim Acta 52(9):3181–3189CrossRefGoogle Scholar
  42. 42.
    Nunes-Pereira J, Sharma P, Fernandes L, Oliveira J, Moreira J, Sharma R, Lanceros-Mendez S (2018) Poly(vinylidene fluoride) composites with carbon nanotubes decorated with metal nanoparticles. Compos Part B Eng 142:1–8CrossRefGoogle Scholar
  43. 43.
    Wu L, Sun J, Wang Q (2006) Poly (vinylidene fluoride)/polyethersulfone blend membranes: effects of solvent sort, polyethersulfone and polyvinylpyrrolidone concentration on their properties and morphology. J Membr Sci 285(1–2):290–298CrossRefGoogle Scholar
  44. 44.
    Huang J, Yan C, Huang K (2009) Removal of p-nitrophenol by a water-compatible hypercrosslinked resin functionalized with formaldehyde carbonyl groups and XAD-4 in aqueous solution: a comparative study. J Colloid Interface Sci 332(1):60–64CrossRefGoogle Scholar
  45. 45.
    Wang H, Dong Z, Na C (2013) Hierarchical carbon nanotube membrane-supported gold nanoparticles for rapid catalytic reduction of p-nitrophenol. ACS Sustain Chem Eng 1(7):746–752CrossRefGoogle Scholar
  46. 46.
    Bolisetty S, Arcari M, Adamcik J, Mezzenga R (2015) Hybrid amyloid membranes for continuous flow catalysis. Langmuir 31(51):13867–13873CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemistry, College of ScienceUniversity of TehranTehranIran

Personalised recommendations