Efficient Route to High-Quality Graphene Materials: Kinetically Controlled Electron Beam Induced Reduction of Graphene Oxide in Aqueous Dispersion
American Journal of Nano Research and Applications
Volume 2, Issue 6-1, December 2014, Pages: 9-18
Received: Nov. 2, 2014;
Accepted: Nov. 4, 2014;
Published: Dec. 23, 2014
Views 4692 Downloads 290
Roman Flyunt, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
Wolfgang Knolle, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
Axel Kahnt, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany
Siegfried Eigler, Department of Chemistry and Pharmacy & Central Institute for New Materials and Processing Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Dr.-Mack Str. 81, 90762 Fürth, Germany
Andriy Lotnyk, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
Tilmann Häupl, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
Andrea Prager, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
Dirk Guldi, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany
Bernd Abel, Leibniz-Institut für Oberflächenmodifizierung (IOM), Permoserstr. 15, 04303 Leipzig, Germany
This work is presenting a highly efficient, cost-efficient and environmentally friendly method for the production of graphene materials (reduced graphene oxide, RedGO) via electron beam (EB) irradiation of aqueous dispersions of graphene oxide (GO). Our strategy here is based on a reduction of GO via EB irradiation under optimally controlled conditions, i.e. dose and dose rate, reducing species, and taking the environmental impact of educt and product into account. The preparation of highly conductive RedGO under these conditions takes only 10-20 minutes at ambient temperature. After our first approach , a somewhat similar study was reported by Jung et al.  for GO dispersions in H2O/EtOH (50:50). However, the latter route , although being similar in spirit, has serious drawbacks for large-scale production because of the formation of acetaldehyde, a very toxic compound, derived from the ethanol in the solvent. The advantages of the present approach compared to  are: (i) the use of water as a solvent with only a small content (0.03 - 2 wt.-%) of 2-PrOH allows the scaling-up, since neither 2-PrOH nor its final product acetone are of high technological or environmental concerns; (ii) a much lower dose is required for GO reduction (about 20 vs. 200 kGy, corresponding to only 1/10 of energy consumed); (iii) the conductivity of RedGO is over 60 times higher. Based on the XPS and conductivity measurements, it was established that the EB treatment is leading also to a more efficient reduction of GO compared to the hydrazine method. The highest conductivity in our systems is identical to the best known value of 3 x 104 S/m for RedGO obtained via HI / acetic acid treatment which takes, however, 40 h at 40 ºC.
Efficient Route to High-Quality Graphene Materials: Kinetically Controlled Electron Beam Induced Reduction of Graphene Oxide in Aqueous Dispersion, American Journal of Nano Research and Applications. Special Issue: Advanced Functional Materials.
Vol. 2, No. 6-1,
2014, pp. 9-18.
R. Flyunt, W. Knolle, B. Abel, B. Rauschenbach, Verfahren zur Herstellung von reduziertem Graphenoxid sowie damit hergestelltes reduziertes Graphenoxid und dessen Verwendung 2012.
J.-M. Jung, C.-H. Jung, M.-S. Oh, I.-T. Hwang, C.-H. Jung, K. Shin, J. Hwang, S.-H. Park, J.-H. Choi, Rapid, facile, and eco-friendly reduction of graphene oxide by electron beam irradiation in an alcohol–water solution, Materials Letters, 126 (2014) 151-153.
K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films, Science, 306 (2004) 666-669.
S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nature Nanotechnology, 4 (2009) 217-224.
O.C. Compton, S.T. Nguyen, Graphene Oxide, Highly Reduced Graphene Oxide, and Graphene: Versatile Building Blocks for Carbon-Based Materials, Small, 6 (2010) 711-723.
D.R. Dreyer, S. Park, C.W. Bielawski, R.S. Ruoff, The chemistry of graphene oxide, Chemical Society Reviews, 39 (2010) 228-240.
H. Kim, A.A. Abdala, C.W. Macosko, Graphene/Polymer Nanocomposites, Macromolecules, 43 (2010) 6515-6530.
C.K. Chua, M. Pumera, Chemical reduction of graphene oxide: a synthetic chemistry viewpoint, Chemical Society Reviews, 43 (2014) 291-312.
S.F. Pei, H.M. Cheng, The reduction of graphene oxide, Carbon, 50 (2012) 3210-3228.
S. Eigler, A. Hirsch, Chemistry with Graphene and graphene oxide - challenges for synthetic chemists, Angewandte Chemie International Edition, (2014).
S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide, Carbon, 45 (2007) 1558-1565.
C. Gomez-Navarro, R.T. Weitz, A.M. Bittner, M. Scolari, A. Mews, M. Burghard, K. Kern, Electronic transport properties of individual chemically reduced graphene oxide sheets, Nano Letters, 7 (2007) 3499-3503.
