A cost-effective and highly efficient method was proposed for preparing reduced graphene (rEG) by modified Hummers approach. The influence of ratio of KMnO4 to graphite, oxidation time and oxidation temperature on oxidative degree of graphite oxide (GO) was investigated by x-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The thermal exfoliated graphene (EG) was characterized with transmission electron microscopy (TEM), FTIR, Raman spectrum and Brunauer–Emmett–Teller (BET) method. The EG was treated for 4 h at 800 °C with H2/Ar mixed atmosphere (15/85, v%) to remove the residual functional groups. The characterization of x-ray photoelectron spectroscopy (XPS) showed that rEG contains less functional groups than EG, which shows the C/O ratio increased from 10.6 (EG) to 34.71 (rEG). The results indicate that treating EG with a mixed H2/Ar atmosphere (15/85, v%) remarkably removes residual functional groups of EG, supplying a simple and feasible approach with large scale production of reduced graphene.
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W. Wei and X. Qu: Extraordinary physical properties of functionalized graphene. Small 8, 2138 (2012).
T. Ji, M. Sun, and P. Han: A review of the preparation and applications of graphene/semiconductor composites. Carbon 70, 1967 (2014).
S. Yang, W. Lin, Y. Huang, H. Tien, J. Wang, and C.C.M. Ma: Synergetic effects of graphene platelets and carbon nanotubes on the mechanical and thermal properties of epoxy composites. Carbon 49, 793 (2011).
J. Kim and S. Kim: Preparation and electrochemical property of ionic liquid-attached graphene nanosheets for an application of supercapacitor electrode. Electrochim. Acta 119, 11 (2014).
W. Li, X. Geng, Y. Guo, J. Rong, Y. Gong, L. Wu, X. Zhang, P. Li, J. Xu, G. Cheng, M. Sun, and L. Liu: Reduced graphene oxide electrically contacted graphene sensor for highly sensitive nitric oxide detection. ACS Nano 5, 6955 (2011).
A. Wisitsoraat and A. Tuantranont: Graphene-based chemical and biosensors. Small 9, 1160 (2013).
B.R. Burg and D. Poulikakos: Large-scale integration of single-walled carbon nanotubes and graphene into sensors and devices using dielectrophoresis: A review. J. Mater. Res. 26, 2123 (2011).
S. Bae, H.K. Kim, Y. Lee, X. Xu, J.S. Park, Y. Zheng, J. Balakrishnan, D. Im, T. Lei, Y.I. Song, Y.J. Kim, K.S. Kim, B. Özyilmaz, J.H. Ahn, B.H. Hong, and S. Iijima: 30 inch roll-based production of high-quality graphene films for flexible transparent electrodes. Physics 5, 574 (2010).
S. Choubak, P.L. Levesque, E. Gaufres, M. Biron, P. Desjardins, and R. Martel: Graphene CVD: Interplay between growth and etching on morphology and stacking by hydrogen and oxidizing impurities. J. Phys. Chem. C 118, 21532 (2014).
L. Zhu, X. Zhao, Y. Li, X. Yu, C. Li, and Q. Zhang: High-quality production of graphene by liquid-phase exfoliation of expanded graphite. Mater. Chem. Phys. 137, 984 (2013).
W. Du, X. Jiang, and L. Zhu: From graphite to graphene: Direct liquid-phase exfoliation of graphite to produce single- and few-layered pristine graphene. J. Mater. Chem. A 1, 10592 (2013).
L. Huang, B. Wu, J. Chen, Y. Xue, D. Geng, Y. Guo, G. Yu, and Y. Liu: Gram-scale synthesis of graphene sheets by a catalytic arc-discharge method. Small 9, 1330 (2013).
N. Li, Z. Wang, K. Zhao, Z. Shi, Z. Gu, and S. Xu: Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method. Carbon 48, 255 (2010).
U.K. Parashar, S. Bhandari, R.K. Srivastava, D. Jariwalab, and A. Srivastava: Single step synthesis of graphene nanoribbons by catalyst particle size dependent cutting of multiwalled carbon nanotubes. Nanoscale 3, 3876 (2011).
S. Zhang, Y. Shao, H. Liao, M.H. Engelhard, G. Yin, and Y. Lin: Polyelectrolyte-induced reduction of exfoliated graphite oxide: A facile route to synthesis of soluble graphene nanosheets. ACS Nano 5, 1785 (2011).
B. Yuana, C. Bao, X. Qian, P. Wen, W. Xing, L. Song, and Y. Hu: A facile approach to prepare graphene via solvothermal reduction of graphite oxide. Mater. Res. Bull. 55, 48 (2014).
E. Zanon, A. Mancini, I.G. Pavanello, M. Bertolino, and M. Grosso: A review on thermal exfoliation of graphene oxide. J. Mater. Res. 95, 5343 (2013).
S. You, S.M. Luzan, T. Szabó, and A.V. Talyzin: Effect of synthesis method on solvation and exfoliation of graphite oxide. Carbon 52, 171 (2013).
W.S. Hummers and R.E. Offeman: Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339 (1958).
