Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Chemical surface modification of graphene oxide by femtosecond laser pulse irradiation in aqueous suspensions

  • 756 Accesses

  • 2 Citations


Reduction of graphene oxide (GO) by femtosecond laser pulse irradiation of an aqueous suspension was studied. Different laser parameters such as laser fluence and irradiation time were scanned to obtain the optimum reduced graphene oxide (rGO) with fewer defect sites and lower electrical resistivity. The fabricated rGO samples were characterized using several techniques such as X-ray diffraction, UV–Visible absorption spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy, and others. The XRD profiles of rGO revealed that the interplanar spacing between carbon layers significantly decreased to 3.51 Å, which is close to that of pristine graphite. Furthermore, the intensity ratio of D and G bands of rGO measured by Raman spectroscopy was more than 20 % smaller than that of GO, indicating the enhancement of sp2 domains. It is noted that the defect sites and the disorder carbon double bond networks on the basal graphene plane were relatively decreased after reduction. In addition, the electrical resistivity of rGO significantly decreased to 3.3 Ω·cm under the optimum condition. From these results, femtosecond laser can be used as a suitable tool for GO reduction because it is a simple, controllable, and flexible method for getting highly reduced graphene oxide.

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

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8


  1. 1

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

  2. 2

    Orlita M, Faugeras C, Plochocka P, Neugebauer P, Martinez G, Maude DK et al (2008) Approaching the dirac point in high-mobility multilayer epitaxial graphene. Phys Rev Lett 101:267601–267604

  3. 3

    Balandin AA, Gosh S, Bao W, Calizo I, Teweldebrhan D, Miao F et al (2008) Superior thermal conductivity of single-layer graphene. Nano Lett 8:902–907

  4. 4

    Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385–388

  5. 5

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

  6. 6

    Zhu Y, Murali S, Stoller MD, Ganesh KJ, Cai W, Ferreira PJ et al (2011) Carbon-based supercapacitors produced by activation of graphene. Science 332:1537–1541

  7. 7

    Bian X, Song ZL, Qian Y, Gao W, Cheng ZQ, Chen L et al (2014) Fabrication of graphene-isolated-Au-nanocrystal nanostructures for multimodal cell imaging and photothermal-enhanced chemotherapy. Sci Rep 4:6093–6101

  8. 8

    Wang X, Zhi L, Müllen K (2008) Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett 8:323–327

  9. 9

    Hummers WS, Offeman EE (1953) Preparation of graphitic oxide. J Am Chem Soc 80:1339

  10. 10

    Eda G, Mattevi C, Yamaguchi H, Kim H, Chhowalla M (2009) Insulator to semimetal transition in graphene oxide. J Phys Chem C 113:15768–15771

  11. 11

    Eda G, Franchini G, Chhowalla M (2008) Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nat Nano 3:270–274

  12. 12

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

  13. 13

    Cote LJ, Silva RC, Huang J (2009) Flash reduction and patterning of graphite oxide and its polymer composite. J Am Chem Soc 131:11027–11032

  14. 14

    Ng YH, Iwase A, Kudo A, Amal R (2010) Reducing graphene oxide on a visible-light BiVO4 photocatalyst for enhanced photoelectrochemical water splitting. J Phys Chem Lett 1:2607–2612

  15. 15

    Zhang Y, Guo L, Wei S, He Y, Xia H, Chen Q et al (2010) Direct imprinting of microcircuits on graphene oxides film by femtosecond laser reduction. Nano Today 5:15–20

  16. 16

    Compagnini G, Russo P, Tomarchio F, Puglisi O, D’Urso L et al (2012) Laser assisted green synthesis of free standing reduced graphene oxides at the water-air interface. Nanotechnology 23:505601–505606

  17. 17

    Gao W, Singh N, Song L, Liu Z, Reddy ALM, Ci L et al (2011) Direct laser writing of micro-supercapacitors on hydrated graphite oxide films. Nat Nanotechnol. doi:10.1038/NNANO.2011.110

  18. 18

    Chichkov BN, Momma S, Nolte S, von Alvensleben F, Tünnermann A (1996) Femtosecond, picosecond and nanosecond laser ablation of solids. Appl Phys A 63:109–115

  19. 19

    Miyamoto Y, Zhang H, Tománek D (2010) Photoexfoliation of graphene from graphite: an ab initio study. Phys Rev Lett 104:208302–208305

  20. 20

    Zhang H, Miyamoto Y (2012) Graphene production by laser shot on graphene oxide; ab initio prediction. Phys Rev B 85:033402–033405

  21. 21

    Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A et al (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814

  22. 22

    Shang J, Ma L, Li J, Ai W, Yu T, Gurzadyan GG (2012) The origin of fluorescence from graphene oxide. Sci Rep 2:792–799

  23. 23

    Zhang J, Yang H, Shen G, Cheng P, Zhang J, Guo S (2010) Reduction of graphene oxide vial-ascorbic acid. Chem Commun 46:1112–1114

