Electrodeposition of nanostructured Pt–Pd bimetallic catalyst on polyaniline-camphorsulfonic acid/graphene nanocomposites for methanol electrooxidation

  • 224 Accesses

  • 1 Citations


Recently, the use of polymer-supported bimetallic catalysts to reduce the cost of direct methanol fuel cells (DMFCs) and increase the efficiency of catalysts has been considered. In this work, the preparation of platinum–palladium supported on polyaniline-doped camphorsulfonic acid/graphene (Pt–Pd@ PANI-CSA/graphene) nanocomposites as an anode material in DMFCs is reported. PANI-CSA/graphene nanocomposite was prepared from aniline-doped CSA and graphene by in situ polymerization in ice water. In order to characterize the structure and the surface properties of prepared materials, Fourier transform infrared spectrum (FTIR), X-ray diffraction spectroscopy (XRD), and scanning electron microscopy (SEM) techniques were employed. The electrochemical properties of the nanocatalysts were evaluated through cyclic voltammetry (CV) and chronoamperometry (CA) measurements. The results suggested that PANI-CSA/graphene nanocomposite as a support material had an especially positive effect on the electrocatalytic activity of Pt–Pd for methanol oxidation reaction (MOR) in alkaline media. Also the results of chronoamperometric studies showed that Pt–Pd@ PANI-CSA/graphene was more stable than unsupported Pt–Pd for methanol electrooxidation.

Graphical abstract

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11


  1. 1.

    Radhakrishnan T, Sandhyarani N (2017) Three dimensional assembly of electrocatalytic platinum nanostructures on reduced graphene oxide–an electrochemical approach for high performance catalyst for methanol oxidation. Int J Hydrog Energy 42(10):7014–7022

  2. 2.

    Dong L, Gari RRS, Li Z, Craig MM, Hou S (2010) Graphene-supported platinum and platinum–ruthenium nanoparticles with high electrocatalytic activity for methanol and ethanol oxidation. Carbon 48(3):781–787

  3. 3.

    Sharma S, Pollet BG (2012) Support materials for PEMFC and DMFC electrocatalysts—a review. J Power Sources 208:96–119

  4. 4.

    Ahmadi R, Amini M, Bennett J (2012) Pt–Co alloy nanoparticles synthesized on sulfur-modified carbon nanotubes as electrocatalysts for methanol electrooxidation reaction. J Catal 292:81–89

  5. 5.

    Long NV, Yang Y, Thi CM, Van Minh N, Cao Y, Nogami M (2013) The development of mixture, alloy, and core-shell nanocatalysts with nanomaterial supports for energy conversion in low-temperature fuel cells. Nano Energy 2(5):636–676

  6. 6.

    Papadimitriou S, Armyanov S, Valova E, Hubin A, Steenhaut O, Pavlidou E, Kokkinidis G, Sotiropoulos S (2010) Methanol oxidation at Pt − Cu, Pt − Ni, and Pt − Co electrode coatings prepared by a galvanic replacement process. J Phy Chem C 114(11):5217–5223

  7. 7.

    Muller DA, Wang D, DiSalvo FJ, Abruña HD, Wang H, Xin HL, Hovden R, Yu Y (2013) Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat Mater 12(1):81

  8. 8.

    Wang Y-J, Zhao N, Fang B, Li H, Bi XT, Wang H (2015) Carbon-supported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chem Rev 115(9):3433–3467

  9. 9.

    Mu Y, Liang H, Hu J, Jiang L, Wan L (2005) Controllable Pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells. J Phys Chem B 109(47):22212–22216

  10. 10.

    Coutanceau C, Brimaud S, Lamy C, Léger J-M, Dubau L, Rousseau S, Vigier F (2008) Review of different methods for developing nanoelectrocatalysts for the oxidation of organic compounds. Electrochim Acta 53(23):6865–6880

  11. 11.

    Hyeon T, Han S, Sung YE, Park KW, Kim YW (2003) High-performance direct methanol fuel cell electrodes using solid-phase-synthesized carbon nanocoils. Angew Chem Int Ed 42(36):4352–4356

  12. 12.

    Liu C-S, Liu X-C, Wang G-C, Liang R-P, Qiu J-D (2014) Preparation of nitrogen-doped graphene supporting Pt nanoparticles as a catalyst for oxygen reduction and methanol oxidation. J Electroanal Chem 728:41–50

  13. 13.

