Skip to main content

Advertisement

SpringerLink
Log in

Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

The production of large-area interfaces and the use of scalable methods to build up designed nanostructures generating advanced functional properties are of high interest for many materials science applications. Nevertheless, large-area coverage remains a major problem even for pristine graphene, and here we present a hybrid, composite graphene-like material soluble in water that can be exploited in many areas such as energy storage, electrodes fabrication, selective membranes and biosensing. Graphene oxide (GO) was produced by the traditional Hummers’ method being further reduced in the presence of poly(styrene sulfonate) sodium salt (PSS), thus creating stable reduced graphene oxide (rGO) nanoplatelets wrapped by PSS (GPSS). Molecular dynamics simulations were carried out to further clarify the interactions between PSS molecules and rGO nanoplatelets, with calculations supported by Fourier transform infrared spectroscopy analysis. The intermolecular forces between rGO nanoplatelets and PSS lead to the formation of a hybrid material (GPSS) stabilized by van der Waals forces, allowing the fabrication of high-quality layer-by-layer (LbL) films with poly(allylamine hydrochloride) (PAH). Raman and electrical characterizations corroborated the successful modifications in the electronic structures from GO to GPSS after the chemical treatment, resulting in (PAH/GPSS) LbL films four orders of magnitude more conductive than (PAH/GO).

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

Explore related subjects

Discover the latest articles, news and stories from top researchers in related subjects.

References

  1. Brownson DAC, Kampouris DK, Banks CE (2011) An overview of graphene in energy production and storage applications. J Power Sour 196:4873–4885

    Article  Google Scholar 

  2. Cai H, Li J, Xu X et al (2017) Nanostructured composites of one-dimensional TiO2 and reduced graphene oxide for efficient dye-sensitized solar cells. J Alloys Compd 697:132–137

    Article  Google Scholar 

  3. Liang B, Guo X, Fang L et al (2015) Study of direct electron transfer and enzyme activity of glucose oxidase on graphene surface. Electrochem Commun 50:1–5

    Article  Google Scholar 

  4. Shao Y, Wang J, Wu H et al (2010) Graphene based electrochemical sensors and biosensors: a review. Electroanalysis 22:1027–1036

    Article  Google Scholar 

  5. Gupta V, Chaudhary N, Srivastava R et al (2011) Luminscent graphene quantum dots for organic photovoltaic devices. J Am Chem Soc 133:9960–9963

    Article  Google Scholar 

  6. Bonaccorso F, Sun Z, Hasan T, Ferrari AC (2010) Graphene photonics and optoelectronics. Nat Photonics 4:611–622

    Article  Google Scholar 

  7. Kholmanov IN, Magnuson CW, Piner R et al (2015) Optical, electrical, and electromechanical properties of hybrid graphene/carbon nanotube films. Adv Mater 27:3053–3059

    Article  Google Scholar 

  8. Novoselov KS, Geim AK, Morozov SV et al (2004) Electric field effect in atomically thin carbon films. Science 306:666–669

    Article  Google Scholar 

  9. Jang J, Son M, Chung S et al (2015) Low-temperature-grown continuous graphene films from benzene by chemical vapor deposition at ambient pressure. Sci Rep 5:17955

    Article  Google Scholar 

  10. Shao J-J, Lv W, Yang Q-H (2014) Self-assembly of graphene oxide at interfaces. Adv Mater 26:5586–5612

    Article  Google Scholar 

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

    Article  Google Scholar 

  12. Wang G, Shen X, Wang B et al (2009) Synthesis and characterisation of hydrophilic and organophilic graphene nanosheets. Carbon 47:1359–1364

    Article  Google Scholar 

  13. Pei S, Cheng H-M (2012) The reduction of graphene oxide. Carbon 50:3210–3228

    Article  Google Scholar 

  14. Loh KP, Bao Q, Eda G, Chhowalla M (2010) Graphene oxide as a chemically tunable platform for optical applications. Nat Chem 2:1015–1024

