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Facile fabrication of holey graphene oxide paper bonded with sulfonic acid for highly efficient proton conduction

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Abstract

In this work, a novel holey graphene oxide bonded with sulfonic acid groups (S-HGO) was developed using a facile and eco-friendly strategy: erosion and oxidation of graphene oxide (GO) by H2O2 and sulfonation by 4-benzenediazoniumsulfonate. The freestanding paper fabricated by S-HGO shows a high proton conductivity of 4.97 × 10−2 S cm−1 at 60 °C and 100% relative humidity (RH), which is comparable to Nafion 115 (7.67 × 10−2 S cm−1) at the same condition. The holes on S-HGO provide shortcut channels for proton transfer across the GO nanosheet. The chemical-linked sulfonic acid groups afford additional hop sites for proton conduction and endow itself an enhanced thermostability. Under 100% RH and ambient pressure, the freestanding S-HGO deliver a peak power density of 103 mW cm−2 at a load current density of 273 mA cm−2, which is about three times more than that of GO at 35 °C. The results demonstrate that this S-HGO paper is a promising nanoscale inorganic material for proton exchange membranes.

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References

  1. Zhang W, Zheng H, Zhang C, Li B, Fang F, Wang Y (2017) Strengthen the performance of sulfonated poly (ether ether ketone) as proton exchange membranes with phosphonic acid functionalized carbon nanotubes. Ionics 23:2103–2112

    Article  CAS  Google Scholar 

  2. Beydaghi H, Javanbakht M, Kowsari E (2016) Preparation and physicochemical performance study of proton exchange membranes based on phenyl sulfonated graphene oxide nanosheets decorated with iron titanate nanoparticles. Polymer 87:26–37

    Article  CAS  Google Scholar 

  3. Pan H, Chen S, Jin M, Chang Z, Pu H (2018) Preparation and properties of sulfonated polybenzimidazole-polyimide block copolymers as electrolyte membranes. Ionics 24:1629–1638

    Article  CAS  Google Scholar 

  4. Karim MR, Hatakeyama K, Matsui T, Takehira H, Taniguchi T, Koinuma M, Matsumoto Y, Akutagawa T, Nakamura T, Noro S, Yamada T, Kitagawa H, Hayami S (2013) Graphene oxide nanosheet with high proton conductivity. J Am Chem Soc 135:8097–8100

    Article  CAS  PubMed  Google Scholar 

  5. Hatakeyama K, Karim MR, Ogata C, Tateishi H, Funatsu A, Taniguchi T, Koinuma M, Hayami S, Matsumoto Y (2014) Proton conductivities of graphene oxide nanosheets: single, multilayer, and modified nanosheets. Angew Chem Int Ed 53:6997–7000

    Article  CAS  Google Scholar 

  6. Qiu X, Dong T, Ueda M, Zhang X, Wang L (2017) Sulfonated reduced graphene oxide as a conductive layer in sulfonated poly (ether ether ketone) nanocomposite membranes. J Membrane Sci 524:663–672

    Article  CAS  Google Scholar 

  7. Cheng T, Feng M, Huang Y, Liu X (2017) SGO/SPEN-based highly selective polymer electrolyte membranes for direct methanol fuel cells. Ionics 23:2143–2152

    Article  CAS  Google Scholar 

  8. Tseng C, Ye Y, Cheng M, Kao K, Shen W, Rick J, Chen J, Hwang B (2011) Sulfonated polyimide proton exchange membranes with graphene oxide show improved proton conductivity, methanol crossover impedance, and mechanical properties. Adv Energy Mater 1:1220–1224

    Article  CAS  Google Scholar 

  9. Rambabu G, Bhat SD (2018) Amino acid functionalized graphene oxide based nanocomposite membrane electrolytes for direct methanol fuel cells. J Membrane Sci 551:1–11

    Article  CAS  Google Scholar 

  10. Kumar R, Mamlouk M, Scott K (2011) A graphite oxide paper polymer electrolyte for direct methanol fuel cells. Int J Electrochem 2011:1–7

    Article  CAS  Google Scholar 

  11. Gao W, Wu G, Janicke MT, Cullen DA, Mukundan R, Baldwin JK, Brosha EL, Galande C, Ajayan PM, More KL, Dattelbaum AM, Zelenay P (2014) Ozonated graphene oxide film as a proton-exchange membrane. Angew Chem Int Ed 53:3588–3593

    Article  CAS  Google Scholar 

  12. Ravikumar SK (2012) Freestanding sulfonated graphene oxide paper: a new polymer electrolyte for polymer electrolyte fuel cells. Chem Commun 48:5584–5586

    Article  CAS  Google Scholar 

  13. Hou H, Hu X, Liu X, Hu W, Meng R, Li L (2015) Sulfonated graphene oxide with improved ionic performances. Ionics 21:1919–1923

    Article  CAS  Google Scholar 

  14. Jiang Z, Shi Y, Jiang Z, Tian X, Luo L, Chen W (2014) High performance of a free-standing sulfonic acid functionalized holey graphene oxide paper as a proton conducting polymer electrolyte for air-breathing direct methanol fuel cells. J Mater Chem A 2:6494

