OJCM  Vol.9 No.2 , April 2019
Synthesis and Fabrication of Graphene and Graphene Oxide: A Review
Abstract: The field of nanotechnology has advanced following the discovery of a two-dimensional material of sp2 hybridized carbon atoms, graphene in 2004 by Geim and Novoselov. Graphene has received so much attention due to its exceptional electronic, thermal, mechanical, and optical properties in addition to its large surface area and single-atom thickness. This has led to the discovery of several techniques to obtain graphene such as chemical exfoliation, chemical vapor deposition (CVD), chemical synthesis etc. However, these techniques are majorly challenged with developing graphene with fewer defects and in large scale; thus, there is an increasing need to produce graphene in large quantities with high quality. Several studies have been carried out to find routes to producing high-quality graphene. This paper focuses majorly on the synthesis and fabrication methods of producing graphene and its derivative, graphene oxide. Characterization techniques to identify graphene such as optical microscopy, scanning electron microscopy (SEM), Raman spectroscopy, scanning probe microscopy (SPM) used to determine number of layers, quality, atomic structures, and defects in graphene is also briefly discussed. This article also covers a short description of graphene applications in transparent electrodes, composites and energy storage devices.
Cite this paper: Adetayo, A. and Runsewe, D. (2019) Synthesis and Fabrication of Graphene and Graphene Oxide: A Review. Open Journal of Composite Materials, 9, 207-229. doi: 10.4236/ojcm.2019.92012.

[1]   Kroto, H.W., Heath, J.R., O’Brien, S.C., Curl, R.F. and Smalley, R.E. (1985) C60: Buckminsterfullerene. Nature, 318, 162-163.

[2]   Iijima, S. (1991) Helical Microtubules of Graphitic Carbon. Nature, 354, 56-58.

[3]   Sharon, M. and Sharon, M. (2015) Graphene: An Introduction to the Fundamentals and Industrial Applications. John Wiley & Sons, Inc., Hoboken.

[4]   Novoselov, K.S., et al. (2004) Electric Field in Atomically Thin Carbon Films. Science, 306, 666-669.

[5]   Das, S., Sudhagar, P., Kang, Y.S. and Choi, W. (2015) Synthesis and Characterization of Graphene. In: Lu, W., Baek, J. and Dai, L., Eds., Carbon Nanomaterials for Advanced Energy Systems, John Wiley & Sons, Inc., Hoboken, NJ, 85-131.

[6]   Choi, W. and Lee, J. (2012) Graphene: Synthesis and Applications. CRC Press, Boca Raton.

[7]   Zhu, Y., et al. (2010) Graphene and Graphene Oxide: Synthesis, Properties, and Applications. Advanced Materials, 22, 3906-3924.

[8]   Bolotin, K.I., et al. (2008) Ultrahigh Electron Mobility in Suspended Graphene. Solid State Communications, 146, 351-355.

[9]   Morozov, S.V., et al. (2008) Giant Intrinsic Carrier Mobilities in Graphene and Its Bilayer. Physical Review Letters, 100, Article ID: 016602.

[10]   Lee, C., Wei, X., Kysar, J.W. and Hone, J. (2008) Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene. Science, 321, 385-388.

[11]   Balandin, A.A., et al. (2008) Superior Thermal Conductivity of Single-Layer Graphene. Nano Letters, 8, 902-907.

[12]   Moser, J., Barreiro, A. and Bachtold, A. (2007) Current-Induced Cleaning of Graphene. Applied Physics Letters, 91, Article ID: 163513.

[13]   Kozlov, S.M., Vines, F. and Gorling, A. (2011) Bandgap Engineering of Graphene by Physisorbed Adsorbates. Advanced Materials, 23, 2638-2643.

[14]   Bunch, J.S., et al. (2008) Impermeable Atomic Membranes from Graphene Sheets. Nano Letters, 8, 2458-2462.

[15]   Xiong, R., et al. (2016) Ultrarobust Transparent Cellulose Nanocrystal-Graphene Membranes with High Electrical Conductivity. Advanced Materials, 28, 1501-1509.

