Synthesis characterization and performance evaluation of tungstic acid functionalized SBA-15/SPEEK composite membrane for proton exchange membrane fuel cell

  • Vijayakumar Elumalai
  • Chivukula Krishna Kavya Sravanthi
  • Dharmalingam SangeethaEmail author
Original Article


Mesoporous Santa Barbara Amorphous (SBA-15) was synthesized and covalently bonded with tungstic acid group using a simple two-step process involving chloromethylation, followed by reaction with disodium tungstate. The tungstic acid functionalized SBA-15 (W-SBA-15) was characterized using FTIR, solid-state 13C CP/MAS NMR, low-angle XRD, SEM, TEM and BET analyses. Sulphonated poly ether ether ketone (SPEEK) was chosen as a base membrane for fabricating the composite membranes. Composite W-SBA-15/SPEEK membranes were prepared with different filler concentrations (2, 4, 6 and 8%) of W-SBA-15. Various studies such as water uptake, ion exchange capacity and proton conductivity of the composite membranes were carried out with respect to fuel cell applications. From the studies, it was found that the W-SBA-15/SPEEK membrane with wt. 6% of filler exhibited superior electrochemical properties. Finally, membrane electrode assembly (MEA) fabricated using 6% W-SBA-15/SPEEK composite membrane, Pt anode and Pt cathode was tested in an in-house built fuel cell setup of area 25 cm2. A maximum power density of 405 mW/cm2 and open circuit voltage of 0.95 V were achieved at 80 °C.


Tungstic acid functionalized SBA-15 Proton exchange membrane Fuel cell performance Ionic conductivity Mesoporus materials 



The authors thank Council of Scientific and Industrial Research (CSIR), New Delhi, India (Vide letter No. 01(2452)/11/EMR-11, letter dated 16.05.2011) and SERB, New Delhi, India for the financial support (Vide file No. EMR/2016/005615).

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.