    Article  Google Scholar 

  15. Richardson JJ, Bjornmalm M, Caruso F (2015) Technology-driven layer-by-layer assembly of nanofilms. Science 348:2491–2491

    Article  Google Scholar 

  16. Hu J, He B, Lu J et al (2012) Facile preparation of Pt/polyallylamine/reduced graphene oxide composites and their application in the electrochemical catalysis on methanol oxidation. Int J Electrochem Sci 7:10094–10107

    Google Scholar 

  17. Huang C, Li C, Shi G (2012) Graphene based catalysts. Energy Environ Sci 5:8848–8868

    Article  Google Scholar 

  18. Cohen-Tanugi D, Lin L-C, Grossman JC (2016) Multilayer nanoporous graphene membranes for water desalination. Nano Lett 16:1027–1033

    Article  Google Scholar 

  19. Long Y, Wang K, Xiang G et al (2017) Molecule channels directed by cation-decorated graphene oxide nanosheets and their application as membrane reactors. Adv Mater 29:1606093–1606097

    Article  Google Scholar 

  20. Bo X, Zhou M, Guo L (2017) Electrochemical sensors and biosensors based on less aggregated graphene. Biosens Bioelectron 89(1):167–186

    Article  Google Scholar 

  21. Mascagni DBT, Miyazaki CM, da Cruz NC et al (2016) Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection. Mater Sci Eng C 68:739–745. https://doi.org/10.1016/j.msec.2016.06.001

    Article  Google Scholar 

  22. Hsiao S-T, Ma C-CM, Liao W-H et al (2014) Lightweight and flexible reduced graphene oxide/water-borne polyurethane composites with high electrical conductivity and excellent electromagnetic interference shielding performance. ACS Appl Mater Interfaces 6:10667–10678

    Article  Google Scholar 

  23. Lee DW, Hong T-K, Kang D et al (2011) Highly controllable transparent and conducting thin films using layer-by-layer assembly of oppositely charged reduced graphene oxides. J Mater Chem 21:3438

    Article  Google Scholar 

  24. Zou J, Kim F (2014) Diffusion driven layer-by-layer assembly of graphene oxide nanosheets into porous three-dimensional macrostructures. Nat Commun 5:5254

    Article  Google Scholar 

  25. Liu Y, Liu Y, Feng H et al (2012) Layer-by-layer assembly of chemical reduced graphene and carbon nanotubes for sensitive electrochemical immunoassay. Biosens Bioelectron 35:63–68

    Article  Google Scholar 

  26. Marmisollé WA, Azzaroni O (2016) Recent developments in the layer-by-layer assembly of polyaniline and carbon nanomaterials for energy storage and sensing applications. From synthetic aspects to structural and functional characterization. Nanoscale 8:9890–9918

    Article  Google Scholar 

  27. Decher G (1997) Fuzzy nanoassemblies: toward layered polymeric multicomposites. Science 277:1232–1237

    Article  Google Scholar 

  28. Decher G, Hong JD, Schmitt J (1992) Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces. Thin Solid Films 2:831–835

    Article  Google Scholar 

  29. Kovtyukhova NI, Ollivier PJ, Martin BR et al (1999) Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem Mater 11:771–778. https://doi.org/10.1021/cm981085u

    Article  Google Scholar 

  30. Stankovich S, Piner RD, Chen X et al (2006) Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). J Mater Chem 16:155

    Article  Google Scholar 

  31. Girotto EM, Santos IA (2002) Medidas de resistividade elétrica DC em sólidos: Como efetuá-las corretamente. Quím Nova 25:639

    Article  Google Scholar 

  32. Bagri A, Mattevi C, Acik M et al (2010) Structural evolution during the reduction of chemically derived graphene oxide. Nat Chem 2:581–587

    Article  Google Scholar 

  33. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2009) The chemistry of graphene oxide. Chem Soc Rev 39:228–240