    Article  CAS  Google Scholar 

  15. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339

    Article  CAS  Google Scholar 

  16. Xu Y, Lin Z, Zhong X, Huang X, Weiss NO, Huang Y, Duan X (2014) Holey graphene frameworks for highly efficient capacitive energy storage. Nat Commun 5:4554

    Article  CAS  PubMed  Google Scholar 

  17. Ji J, Zhang G, Chen H, Wang S, Zhang G, Zhang F, Fan X (2011) Sulfonated graphene as water-tolerant solid acid catalyst. Chem Sci 2:484–487

    Article  CAS  Google Scholar 

  18. Bayer T, Bishop SR, Nishihara M, Sasaki K, Lyth SM (2014) Characterization of a graphene oxide membrane fuel cell. J Power Sources 272:239–247

    Article  CAS  Google Scholar 

  19. Heo Y, Im H, Kim J (2013) The effect of sulfonated graphene oxide on sulfonated poly (ether ether ketone) membrane for direct methanol fuel cells. J Membrane Sci 425:11–22

    Article  CAS  Google Scholar 

  20. Xu Y, Chen C, Zhao Z, Lin Z, Lee C, Xu X, Wang C, Huang Y, Shakir MI, Duan X (2015) Solution processable holey graphene oxide and its derived macrostructures for high-performance supercapacitors. Nano Lett 15:4605–4610

    Article  CAS  PubMed  Google Scholar 

  21. Nishimura O, Yabe K, Iwaki M (1989) X-ray photoelectron spectroscopy studies of high-dose nitrogen ion implanted-chromium: a possibility of a standard material for chemical state analysis. J Electron Spectrosc Relat Phemon 49:335–342

    Article  CAS  Google Scholar 

  22. Vinothkannan M, Kannan R, Kim AR, Kumar GG, Nahm KS, Yoo DJ (2016) Facile enhancement in proton conductivity of sulfonated poly (ether ether ketone) using functionalized graphene oxide—synthesis, characterization, and application towards proton exchange membrane fuel cells. Colloid Polym Sci 294:1197–1207

    Article  CAS  Google Scholar 

  23. Kumar R, Mamlouk M, Scott K (2014) Sulfonated polyether ether ketone - sulfonated graphene oxide composite membranes for polymer electrolyte fuel cells. RSC Adv 4:617–623

    Article  CAS  Google Scholar 

  24. Beydaghi H, Javanbakht M, Bagheri A, Salarizadeh P, Ghafarian-Zahmatkesh H, Kashefi S, Kowsari E (2015) Novel nanocomposite membranes based on blended sulfonated poly (ether ether ketone)/poly (vinyl alcohol) containing sulfonated graphene oxide/Fe3O4 nanosheets for DMFC applications. RSC Adv 5:74054–74064

    Article  CAS  Google Scholar 

  25. Zhao Y, Tang K, Ruan H, Xue L, Van der Bruggen B, Gao C, Shen J (2017) Sulfonated reduced graphene oxide modification layers to improve monovalent anions selectivity and controllable resistance of anion exchange membrane. J Membrane Sci 536:167–175

    Article  CAS  Google Scholar 

  26. Sharma PP, Kulshrestha V (2015) Synthesis of highly stable and high water retentive functionalized biopolymer-graphene oxide modified cation exchange membranes. RSC Adv 5:56498–56506

    Article  CAS  Google Scholar 

  27. Neelakandan S, Jacob NK, Kanagaraj P, Sabarathinam RM, Muthumeenal A, Nagendran A (2016) Effect of sulfonated graphene oxide on the performance enhancement of acid-base composite membranes for direct methanol fuel cells. RSC Adv 6:51599–51608

    Article  CAS  Google Scholar 

  28. Chien H, Tsai L, Huang C, Kang C, Lin J, Chang F (2013) Sulfonated graphene oxide/Nafion composite membranes for high-performance direct methanol fuel cells. Int J Hydrogen Energ 38:13792–13801

    Article  CAS  Google Scholar 

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Funding

This work was supported by the National Natural Science Foundation of China (11705126) and Science and Technology Program of Tianjin (16JCQNIC06000 and 16JCYBJC21100).

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Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, Tianjin Key Laboratory of Membrane Science & Desalination Technology and School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Chengyi Zhang, Wen Zhang, Yingxin Mu, Feifei Fang & Yuxin Wang

  2. Department of Applied Chemistry, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Chengde Huang

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  1. Chengyi Zhang
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  2. Wen Zhang
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  3. Yingxin Mu
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  4. Feifei Fang
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Correspondence to Wen Zhang or Chengde Huang.

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Zhang, C., Zhang, W., Mu, Y. et al. Facile fabrication of holey graphene oxide paper bonded with sulfonic acid for highly efficient proton conduction. Ionics 25, 573–581 (2019). https://doi.org/10.1007/s11581-018-2789-7

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  • DOI: https://doi.org/10.1007/s11581-018-2789-7

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