C.H.A. Wong, O. Jankovský, Z. Sofer, and M. Pumera: Vacuum-assisted microwave reduction/exfoliation of graphite oxide and the influence of precursor graphite oxide. Carbon 77, 508 (2014).
K. Krishnamoorthy, M. Veerapandian, K. Yun, and S.J. Kima: The chemical and structural analysis of graphene oxide with different degrees of oxidation. Carbon 53, 38 (2013).
H. Wang, J.T. Robinson, G. Diankov, and H. Dai: Nanocrystal growth on graphene with various degrees of oxidation. J. Am. Chem. Soc. 132, 3270 (2010).
C. Botas, P. Álvarez, C. Blanco, R. Santamaría, M. Granda, P. Ares, F.R. Reinoso, and R. Menéndez: The effect of the parent graphite on the structure of graphene oxide. Carbon 50, 275 (2012).
D.R. Chowdhury, C. Singh, and A. Paul: Role of graphite precursor and sodium nitrate in graphite oxide synthesis. RSC Adv. 4, 3777 (2014).
D.R. Dreyer, S. Park, C.W. Bielawski, and R.S. Ruoff: The chemistry of graphene oxide. Chem. Soc. Rev. 39, 228 (2010).
H. Wang and Y.H. Hu: Effect of oxygen content on structures of graphite oxides. Ind. Eng. Chem. Res. 50, 6132 (2011).
W. Lee, S. Suzuki, and M. Miyayama: Lithium storage properties of graphene sheets derived from graphite oxides with different oxidation degree. Ceram. Int. 39, S753 (2013).
Y. Zhu, M.D. Stoller, W. Cai, A. Velamakanni, R.D. Piner, D. Chen, and R.S. Ruoff: Exfoliation of graphite oxide in propylene carbonate and thermal reduction of the resulting graphene oxide platelets. ACS Nano 4, 1227 (2010).
L. Qiu, H. Zhang, W. Wang, Y. Chen, and R. Wang: Effects of hydrazine hydrate treatment on the performance of reduced graphene oxide film as counter electrode in dye-sensitized solar cells. Appl. Surf. Sci. 319, 339 (2014).
D.W. Lee, L. De Los Santos V., J.W. Seo, L.L. Felix, A. Bustamante D.J.M. Cole, and C.H.W. Barnes: The structure of graphite Oxide: Investigation of its surface chemical groups. J. Phys. Chem. B 14, 5723 (2010).
H.K. Jeong, Y.P. Lee, R.J.W.E. Lahaye, M.H. Park, K.H. An, I.J. Kim, C.W. Yang, C.Y. Park, R.S. Ruoff, and Y.H. Lee: Evidence of graphitic AB stacking order of graphite oxides. J. Am. Chem. Soc. 130, 1362 (2008).
D.W. Boukhvalov and M.I. Katsnelson: Modeling of graphite oxide. J. Am. Chem. Soc. 130, 10697 (2008).
X. Wang and W. Dou: Preparation of graphite oxide (GO) and the thermal stability of silicone rubber/GO nanocomposites. Thermochim. Acta 529, 25 (2012).
S. Park, J. An, J.R. Potts, A. Velamakanni, S. Murali, and R.S. Ruoff: Hydrazine-reduction of graphite and graphene oxide. Carbon 49, 3019 (2011).
K.N. Kudin, B. Ozbas, H.C. Schniepp, R.K. Prud’homme, I.A. Aksay, and R. Car: Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett. 8, 36 (2008).
O. Akhavan, M. Kalaee, Z.S. Alavi, S.M.A. Ghiasi, and A. Esfandiar: Increasing the antioxidant activity of green tea polyphenols in the presence of iron for the reduction of graphene oxide. Carbon 50, 3015 (2012).
B. Yuan, C. Bao, X. Qian, P. Wen, W. Xing, L. Song, and Y. Hu: A facile approach to prepare graphene via solvothermal reduction of graphite oxide. Mater. Res. Bull. 55, 48 (2014).
D. Yanga, A. Velamakannia, G. Bozoklub, S. Parka, M. Stollera, R.D. Pinera, S. Stankovichc, I. Junga, D.A. Fieldd, C.A. Ventrice, Jr, and R.S. Ruoff: Chemical analysis of graphene oxide films after heat and chemical treatments by x-ray photoelectron and Micro-Raman spectroscopy. Carbon 47, 145 (2009).
H.J. Shin, K.K. Kim, A. Benayad, S.M. Yoon, H.K. Park, I.S. Jung, M.H. Jin, H.K. Jeong, J.M. Kim, J.Y. Choi, and Y.H. Lee: Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance. Adv. Funct. Mater. 19, 1987 (2009).
This work was supported by the Joint Funds of the National Natural Science Foundation of China (Grant No. U1202272).We acknowledge operator Dan zhi Xu for their help in the measurement of Raman spectral. The BET detection work with the help of Yuanfeng Huan professor in Kunming Sino-Platinum Metals Co., Ltd.
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Xu, S., Zhang, Z., Liu, J. et al. Facile preparation of reduced graphene by optimizing oxidation condition and further reducing the exfoliated products. Journal of Materials Research 32, 383–391 (2017). https://doi.org/10.1557/jmr.2016.476