    Article  Google Scholar 

  34. Berendsen HJC, Postma JPM, van Gunsteren WF et al (1984) Molecular dynamics with coupling to an external bath. J Chem Phys 81:3684–3690

    Article  Google Scholar 

  35. Hoover W (1985) Canonical dynamics: equilibrium phase-space distributions. Phys Rev A 31:1695–1697

    Article  Google Scholar 

  36. Martyna GJ, Klein ML, Tuckerman M (1992) Nosé–Hoover chains: the canonical ensemble via continuous dynamics. J Chem Phys 97:2635–2643

    Article  Google Scholar 

  37. Jorgensen WL, Chandrasekhar J, Madura JD et al (1983) Comparison of simple potential functions for simulating liquid water. J Chem Phys 79:926–935

    Article  Google Scholar 

  38. Carrillo J-MY, Dobrynin AV (2010) Detailed molecular dynamics simulations of a model NaPSS in water. J Phys Chem B 114:9391–9399

    Article  Google Scholar 

  39. Jiao S, Xu Z (2015) Selective gas diffusion in graphene oxides membranes: a molecular dynamics simulations study. ACS Appl Mater Interf 7:9052–9059

    Article  Google Scholar 

  40. Martínez L, Andrade R, Birgin EG, Martínez JM (2009) PACKMOL: a package for building initial configurations for molecular dynamics simulations. J Comput Chem 30:2157–2164

    Article  Google Scholar 

  41. Plimpton S (1995) Fast parallel algorithms for short-range molecular dynamic. J Comput Phys 117:1–19

    Article  Google Scholar 

  42. Khanra P, Kuila T, Kim NH et al (2012) Simultaneous bio-functionalization and reduction of graphene oxide by baker’s yeast. Chem Eng J 183:526–533

    Article  Google Scholar 

  43. Liu Y, Gao L, Sun J et al (2009) Stable nafion-functionalized graphene dispersions for transparent conducting films. Nanotechnology 20:465605

    Article  Google Scholar 

  44. Jiang G, Baba A, Advincula R (2007) Nanopatterning and fabrication of memory devices from layer-by-layer poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonate) ultrathin films. Langmuir 23:817–825

    Article  Google Scholar 

  45. Pimenta MA, Dresselhaus G, Dresselhaus MS et al (2007) Studying disorder in graphite-based systems by Raman spectroscopy. Phys Chem Chem Phys 9:1276

    Article  Google Scholar 

  46. Ferrari AC, Meyer JC, Scardaci V et al (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97:187401

    Article  Google Scholar 

  47. Wang Y, Alsmeyer DC, McCreery RL (1990) Raman spectroscopy of carbon materials: structural basis of observed spectra. Chem Mater 2:557–563

    Article  Google Scholar 

  48. Yang D, Velamakanni A, Bozoklu G et al (2009) Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy. Carbon 47:145–152

    Article  Google Scholar 

  49. Pham VH, Cuong TV, Hur SH et al (2010) Fast and simple fabrication of a large transparent chemically-converted graphene film by spray-coating. Carbon 48:1945–1951

    Article  Google Scholar 

  50. Rani A, Oh KA, Koo H et al (2011) Multilayer films of cationic graphene-polyelectrolytes and anionic graphene-polyelectrolytes fabricated using layer-by-layer self-assembly. Appl Surf Sci 257:4982–4989

    Article  Google Scholar 

  51. Wang S, Yu D, Dai L et al (2011) Polyelectrolyte-functionalized graphene as metal-free electrocatalysts for oxygen reduction. ACS Nano 5:6202–6209

    Article  Google Scholar 

  52. Zhang Y, Hu W, Li B et al (2011) Synthesis of polymer-protected graphene by solvent-assisted thermal reduction process. Nanotechnology 22:345601

    Article  Google Scholar 

  53. Lu J, Do I, Fukushima H et al (2010) Stable aqueous suspension and self-assembly of graphite nanoplatelets coated with various polyelectrolytes. J Nanomater 2010:11