  24. 24

    Spanò SF, Isgrò G, Russo P, Fragalà ME, Compagnini G (2014) Tunable properties of graphene oxide reduced by laser irradiation. Appl Phys A 117:19–23

  25. 25

    Nethravathi C, Rajamathi M (2008) Chemical modified graphene sheets produced by the solvothermal reduction of colloidal dispersions of graphite oxide. Carbon 46:1994–1998

  26. 26

    Kim MC, Hwang GS, Ruoff RS (2009) Epoxide reduction with hydrazine on graphene: a first principles study. J Chem Phys 131:064704–064708

  27. 27

    Shin HJ, Kim KK, Benayad A, Yoon SM, Park HK, Jung IS et al (2009) Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance. Adv Funct Mater 19:1987–1992

  28. 28

    Lerf A, He H, Forster M, Klinowski J (1998) Structure of graphite oxide revisited. J Phys Chem B 102:4477–4482

  29. 29

    Whitby RLD, Gun’ko VM, Korobeinyk A, Busquets R, Cundy AB, Lászlo K (2012) Driving forces of conformational changes in single-layer graphene oxide. ACS Nano 6:3967–3973

  30. 30

    Yan J, Zhang Y, Kim P, Pinczuk A (2007) Electric field effect tuning of electron-phonon coupling in graphene. Phys Rev Lett 98:166802–166805

  31. 31

    Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 61:14095–14107

  32. 32

    Valipour A, Hamnabard N, Ahn YH (2015) Performance evaluation of highly conductive graphene (RGOHI-AcOH) and graphene/metal nanoparticles composite (RGO/Ni) coated on carbon cloth for supercapacitor application. RSC Adv 5:92970–92979

  33. 33

    Chen W, Yan L, Bangal PR (2010) Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves. Carbon 48:1146–1152

  34. 34

    Ji T, Hua Y, Sun M, Ma N (2013) The mechanism of the reaction of graphite oxide to reduced graphene oxide under ultraviolet irradiation. Carbon 54:412–418

  35. 35

    Nipane SV, Mali MG, Gokavi GS (2014) Reduced graphene oxide supported silicotungstic acid for efficient conversion of thiols to disulfides by hydrogen peroxide. Ind Eng Chem Res 53:3924–3930

  36. 36

    Pommeret S, Gobert F, Mostafavi M, Lampre I, Mialocq JC (2001) Femtochemistry of the hydrated electron at decimolar concentration. J Phys Chem A 105:11400–11406

  37. 37

    Xu SC, Irle S, Musaev DG, Lin MC (2006) Quantum chemical study of the dissociative adsorption of OH and H2O on pristine and defective graphite (0001) surfaces: reaction mechanisms and kinetics. J Phys Chem C 111:1355–1365

  38. 38

    Gao X, Jang J, Nagase S (2009) Hydrazine and thermal reduction of graphene oxide: reaction mechanisms, product structures, and reaction design. J Phys Chem C 114:832–842

  39. 39

    Chin SL, Lagacé S (1996) Generation of H2, O2 and H2O from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization. Appl Opt 35:907–911

  40. 40

    Besner S, Meunir M (2010) Femtosecond laser synthesis of Au Ag nanoalloys: photoinduced oxidation and ions release. J Phys Chem C 114:10403–10409

  41. 41

    Xing WL, Lalwani G, Rusakova I, Sitharaman B (2014) Degradation of graphene by hydrogen peroxide. Part Part Syst Char 31:745–750

  42. 42

    Wittmann G, Horváth I, Dombi A (2002) UV-induced decomposition of ozone and hydrogen peroxide in the aqueous phase at pH 2–7. Ozone Sci Eng 24:281–291

  43. 43

    Liu B, Yin S, Wang Y, Guo C, Wu X, Dong Q et al (2015) A facile one-step solvothermal synthesis and electrical properties of reduced graphene oxide/rod-shaped potassium tungsten bronze nanocomposite. J Nanosci Nanotechnol 15:7305–7310

Download references


The authors would like to acknowledge Mr. Yoshihiro Ojiro, Dr. Shuichi Ogawa, and Prof. Yuji Takakuwa for measurement of electrical resistibility of GO and rGO using a four-point probe method. The first author is financially supported by Indonesia Endowment Fund for Education (LPDP).

Author information

Correspondence to Muttaqin.

Ethics declarations

Conflict of interests

The authors declare that there is no conflict of interests.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (TIFF 75 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Muttaqin, Nakamura, T., Nishina, Y. et al. Chemical surface modification of graphene oxide by femtosecond laser pulse irradiation in aqueous suspensions. J Mater Sci 52, 749–759 (2017). https://doi.org/10.1007/s10853-016-0368-8

Download citation


  • Graphene Oxide
  • Femtosecond Laser
  • Graphene Sheet
  • Reduce Graphene Oxide
  • Laser Fluence