[16]   Eda, G., Fanchini, G. and Chhowalla, M. (2008) Large-Area Ultrathin Films of Reduced Graphene Oxide as a Transparent and Flexible Electronic Material. Nature Nanotechnology, 3, 270-274.

[17]   Gilje, S., Han, S., Wang, M., Wang, K.L. and Kaner, R.B. (2007) A Chemical Route to Graphene for Device Applications. Nano Letters, 7, 3394-3398.

[18]   Li, X., Wang, X., Zhang, L., Lee, S. and Dai, H. (2008) Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors. Science, 319, 1229-1232.

[19]   Yoo, E., Kim, J., Hosono, E., Zhou, H., Kudo, T. and Honma, I. (2008) Large Reversible Li Storage of Graphene Nanosheet Families for Use in Rechargeable Lithium Ion Batteries. Nano Letters, 8, 2277-2282.

[20]   Tung, T.T., et al. (2016) Graphene Oxide-Assisted Liquid Phase Exfoliation of Graphite into Graphene for Highly Conductive Film and Electromechanical Sensors. ACS Applied Materials & Interfaces, 8, 16521-16532.

[21]   Cai, W., Zhu, Y., Li, X., Piner, R.D. and Ruoff, R.S. (2009) Large Area Few-Layer Graphene/Graphite Films as Transparent Thin Conducting Electrodes. Applied Physics Letters, 95, 123115.

[22]   Li, X., et al. (2009) Transfer of Large-Area Graphene Films for High-Performance Transparent Conductive Electrodes. Nano Letters, 9, 4359-4363.

[23]   Stoller, M.D., Park, S., Zhu, Y., An, J. and Ruoff, R.S. (2008) Graphene-Based Ultracapacitors. Nano Letters, 8, 3498-3502.

[24]   Sharma, V., Jain, Y., Kumari, M., Gupta, R., Sharma, S.K. and Sachdev, K. (2017) Synthesis and Characterization of Graphene Oxide (GO) and Reduced Graphene Oxide (rGO) for Gas Sensing Application. Macromolecular Symposia, 376, 1-5.

[25]   Liu, Z., Robinson, J.T., Sun, X. and Dai, H. (2008) PEGylated Nanographene Oxide for Delivery of Water-Insoluble Cancer Drugs. Journal of Amercain Chemical Society, 130, 10876-10877.

[26]   Das, S. and Drucker, J. (2017) Nucleation and Growth of Single Layer Graphene on Electrodeposited Cu by Cold Wall Chemical Vapor Deposition. Nanotechnology, 28, Article ID: 105601.

[27]   Wei, D., Liu, Y., Wang, Y., Zhang, H., Huang, L. and Yu, G. (2009) Synthesis of N-Doped Graphene by Chemical Vapor Deposition and Its Electrical Properties. Nano Letters, 9, 1752-1758.

[28]   Seyller, T., et al. (2008) Epitaxial Graphene: A New Material. Physica Status Solidi, 245, 1436-1446.

[29]   Paredes, J.I., Villar-Rodil, S., Solis-Fernandez, P., Martinez-Alonso, A. and Tascon, J.M.D. (2009) Atomic Force and Scanning Tunneling Microscopy Imaging of Graphene Nanosheets Derived from Graphite Oxide. Langmuir, 25, 5957-5968.

[30]   Park, S. and Ruoff, R.S. (2009) Chemical Methods for the Production of Graphenes. Nature Nanotechnology, 4, 217-224.

[31]   Allen, M.J., Tung, V.C. and Kaner, R.B. (2010) Honeycomb Carbon: A Review of Graphene. Chemical Reviews, 110, 132-145.

[32]   Viculis, L.M., Mack, J.J. and Kaner, R.B. (2003) A Chemical Route to Carbon Nanoscrolls. Science, 299, 1361.