M.J. Fernandez-Merino, L. Guardia, J.I. Paredes, S. Villar-Rodil, P. Solis-Fernandez, A. Martinez-Alonso, J.M.D. Tascon, Vitamin C Is an Ideal Substitute for Hydrazine in the Reduction of Graphene Oxide Suspensions, Journal of Physical Chemistry C, 114 (2010) 6426-6432.
S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A. Stach, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Graphene-based composite materials, Nature, 442 (2006) 282-286.
X.J. Zhou, J.L. Zhang, H.X. Wu, H.J. Yang, J.Y. Zhang, S.W. Guo, Reducing Graphene Oxide via Hydroxylamine: A Simple and Efficient Route to Graphene, Journal of Physical Chemistry C, 115 (2011) 11957-11961.
G.X. Wang, J. Yang, J. Park, X.L. Gou, B. Wang, H. Liu, J. Yao, Facile synthesis and characterization of graphene nanosheets, Journal of Physical Chemistry C, 112 (2008) 8192-8195.
Y. Si, E.T. Samulski, Synthesis of water soluble graphene, Nano Letters, 8 (2008) 1679-1682.
I.K. Moon, J. Lee, R.S. Ruoff, H. Lee, Reduced graphene oxide by chemical graphitization, Nat Commun, 1 (2010) 73.
W.F. Chen, L.F. Yan, P.R. Bangal, Chemical Reduction of Graphene Oxide to Graphene by Sulfur-Containing Compounds, Journal of Physical Chemistry C, 114 (2010) 19885-19890.
J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang, S. Guo, Reduction of graphene oxide via L-ascorbic acid, Chem Commun, 46 (2010) 1112-1114.
J. Gao, F. Liu, Y.L. Liu, N. Ma, Z.Q. Wang, X. Zhang, Environment-Friendly Method To Produce Graphene That Employs Vitamin C and Amino Acid, Chemistry of Materials, 22 (2010) 2213-2218.
V. Dua, S.P. Surwade, S. Ammu, S.R. Agnihotra, S. Jain, K.E. Roberts, S. Park, R.S. Ruoff, S.K. Manohar, All-Organic Vapor Sensor Using Inkjet-Printed Reduced Graphene Oxide, Angewandte Chemie International Edition, 49 (2010) 2154-2157.
Z.J. Fan, K. Wang, T. Wei, J. Yan, L.P. Song, B. Shao, An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder, Carbon, 48 (2010) 1686-1689.
X. Fan, W. Peng, Y. Li, X. Li, S. Wang, G. Zhang, F. Zhang, Deoxygenation of Exfoliated Graphite Oxide under Alkaline Conditions: A Green Route to Graphene Preparation, Adv Mater, 20 (2008) 4490-4493.
M.J. McAllister, J.L. Li, D.H. Adamson, H.C. Schniepp, A.A. Abdala, J. Liu, M. Herrera-Alonso, D.L. Milius, R. Car, R.K. Prud'homme, I.A. Aksay, Single sheet functionalized graphene by oxidation and thermal expansion of graphite, Chemistry of Materials, 19 (2007) 4396-4404.
P. Steurer, R. Wissert, R. Thomann, R. Mulhaupt, Functionalized Graphenes and Thermoplastic Nanocomposites Based upon Expanded Graphite Oxide, Macromolecular Rapid Communications, 30 (2009) 316-327.
Y. Zhou, Q. Bao, L.A.L. Tang, Y. Zhong, K.P. Loh, Hydrothermal Dehydration for the "Green" Reduction of Exfoliated Graphene Oxide to Graphene and Demonstration of Tunable Optical Limiting Properties, Chemistry of Materials, 21 (2009) 2950-2956.
Y.W. Zhu, M.D. Stoller, W.W. Cai, A. Velamakanni, R.D. Piner, D. Chen, R.S. Ruoff, Exfoliation of Graphite Oxide in Propylene Carbonate and Thermal Reduction of the Resulting Graphene Oxide Platelets, Acs Nano, 4 (2010) 1227-1233.
M. Zhou, Y.L. Wang, Y.M. Zhai, J.F. Zhai, W. Ren, F.A. Wang, S.J. Dong, Controlled Synthesis of Large-Area and Patterned Electrochemically Reduced Graphene Oxide Films, Chem-Eur J, 15 (2009) 6116-6120.
R.S. Sundaram, C. Gomez-Navarro, K. Balasubramanian, M. Burghard, K. Kern, Electrochemical modification of graphene, Adv Mater, 20 (2008) 3050-3053.
G. Williams, P.V. Kamat, Graphene-Semiconductor Nanocomposites: Excited-State Interactions between ZnO Nanoparticles and Graphene Oxide, Langmuir, 25 (2009) 13869-13873.
G. Williams, B. Seger, P.V. Kamat, TiO2-graphene nanocomposites. UV-assisted photocatalytic reduction of graphene oxide, Acs Nano, 2 (2008) 1487-1491.
