Abstract
Controlled assembly in aqueous solution was used to synthesize the well-organized Pt/CS/PW12-GNs composite. By the aid of linear cationic polysaccharide chitosan, 2-D distribution worm-like Pt nanoparticles with their length and width of 15–20 and 3–4 nm, respectively, were formed on the surface of CS/PW12-GNs using HCOOH as a reducing agent at room temperature. The introduction of CS leads to well dispersion of worm-like Pt nanoparticles, the electroactivity of H3PW12O40 (PW12) alleviates CO poisoning toward Pt particles, and graphene nanosheets (GNs) ensure excellent electrical conductivity of the composites. The combined action among different components results in significantly enhanced catalytic activity of Pt/CS/PW12-GNs toward methanol oxidation and better tolerance of CO. The as-synthesized Pt/CS/PW12-GNs exhibit the forward peak current density of 445 mA mg−1, which is much higher than that (220 mA mg−1) for Pt/C-JM (the commercially available Johnson Matthey Hispec4000 catalyst, simplified as Pt/C-JM) and some recently reported Pt/graphene-based nanomaterials. The construction of 2-D distribution worm-like Pt nanoparticles and facile wet chemical synthesis strategy provide a promising way to develop superior performance electrocatalysts for direct methanol fuel cells applications.
Similar content being viewed by others
References
Almeida TS, Palma LM, Leonello PH, Morais C, Kokoh KB, De Andrade AR (2012) An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: effect of the preparation method on the electrocatalytic activity of the catalysts. J Power Sour 215:53–62
Bao H et al (2011) Chitosan-functionalized graphene oxide as a nanocarrier for drug and gene delivery. Small 7:1569–1578
Cui ZM, Jiang SP, Li CM (2011) Highly dispersed MoO x on carbon nanotube as support for high performance Pt catalyst towards methanol oxidation. Chem Commun 47:8418–8420
Cui Z, Guo CX, Li CM (2013) Self-assembled phosphomolybdic acid-polyaniline-graphene composite-supported efficient catalyst towards methanol oxidation. J Mater Chem A 1:6687–6692
Fan Y, Liu J, Lu H, Huang P, Xu D (2012) Hierarchical structure SnO2 supported Pt nanoparticles as enhanced electrocatalyst for methanol oxidation. Electrochim Acta 76:475–479
Guo S, Dong S, Wang E (2009) Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: facile synthesis and used as an advanced nanoelectrocatalyst for methanol oxidation. ACS Nano 4:547–555
Guo W, Xu L, Li F, Xu B, Yang Y, Liu S, Sun Z (2010) Chitosan-assisted fabrication and electrocatalytic activity of the composite film electrode of heteropolytungstate/carbon nanotubes. Electrochim Acta 55:1523–1527
Huang M, Bi L, Shen Y, Liu B, Dong S (2004) Nanocomposite multilayer film of preyssler-type polyoxometalates with fine tunable electrocatalytic activities. J Phys Chem B 108:9780–9786
Huang H, Liu Y, Gao Q, Ruan W, Lin X, Li X (2014) Rational construction of strongly coupled metal–metal oxide–graphene nanostructure with excellent electrocatalytic activity and durability. ACS Appl Mater Interfaces 6:10258–10264
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339
Ji K, Chang G, Oyama M, Shang X, Liu X, He Y (2012) Efficient and clean synthesis of graphene supported platinum nanoclusters and its application in direct methanol fuel cell. Electrochim Acta 85:84–89
Kim Y, Noh Y, Lim EJ, Lee S, Choi SM, Kim WB (2014) Star-shaped Pd@Pt core-shell catalysts supported on reduced graphene oxide with superior electrocatalytic performance. J Mater Chem A 2:6976–6986
Kovtyukhova NI, Ollivier PJ, Martin BR, Mallouk TE, Chizhik SA, Buzaneva EV, Gorchinskiy AD (1999) Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem Mater 11:771–778
Li H, Pang S, Feng X, Mullen K, Bubeck C (2010) Polyoxometalate assisted photoreduction of graphene oxide and its nanocomposite formation. Chem Commun 46:6243–6245
Li Z, Huang X, Zhang X, Zhang L, Lin S (2012) The synergistic effect of graphene and polyoxometalates enhanced electrocatalytic activities of Pt-{PEI-GNs/[PMo12O40]3−} n composite films regarding methanol oxidation. J Mater Chem 22:23602–23607
Li Z, Zhang L, Huang X, Ye L, Lin S (2014) Shape-controlled synthesis of Pt nanoparticles via integration of graphene and β-cyclodextrin and using as a noval electrocatalyst for methanol oxidation. Electrochim Acta 121:215–222
Liu R et al (2012a) Facile synthesis of Au-nanoparticle/polyoxometalate/graphene tricomponent nanohybrids: an enzyme-free electrochemical biosensor for hydrogen peroxide. Small 8:1398–1406
Liu R, Li S, Yu X, Zhang G, Zhang S, Yao J, Zhi L (2012b) A general green strategy for fabricating metal nanoparticles/polyoxometalate/graphene tri-component nanohybrids: enhanced electrocatalytic properties. J Mater Chem 22:3319–3322