[33]   Rollings, E., et al. (2006) Synthesis and Characterization of Atomically Thin Graphite Films on a Silicon Carbide Substrate. Journal of Physics and Chemistry of Solids, 67, 2172-2177.

[34]   Reina, A., et al. (2009) Large Area, Few-Layer Graphene Films on Arbitrary Substrates by Chemical Vapor Deposition. Nano Letters, 9, 30-35.

[35]   Liu, N., Luo, F., Wu, H., Liu, Y., Zhang, C. and Chen, J. (2008) One-Step Ionic-Liquid-Assisted Electrochemical Synthesis of Ionic-Liquid-Functionalized Graphene Sheets Directly from Graphite. Advanced Functional Materials, 18, 1518-1525.

[36]   Xin, G., Hwang, W., Kim, N., Cho, S.M. and Chae, H. (2010) A Graphene Sheet Exfoliated with Microwave Irradiation and Interlinked by Carbon Nanotubes for High-Performance Transparent Flexible Electrodes. Nanotechnology, 21, Article ID: 405201.

[37]   Jiao, L., Wang, X., Diankov, G., Wang, H. and Dai, H. (2010) Facile Synthesis of High-Quality Graphene Nanoribbons. Nature Nanotechnology, 5, 321-325.

[38]   Kosynkin, D.V., et al. (2009) Longitudinal Unzipping of Carbon Nanotubes to Form Graphene Nanoribbons. Nature, 458, 872-876.

[39]   Jiao, L., Zhang, L., Wang, X., Diankov, G. and Dai, H. (2009) Narrow Graphene Nanoribbons from Carbon Nanotubes. Nature, 458, 877-880.

[40]   Ebbesen, T.W. and Hiura, H. (1995) Graphene in 3-Dimensions: Towards Graphite origami. Advanced Materials, 7, 582-586.

[41]   Lu, X., Yu, M., Huang, H. and Ruoff, R.S. (1999) Tailoring Graphite with the Goal of Achieving Single Sheets. Nanotechnology, 10, 269-272.

[42]   Lang, B. (1975) A LEED Study of the Deposition of Carbon on Platinum Crystal Surfaces. Surface Science, 53, 317-329.

[43]   Liang, X., et al. (2009) Electrostatic Force Assisted Exfoliation of Prepatterned Few-Layer Graphenes into Device Sites. Nano Letters, 9, 467-472.

[44]   Ci, L., et al. (2009) Graphene Shape Control by Multistage Cutting and Transfer, Advanced Materials, 21, 4487-4491.

[45]   Rao, C.N.R. and Sood, A.K. (2013) Graphene: Synthesis, Properties, and Phenomena. John Wiley & Sons, Inc., Weinheim, Germany.

[46]   Viculis, L.M., Mack, J.J., Mayer, O.M., Hahn, H.T. and Kaner, R.B. (2005) Intercalation and Exfoliation Routes to Graphite Nanoplatelets. Journal of Materials Chemitry, 15, 974-978.

[47]   Bhuyan, M.S.A., Uddin, M.N., Islam, M.M., Bipasha, F.A. and Hossain, S.S. (2016) Synthesis of Graphene. International Nano Letters, 6, 65-83.

[48]   Valles, C., et al. (2008) Solutions of Negatively Charged Graphene Sheets and Ribbons. Journal of the American Chemical Society, 130, 15802-15804.

[49]   Kamali, A.R. and Fray, D.J. (2013) Molten Salt Corrosion of Graphite as a Possible Way to Make Carbon Nanostructures. Carbon, 56, 121-131.

[50]   Pu, N.-W., Wang, C.-A., Sung, Y., Liu, Y.-M. and Ger, M.-D. (2009) Production of Few-Layer Graphene by Supercritical CO2 Exfoliation of Graphite. Materials Letters, 63, 1987-1989.

[51]   Safavi, A., Tohidi, M., Mahyari, F.A. and Shahbaazi, H. (2012) One-Pot Synthesis of Large Scale Graphene Nanosheets from Graphite-Liquid Crystal Composite via Thermal Treatment. Journal of Materials Chemistry, 22, 3825-3831.