B. Zhang, L. Li, Z. Wang, S. Xie, Y. Zhang, Y. Shen, M. Yu, B. Deng, Q. Huang, C. Fan, J. Li, Radiation induced reduction: an effective and clean route to synthesize functionalized graphene, Journal of Materials Chemistry, 22 (2012) 7775-7781.
R. Flyunt, W. Knolle, A. Kahnt, A. Prager, A. Lotnyk, J. Malig, D. Guldi, A. Abel, Mechanistic Aspects of the Radiation-Chemical Reduction of Graphene Oxide to Graphene-Like Materials International Journal of Radiation Biology, 90 (2014) 486-494.
S. Eigler, M. Enzelberger-Heim, S. Grimm, P. Hofmann, W. Kroener, A. Geworski, C. Dotzer, M. Rockert, J. Xiao, C. Papp, O. Lytken, H.P. Steinruck, P. Muller, A. Hirsch, Wet Chemical Synthesis of Graphene, Adv Mater, 25 (2013) 3583-3587.
S. Eigler, C. Dotzer, F. Hof, W. Bauer, A. Hirsch, Sulfur Species in Graphene Oxide, Chem-Eur J, 19 (2013) 9490-9496.
G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical-Review of Rate Constants for Reactions of Hydrated Electrons, Hydrogen-Atoms and Hydroxyl Radicals (°OH/°O-) in Aqueous-Solution, Journal of Physical and Chemical Reference Data, 17 (1988) 513-886.
P. Wardman, Reduction Potentials of One-Electron Couples Involving Free-Radicals in Aqueous-Solution, Journal of Physical and Chemical Reference Data, 18 (1989) 1637-1755.
D. Li, M.B. Muller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous dispersions of graphene nanosheets, Nature Nanotechnology, 3 (2008) 101-105.
J.I. Paredes, S. Villar-Rodil, P. Solis-Fernandez, A. Martinez-Alonso, J.M.D. Tascon, Atomic Force and Scanning Tunneling Microscopy Imaging of Graphene Nanosheets Derived from Graphite Oxide, Langmuir, 25 (2009) 5957-5968.
A. Kaniyoor, S. Ramaprabhu, A Raman spectroscopic investigation of graphite oxide derived graphene, Aip Adv, 2 (2012).
S. Eigler, S. Grimm, M. Enzelberger-Heim, P. Muller, A. Hirsch, Graphene oxide: efficiency of reducing agents, Chem Commun, 49 (2013) 7391-7393.
S. Eigler, F. Hof, M. Enzelberger-Heim, S. Grimm, P. Müller, A. Hirsch, Statistical Raman Microscopy and Atomic Force Microscopy on Heterogeneous Graphene Obtained after Reduction of Graphene Oxide, The Journal of Physical Chemistry C, 118 (2014) 7698-7704.
A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys Rev B, 61 (2000) 14095-14107.
M.M. Lucchese, F. Stavale, E.H.M. Ferreira, C. Vilani, M.V.O. Moutinho, R.B. Capaz, C.A. Achete, A. Jorio, Quantifying ion-induced defects and Raman relaxation length in graphene, Carbon, 48 (2010) 1592-1597.
V.H. Pham, H.D. Pham, T.T. Dang, S.H. Hur, E.J. Kim, B.S. Kong, S. Kim, J.S. Chung, Chemical reduction of an aqueous suspension of graphene oxide by nascent hydrogen, Journal of Materials Chemistry, 22 (2012) 10530-10536.
Y.X. Xu, K.X. Sheng, C. Li, G.Q. Shi, Highly conductive chemically converted graphene prepared from mildly oxidized graphene oxide, Journal of Materials Chemistry, 21 (2011) 7376-7380.
I.K. Moon, J. Lee, R.S. Ruoff, H. Lee, Reduced graphene oxide by chemical graphitization, Nat Commun, 1 (2010).
J.C. Meyer, A.K. Geim, M.I. Katsnelson, K.S. Novoselov, D. Obergfell, S. Roth, C. Girit, A. Zettl, On the roughness of single- and bi-layer graphene membranes, Solid State Commun, 143 (2007) 101-109.
Y. Hernandez, V. Nicolosi, M. Lotya, F.M. Blighe, Z.Y. Sun, S. De, I.T. McGovern, B. Holland, M. Byrne, Y.K. Gun'ko, J.J. Boland, P. Niraj, G. Duesberg, S. Krishnamurthy, R. Goodhue, J. Hutchison, V. Scardaci, A.C. Ferrari, J.N. Coleman, High-yield production of graphene by liquid-phase exfoliation of graphite, Nature Nanotechnology, 3 (2008) 563-568.
Y. Geng, S.J. Wang, J.-K. Kim, Preparation of graphite nanoplatelets and graphene sheets, Journal of Colloid and Interface Science, 336 (2009) 592-598.