    Google Scholar 

  54. Si Y, Samulski ET (2008) Synthesis of water soluble graphene. Nano Lett 8:1679–1682

    Article  Google Scholar 

  55. He P, Derby B (2017) Inkjet printing ultra-large graphene oxide flakes. 2D Mater 4:021021

    Article  Google Scholar 

  56. Gross MA, Sales MJA, Soler MAG et al (2014) Reduced graphene oxide multilayers for gas and liquid phases chemical sensing. RSC Adv 4:17917–17924

    Article  Google Scholar 

  57. Zheng Q, Kim J-K (2015) Graphene for transparent conductors—synthesis properties. Springer, New York

    Book  Google Scholar 

  58. Kotov NA, Dékány I, Fendler JH (1996) Ultrathin graphite oxide-polyelectrolyte composites prepared by self-assembly: transition between conductive and non-conductive states. Adv Mater 8:637–641

    Article  Google Scholar 

  59. Kim Y-K, Min D-H (2009) Durable large-area thin films of graphene/carbon nanotube double layers as a transparent electrode. Langmuir 25:11302–11306

    Article  Google Scholar 

  60. Jimenez MJM, Oliveira RF, Almeida TP et al (2017) Charge carrier transport in defective reduced graphene oxide as quantum dots and nanoplatelets in multilayer films. Nanotechnology 28:495711

    Article  Google Scholar 

Download references

Acknowledgements

Authors are grateful to FAPESP (2010/13033-6, 2012/01484-9, 2015/14703-9, 2016/00023-9, 2014/24547-1 and 2014/11410-8), INEO (CNPq) for financial support, and also Bernhard Gross Polymer Group (IFSC–USP), Ângelo L. Gobbi and Maria Helena O. Piazzetta at Laboratory of Microfabrication (LNNano/CNPEM) for the cooperation in microelectrodes fabrication. This research also used the computing resources and assistance of the John David Rogers Computing Center (CCJDR) in the Institute of Physics “Gleb Wataghin,” University of Campinas.

Author information

Authors and Affiliations

  1. POSMAT – Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, UNESP – Univ Estadual Paulista, Bauru, SP, Brazil

    Celina M. Miyazaki & Marco A. E. Maria

  2. Universidade Federal de São Carlos – DFQM, Sorocaba, SP, Brazil

    Celina M. Miyazaki

  3. Faculdade de Engenharia de Sorocaba – FACENS, Sorocaba, SP, Brazil

    Marco A. E. Maria

  4. Applied Physics Department, State University of Campinas, Campinas, SP, 13083-970, Brazil

    Marco A. E. Maria, Daiane Damasceno Borges, Cristiano F. Woellner, Gustavo Brunetto, Alexandre F. Fonseca, Abner de Siervo, Douglas S. Galvao & Antonio Riul Jr.

  5. UNESP – Univ Estadual Paulista, Presidente Prudente, SP, Brazil

    Carlos J. L. Constantino

  6. Centro Universitário Central Paulista – UNICEP, São Carlos, SP, Brazil

    Marcelo A. Pereira-da-Silva

  7. Instituto de Física de São Carlos – USP, São Carlos, SP, Brazil

    Marcelo A. Pereira-da-Silva

Authors
  1. Celina M. Miyazaki
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Marco A. E. Maria
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Daiane Damasceno Borges
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cristiano F. Woellner
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Gustavo Brunetto
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Alexandre F. Fonseca
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Carlos J. L. Constantino
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Marcelo A. Pereira-da-Silva
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Abner de Siervo
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Douglas S. Galvao
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Antonio Riul Jr.
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Antonio Riul Jr..

Ethics declarations

Conflicts of interest

No conflicts of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1909 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Miyazaki, C.M., Maria, M.A.E., Borges, D.D. et al. Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt. J Mater Sci 53, 10049–10058 (2018). https://doi.org/10.1007/s10853-018-2325-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2325-1

Keywords

Search

Navigation