Liu Y, Xia Y, Yang H, Zhang Y, Zhao M, Pan G (2013) Facile preparation of high-quality Pt/reduced graphene oxide nanoscrolls for methanol oxidation. Nanotechnology 24:235401
Liu A, Yuan M, Zhao M, Lu C, Zhao T, Li P, Tang W (2014) Graphene modulated assembly of PtPd bimetallic catalysts for electro-oxidation of methanol. J Alloys Compd 586:99–104
Long NV, Yang Y, Thi CM, Minh NV, 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 2:636–676
Lu H, Fan Y, Huang P, Xu D (2012) SnO2 nanospheres supported Pd catalyst with enhanced performance for formic acid oxidation. J Power Sour 215:48–52
Luo Z, Yuwen L, Bao B, Tian J, Zhu X, Weng L, Wang L (2012) One-pot, low-temperature synthesis of branched platinum nanowires/reduced graphene oxide (BPtNW/RGO) hybrids for fuel cells. J Mater Chem 22:7791–7796
Mondal A, Jana NR (2012) Fluorescent detection of cholesterol using β-cyclodextrin functionalized graphene. Chem Commun 48:7316–7318
Pan Y, Bao H, Li L (2011) Noncovalently functionalized multiwalled carbon nanotubes by chitosan-grafted reduced graphene oxide and their synergistic reinforcing effects in chitosan films. ACS Appl Mater Interfaces 3:4819–4830
Qiu JD, Wang GC, Liang RP, Xia XH, Yu HW (2011) Controllable deposition of platinum nanoparticles on graphene as an electrocatalyst for direct methanol fuel cells. J Phys Chem C 115:15639–15645
Tessonnier JP, Goubert Renaudin S, Alia S, Yan Y, Barteau MA (2012) Structure, stability, and electronic interactions of polyoxometalates on functionalized graphene sheets. Langmuir 29:393–402
Tsai HY, Shih ZY, Lin ZH, Chang HT (2013) Te/Pt nanonetwork modified carbon fiber microelectrodes for methanol oxidation. Nanotechnology 24:195402
Wang P, Li F, Huang X, Li Y, Wang L (2008) In situ electrodeposition of Pt nanoclusters on glassy carbon surface modified by monolayer choline film and their electrochemical applications. Electrochem Commun 10:195–199
Wang Y, Nguyen TS, Liu X, Wang X (2010) Novel palladium–lead (Pd–Pb/C) bimetallic catalysts for electrooxidation of ethanol in alkaline media. J Power Sources 195:2619–2622
Wang X, Li X, Liu D, Song S, Zhang H (2012) Green synthesis of Pt/CeO2/graphene hybrid nanomaterials with remarkably enhanced electrocatalytic properties. Chem Commun 48:2885–2887
Wietecha MS et al (2012) Platinum nanoparticles anchored on chelating group-modified graphene for methanol oxidation. J Power Sour 198:30–35
Wu Z et al (2007) Preparation and characterization of chitosan-grafted multiwalled carbon nanotubes and their electrochemical properties. Carbon 45:1212–1218
Wu LJ et al (2013) Thermally treated 3-D nanostructured graphene-supported Pd catalyst for significantly improved electrocatalytic performance towards ethanol electrooxidation. RSC Adv 3:5196–5203
Xin Y et al (2011) Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell. J Power Sour 196:1012–1018
Yang S, Shen C, Lu X, Tong H, Zhu J, Zhang X, Gao H (2012) Preparation and electrochemistry of graphene nanosheets–multiwalled carbon nanotubes hybrid nanomaterials as Pd electrocatalyst support for formic acid oxidation. Electrochim Acta 62:242–249
Ye L, Li Z, Zhang L, Lei F, Lin S (2014a) A green one-pot synthesis of Pt/TiO2/Graphene composites and its electro-photo-synergistic catalytic properties for methanol oxidation. J Colloid Interface Sci 433:156–162
Ye L, Li Z, Zhang X, Lei F, Lin S (2014b) One-step microwave synthesis of Pt (Pd)/Cu2O/GNs composites and their electro-photo-synergistic catalytic properties for methanol oxidation. J Mater Chem A 2:21010–21019
Yu DS, Dai LM (2010) Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J Phys Chem Lett 1:467–470
Zhao X, Zhu J, Liang L, Liu C, Liao J, Xing W (2012) Enhanced electroactivity of Pd nanocrystals supported on H3PMo12O40/carbon for formic acid electrooxidation. J Power Sour 210:392–396
Zhou D, Han B-H (2010) Graphene-based nanoporous materials assembled by mediation of polyoxometalate nanoparticles. Adv Funct Mater 20:2717–2722
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No.21171037), Research Foundation of the Education Department of Fujian Province (No. JA13082 & No. JB13010), and "333" Research Promotion Project of Fujian Normal University.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, Z., Lei, F., Ye, L. et al. Controlled synthesis of Pt/CS/PW12-GNs composite as an anodic electrocatalyst for direct methanol fuel cells. J Nanopart Res 17, 192 (2015). https://doi.org/10.1007/s11051-015-2995-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-015-2995-4