  1. Ahn MK, Lee B, Jang J et al. (2018) Facile preparation of blend proton exchange membranes with highly sulfonated poly(arylene ether) and poly(arylene ether sulfone) bearing dense triazoles. J Memb Sci 560:58–66. CrossRefGoogle Scholar
  2. Ayyaru S, Dharmalingam S (2015) A study of influence on nanocomposite membrane of sulfonated TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene for microbial fuel cell application. Energy 88:202–208. CrossRefGoogle Scholar
  3. Bhavani P, Sangeetha D (2011) Proton conducting composite membranes for fuel cell application. Int J Hydrog Energy 36:14858–14865. CrossRefGoogle Scholar
  4. Cesarino I, Marino G, Matos JDR, Cavalheiro ÉTG (2007) Using the organofunctionalised SBA-15 nanostructured silica as a carbon paste electrode modifier: Determination of cadmium ions by differential anodic pulse stripping voltammetry. J Braz Chem Soc 18:810–817. CrossRefGoogle Scholar
  5. Chandan A, Hattenberger M, El-Kharouf A et al. (2013) High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC)—a review. J Power Sources 231:264–278. CrossRefGoogle Scholar
  6. Das V, Padmanaban S, Venkitusamy K et al. (2017) Recent advances and challenges of fuel cell based power system architectures and control—a review. Renew Sustain Energy Rev 73:10–18. CrossRefGoogle Scholar
  7. Davarpanah J, Kiasat AR (2014) Covalently anchored n-propyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride on SBA-15 as a basic nanocatalyst for the synthesis of pyran heterocyclic compounds. RSC Adv 4:4403–4412. CrossRefGoogle Scholar
  8. Divya K, Sri Abirami Saraswathi MS, Rana D et al. (2018) Custom-made sulfonated poly (ether sulfone) nanocomposite proton exchange membranes using exfoliated molybdenum disulfide nanosheets for DMFC applications. Polymer 147:48–55. CrossRefGoogle Scholar
  9. Elumalai V, Dharmalingam S (2016) Synthesis characterization and performance evaluation of ionic liquid immobilized SBA-15/quaternised polysulfone composite membrane for alkaline fuel cell. Microporous Mesoporous Mater 236:260–268. CrossRefGoogle Scholar
  10. Elumalai V, Sangeetha D (2018) Anion exchange composite membrane based on octa quaternary ammonium Polyhedral Oligomeric Silsesquioxane for alkaline fuel cells. J Power Sources 375:412–420. CrossRefGoogle Scholar
  11. Elumalai V, Annapooranan R, Ganapathikrishnan M, Sangeetha D (2018) A synthesis study of phosphonated PSEBS for high temperature proton exchange membrane fuel cells. J Appl Polym Sci 135:45954-. CrossRefGoogle Scholar
  12. Erce Ş, Erdener H, Akay RG et al. (2009) Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance. Int J Hydrog Energy 34:4645–4652. CrossRefGoogle Scholar
  13. Fattori N, Maroneze CM, Da Costa LP et al. (2012) Ion-exchange properties of imidazolium-grafted SBA-15 toward AuCl 4- anions and their conversion into supported gold nanoparticles. Langmuir 28:10281–10288. CrossRefGoogle Scholar
  14. Hjuler HA, Aili D, Jensen JO (2016) High temperature polymer electrolyte membrane fuel cells. In: High temperature polymer electrolyte membrane fuel cells. Springer, Cham, pp 1–545. Google Scholar
  15. Hong LY, Oh SY, Matsuda A et al. (2011) Hydrophilic and mesoporous SiO2-TiO2-SO3H system for fuel cell membrane applications. Electrochim Acta 56:3108–3114. CrossRefGoogle Scholar
  16. Ioroi T, Siroma Z, Fujiwara N et al. (2005) Sub-stoichiometric titanium oxide-supported platinum electrocatalyst for polymer electrolyte fuel cells. Electrochem commun 7:183–188. CrossRefGoogle Scholar
  17. Janeta M, John Ł, Ejfler J et al. (2016) Multifunctional imine-POSS as uncommon 3D nanobuilding blocks for supramolecular hybrid materials: synthesis, structural characterization, and properties. Dalt Trans 45:12312–12321. CrossRefGoogle Scholar
  18. Jang H, Sutradhar SC, Yoo J et al. (2016) Synthesis and characterization of sulfonated poly(phenylene) containing a non-planar structure and dibenzoyl groups. Energies 9:1–11. Google Scholar
  19. Jiang SP (2014) Functionalized mesoporous materials as new class high temperature proton exchange membranes for fuel cells. Solid State Ionics 262:307–312. CrossRefGoogle Scholar
  20. Jin Y, Qiao S, Zhang L et al. (2008) Novel Nafion composite membranes with mesoporous silica nanospheres as inorganic fillers. J Power Sources 185:664–669. CrossRefGoogle Scholar
  21. Jun Y, Zarrin H, Fowler M, Chen Z (2011) Functionalized titania nanotube composite membranes for high temperature proton exchange membrane fuel cells. Int J Hydrogen Energy 36:6073–6081. CrossRefGoogle Scholar
  22. Kao HM, Ting CC, Chao SW (2005) Post-synthesis alumination of mesoporous silica SBA-15 with high framework aluminum content using ammonium hexafluoroaluminate. J Mol Catal A Chem 235:200–208. CrossRefGoogle Scholar
  23. Kundu SK, Mondal J, Bhaumik A (2013) Tungstic acid functionalized mesoporous SBA-15: A novel heterogeneous catalyst for facile one-pot synthesis of 2-amino-4H-chromenes in aqueous medium. Dalt Trans 42:10515–10524. CrossRefGoogle Scholar
  24. Laoun B, Kasat HA, Ahmad R, Kannan AM (2018) Gas diffusion layer development using design of experiments for the optimization of a proton exchange membrane fuel cell performance. Energy 151:689–695. CrossRefGoogle Scholar