    Jin Y, Fang M, Jia M (2014) In situ one-pot synthesis of graphene–polyaniline nanofiber composite for high-performance electrochemical capacitors. Appl Surf Sci 308:333–340

  14. 14.

    Westervelt R (2008) Graphene nanoelectronics. Science 320(5874):324–325

  15. 15.

    Qu L, Liu Y, Baek J-B, Dai L (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3):1321–1326

  16. 16.

    Miao X, Tongay S, Petterson MK, Berke K, Rinzler AG, Appleton BR, Hebard AF (2012) High efficiency graphene solar cells by chemical doping. Nano Lett 12(6):2745–2750

  17. 17.

    Wu Z-S, Ren W, Xu L, Li F, Cheng H-M (2011) Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries. ACS Nano 5(7):5463–5471

  18. 18.

    Wang R, Han M, Zhao Q, Ren Z, Guo X, Xu C, Hu N, Lu L (2017) Hydrothermal synthesis of nanostructured graphene/polyaniline composites as high-capacitance electrode materials for supercapacitors. Sc Rep 7:44562

  19. 19.

    Li K, Liu J, Huang Y, Bu F, Xu Y (2017) Integration of ultrathin graphene/polyaniline composite nanosheets with a robust 3D graphene framework for highly flexible all-solid-state supercapacitors with superior energy density and exceptional cycling stability. J Mater Chem A 5(11):5466–5474

  20. 20.

    Wang H, Lin J, Shen ZX (2016) Polyaniline (PANi) based electrode materials for energy storage and conversion. J Sci 1(3):225–255

  21. 21.

    Gnana kumar G, Kirubaharan CJ, Udhayakumar S, Karthikeyan C, Nahm KS (2014) Conductive polymer/graphene supported platinum nanoparticles as anode catalysts for the extended power generation of microbial fuel cells. Ind Eng Chem Res 53(43):16883–16893

  22. 22.

    Cui Z, Guo CX, Li CM (2013) Self-assembled phosphomolybdic acid–polyaniline–graphene composite-supported efficient catalyst towards methanol oxidation. J Mater Chem A 1(22):6687–6692

  23. 23.

    Eris S, Daşdelen Z, Yıldız Y, Sen F (2017) Nanostructured polyaniline-rGO decorated platinum catalyst with enhanced activity and durability for methanol oxidation. Int J Hydrog Energy 43:1337–1343

  24. 24.

    Lu XM, Wu QF, Mi HY, Zhang XG (2007) Electrochemical capacitance of camphorsulfonic acid doped polyaniline microtubes prepared at low temperature. Acta Phys Chim Sin 23(06):820–824

  25. 25.

    Łużny W, Piwowarczyk K (2011) Hydrogen bonds in camphorsulfonic acid doped polyaniline. Polimery 56(9):652–656

  26. 26.

    Park SH, Shin KH, Kim JY, Yoo SJ, Lee KJ, Shin J, Choi JW, Jang J, Sung YE (2012) The application of camphorsulfonic acid doped polyaniline films prepared on TCO-free glass for counter electrode of bifacial dye-sensitized solar cells. J Photochem Photobiol, A 245:1–8

  27. 27.

    Tabrizi AG, Arsalani N, Mohammadi A, Ghadimi LS, Ahadzadeh I, Namazi H (2018) A new route for the synthesis of polyaniline nanoarrays on graphene oxide for high-performance supercapacitors. Electrochim Acta 265:379–390

  28. 28.

    Bienkowski K (2006) Polyaniline and its derivatives doped with Lewis acids-synthesis and spectroscopic properites. Dissertation, Université Joseph-Fourier-Grenoble I; Warsaw University of Technology

  29. 29.

    Huang J, Wan M (1999) In situ doping polymerization of polyaniline microtubules in the presence of β-naphthalenesulfonic acid. J Polym Sci A 37(2):151–157

  30. 30.

    Fard LA, Ojani R, Raoof JB, Zare EN, Lakouraj MM (2017) Poly (pyrrole-co-aniline) hollow nanosphere supported Pd nanoflowers as high-performance catalyst for methanol electrooxidation in alkaline media. Energy 127:419–427

  31. 31.

    Fard LA, Ojani R, Raoof JB, Zare EN, Lakouraj MM (2017) PdCo porous nanostructures decorated on polypyrrole@ MWCNTs conductive nanocomposite—modified glassy carbon electrode as a powerful catalyst for ethanol electrooxidation. Appl Surf Sci 401:40–48

  32. 32.