  25. Liang P, Qiu D, Peng L et al. (2018) Contact resistance prediction of proton exchange membrane fuel cell considering fabrication characteristics of metallic bipolar plates. Energy Convers Manag 169:334–344. CrossRefGoogle Scholar
  26. Liu B, Robertson GP, Kim DS et al. (2007) Aromatic poly(ether ketone)s with pendant sulfonic acid phenyl groups prepared by a mild sulfonation method for proton exchange membranes. Macromolecules 40:1934–1944.; CrossRefGoogle Scholar
  27. Maroneze CM, Magosso HA, Panteleimonov AV et al. (2011) Surface functionalization of SBA-15 and a nonordered mesoporous silica with a 1,4-diazabicyclo[2.2.2]octane derivative: study of CuCl2 adsorption from ethanol solution. J Colloid Interface Sci 356:248–256. CrossRefGoogle Scholar
  28. Meenakshi S, Sahu AK, Bhat SD et al. (2013) Mesostructured-aluminosilicate-Nafion hybrid membranes for direct methanol fuel cells. Electrochim Acta 89:35–44. CrossRefGoogle Scholar
  29. Narayanaswamy Venkatesan P, Dharmalingam S (2015) Effect of cation transport of SPEEK - Rutile TiO2 electrolyte on microbial fuel cell performance. J Memb Sci 492:518–527. CrossRefGoogle Scholar
  30. Özdemir Y, Üregen N, Devrim Y (2017) Polybenzimidazole based nanocomposite membranes with enhanced proton conductivity for high temperature PEM fuel cells. Int J Hydrog Energy 42:2648–2657. CrossRefGoogle Scholar
  31. Parnian MJ, Rowshanzamir S, Prasad AK, Advani SG (2018) High durability sulfonated poly (ether ether ketone)-ceria nanocomposite membranes for proton exchange membrane fuel cell applications. J Memb Sci 556:12–22. CrossRefGoogle Scholar
  32. Pei P, Jia X, Xu H et al. (2018) The recovery mechanism of proton exchange membrane fuel cell in micro-current operation. Appl Energy 226:1–9. CrossRefGoogle Scholar
  33. Prithi JA, Rajalakshmi N, Ranga Rao G (2018) Nitrogen doped mesoporous carbon supported Pt electrocatalyst for oxygen reduction reaction in proton exchange membrane fuel cells. Int J Hydrog Energy 43:4716–4725. CrossRefGoogle Scholar
  34. Sang S, Zhang J, Wu Q, Liao Y (2007) Influences of Bentonite on conductivity of composite solid alkaline polymer electrolyte PVA-Bentonite-KOH-H2O. Electrochim Acta 52:7315–7321. CrossRefGoogle Scholar
  35. Scipioni R, Gazzoli D, Teocoli F et al. (2014) Preparation and characterization of nanocomposite polymer membranes containing functionalized SnO2 additives. Membranes (Basel) 4:123–142. CrossRefGoogle Scholar
  36. Shukla G, Shahi VK (2018) Sulfonated poly(ether ether ketone)/imidized graphene oxide composite cation exchange membrane with improved conductivity and stability for electrodialytic water desalination. Desalination 451:200–208. CrossRefGoogle Scholar
  37. Shyuan LK, Tan EL, Wan Daud WR, Mohamad AB (2013) Synthesis and characterization of sulfonated polybenzimidazole (SPBI) copolymer for polymer exchange membrane fuel cell. Adv Mater Res 860–863:803–806. CrossRefGoogle Scholar
  38. Sonpingkam S, Pattavarakorn D (2014) Mechanical properties of sulfonated poly (ether ether ketone) nanocomposite membranes. Int J Chem Eng Appl 5:181–185. Google Scholar
  39. Srivastava R (2007) An efficient, eco-friendly process for aldol and Michael reactions of trimethylsilyl enolate over organic base-functionalized SBA-15 catalysts. J Mol Catal A Chem 264:146–152. CrossRefGoogle Scholar
  40. Vijayakumar E, Sangeetha D (2015) A quaternized mesoporous silica/polysulfone composite membrane for an efficient alkaline fuel cell application. RSC Adv 5:42828–42835. CrossRefGoogle Scholar
  41. Vinodh R, Sangeetha D (2013) Quaternized poly(styrene ethylene butylene poly styrene)/multiwalled carbon nanotube composites for alkaline fuel cell applications. J Nanosci Nanotechnol 13:5522–5533. CrossRefGoogle Scholar
  42. Won J, Choi SW, Kang YS et al. (2003) Structural characterization and surface modification of sulfonated polystyrene-(ethylene-butylene)-styrene triblock proton exchange membranes. J Memb Sci 214:245–257. CrossRefGoogle Scholar
  43. Wu J, Cui Z, Zhao C et al. (2009) High proton conductive advanced hybrid membrane based on sulfonated Si-SBA-15. Int J Hydrog Energy 34:6740–6748. CrossRefGoogle Scholar
  44. Xu X, Li R, Tang C et al. (2018) Cellulose nanofiber-embedded sulfonated poly (ether sulfone) membranes for proton exchange membrane fuel cells. Carbohydr Polym 184:299–306. CrossRefGoogle Scholar
  45. Yan WM, Chen CY, Jhang Y, kai et al. (2018) Performance evaluation of a multi-stage plate-type membrane humidifier for proton exchange membrane fuel cell. Energy Convers Manag 176:123–130. CrossRefGoogle Scholar
  46. Yao Z, Zhang Z, Hu M et al. (2018) Perylene-based sulfonated aliphatic polyimides for fuel cell applications: performance enhancement by stacking of polymer chains. J Memb Sci 547:43–50. CrossRefGoogle Scholar
  47. Zhao D, Sun J, Li Q et al. (2000) Morphological control of highly ordered mesoporous silica SBA-15 mesoporous materials are of great interest to the materials community because their pore structures as well as catalytic, adsorbed, conductive and magnetic ordered large mesoporous silica. Chem Mater 12:275–279. CrossRefGoogle Scholar

Copyright information

© King Abdulaziz City for Science and Technology 2019

Authors and Affiliations

  1. 1.Department of Mechanical EngineeringAnna UniversityChennaiIndia
  2. 2.SRM UniversityKattankulathurIndia

Personalised recommendations