    Goswami S, Maiti U, Maiti S, Nandy S, Mitra M, Chattopadhyay K (2011) Preparation of graphene–polyaniline composites by simple chemical procedure and its improved field emission properties. Carbon 49(7):2245–2252

  33. 33.

    Trchova M, Stejskal J, Prokeš J (1999) Infrared spectroscopic study of solid-state protonation and oxidation of polyaniline. Synth Met 101(1–3):840–841

  34. 34.

    Chaudhari H, Kelkar D (1997) Investigation of structure and electrical conductivity in doped polyaniline. Polym Int 42(4):380–384

  35. 35.

    Elnaggar EM, Kabel KI, Farag AA, Al-Gamal AG (2017) Comparative study on doping of polyaniline with graphene and multi-walled carbon nanotubes. J. Nanostruct Chem 7(1):75–83

  36. 36.

    Trung NB, Van Tam T, Kim HR, Hur SH, Kim EJ, Choi WM (2014) Three-dimensional hollow balls of graphene–polyaniline hybrids for supercapacitor applications. Chem Eng J 255:89–96

  37. 37.

    Li Y, Tang L, Li J (2009) Preparation and electrochemical performance for methanol oxidation of Pt/graphene nanocomposites. Electrochem Commun 11(4):846–849

  38. 38.

    Yang X, Yang Q, Xu J, Lee C-S (2012) Bimetallic PtPd nanoparticles on Nafion–graphene film as catalyst for ethanol electro-oxidation. J Mater Chem 22(16):8057–8062

  39. 39.

    Wang L, Lu X, Lei S, Song Y (2014) Graphene-based polyaniline nanocomposites: preparation, properties and applications. J Mater Chem A 2(13):4491–4509

  40. 40.

    Xu J, Wang K, Zu S-Z, Han B-H, Wei Z (2010) Hierarchical nanocomposites of polyaniline nanowire arrays on graphene oxide sheets with synergistic effect for energy storage. ACS Nano 4(9):5019–5026

  41. 41.

    Zhu H, Wang J, Liu X, Zhu X (2017) Three-dimensional porous graphene supported Ni nanoparticles with enhanced catalytic performance for methanol electrooxidation. Int J Hydrog Energy 42(16):11206–11214

  42. 42.

    Fard LA, Ojani R, Raoof JB (2016) Electrodeposition of three-dimensional Pd nanoflowers on a PPy@ MWCNTs with superior electrocatalytic activity for methanol electrooxidation. Int J Hydrog Energy 41(40):17987–17994

  43. 43.

    Liang R, Hu A, Persic J, Zhou YN (2013) Palladium nanoparticles loaded on carbon modified TiO2 nanobelts for enhanced methanol electrooxidation. Nano Micro Lett 5(3):202–212

  44. 44.

    Rahim MA, Hameed RA, Khalil M (2004) Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium. J Power Sources 134(2):160–169

  45. 45.

    Li X, Niu X, Zhang W, He Y, Pan J, Yan Y, Qiu F (2017) One-pot anchoring of Pd nanoparticles on nitrogen-doped carbon through dopamine self-polymerization and activity in the electrocatalytic methanol oxidation reaction. Chemsuschem 10(5):976–983

  46. 46.

    Gharibi H, Kakaei K, Zhiani M, Taghiabadi MM (2011) Effect of polyaniline-doped trifluoromethane sulfonic acid nanofiber composite film thickness on electrode for methanol oxidation. Int J Hydrog Energy 36(20):13301–13309

  47. 47.

    Yao Z, Yue R, Zhai C, Jiang F, Wang H, Du Y, Wang C, Yang P (2013) Electrochemical layer-by-layer fabrication of a novel three-dimensional Pt/graphene/carbon fiber electrode and its improved catalytic performance for methanol electrooxidation in alkaline medium. Int J Hydrog Energy 38(15):6368–6376

Download references

Author information

Correspondence to Moslem Mansour Lakouraj.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Oskueyan, G., Mansour Lakouraj, M. Electrodeposition of nanostructured Pt–Pd bimetallic catalyst on polyaniline-camphorsulfonic acid/graphene nanocomposites for methanol electrooxidation. J Appl Electrochem 49, 755–765 (2019) doi:10.1007/s10800-019-01321-2

Download citation


  • Platinum
  • Palladium
  • Polyaniline
  • Camphorsulfonic acid
  • Graphene
  • Methanol oxidation