[52]   Dhakate, S.R., et al. (2011) An Approach to Produce Single and Double Layer Graphene from Re-Exfoliation of Expanded Graphite. Carbon, 49, 1946-1954.

[53]   Staudenmaier, L. (1898) Verfahren zur Darstellung der Graphitsaure. Berichte der Deutschen Chemischen Gesellschaft, 31, 1481-1487.

[54]   Hummers, W.S. and Offeman, R.E. (1958) Preparation of Graphitic Oxide. Journal of the American Chemical Society, 80, 1339.

[55]   Eda, G., Lin, Y.-Y., Miller, S., Chen, C.-W., Su, W.-F. and Chhowalla, M. (2008) Transparent and Conducting Electrodes for Organic Electronics from Reduced Graphene Oxide. Applied Physics Letters, 92, Article ID: 233305.

[56]   Shin, H.-J., et al. (2009) Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance. Advanced Functional Materials, 19, 1987-1992.

[57]   Zhou, X., Zhang, J., Wu, H., Yang, H., Zhang, J. and Guo, S. (2011) Reducing Graphene Oxide via Hydroxylamine: A Simple and Efficient Route to Graphene. The Journal of Physical Chemistry C, 115, 11957-11961.

[58]   Bourlinos, A.B., Gournis, D., Petridis, D., Szabó, T., Szeri, A. and Dékány, I. (2003) Graphite Oxide: Chemical Reduction to Graphite and Surface Modification with Primary Aliphatic Amines and Amino Acids. Langmuir, 19, 6050-6055.

[59]   Zhang, J., Yang, H., Shen, G., Cheng, P., Zhang, J. and Guo, S. (2010) Reduction of Graphene Oxide via L-Ascorbic Acid. Chemical Communications, 46, 1112-1114.

[60]   Goncalves, G., Marques, P.A.A.P., Granadeiro, C.M., Nogueira, H.I.S., Singh, M.K. and Grácio, J. (2009) Surface Modification of Graphene Nanosheets with Gold Nanoparticles: The Role of Oxygen Moieties at Graphene Surface on Gold Nucleation and Growth. Chemistry of Materials, 21, 4796-4802.

[61]   Marcano, D.C., et al., (2010) Improved Synthesis of Graphene Oxide. ACS Nano, 4, 4806-4814.

[62]   Zhang, L., Li, Y., Zhang, L., Li, D.W., Karpuzov, D. and Long, Y.T. (2011) Electrocatalytic Oxidation of NADH on Graphene Oxide and Reduced Graphene Oxide Modified Screen-Printed Electrode. International Journal of Electrochemical Science, 6, 819-829.

[63]   Larciprete, R., Fabris, S., Sun, T., Lacovig, P., Baraldi, A. and Lizzit, S. (2011) Dual Path Mechanism in the Thermal Reduction of Graphene Oxide. Journal of the American Chemical Society, 133, 17315-17321.

[64]   Liao, K.H., Mittal, A., Bose, S., Leighton, C., Mkhoyan, K.A. and MacOsko, C.W. (2011) Aqueous Only Route toward Graphene from Graphite Oxide. ACS Nano, 5, 1253-1258.

[65]   An, Wong, C.H., Ambrosi, A. and Pumera, M. (2012) Thermally Reduced Graphenes Exhibiting a Close Relationship to Amorphous Carbon. Nanoscale, 4, 4972-4977.

[66]   Viinikanoja, A., Wang, Z., Kauppila, J. and Kvarnstrom, C. (2012) Electrochemical Reduction of Graphene Oxide and Its in Situ Spectroelectrochemical Characterization. Physical Chemistry Chemical Physics, 14, 14003-14009,.

[67]   Shao, Y., Wang, J., Engelhard, M., Wang, C. and Lin, Y. (2010) Facile and Controllable Electrochemical Reduction of Graphene Oxide and Its Applications. Journal of Materials Chemistry, 20, 743-748.

[68]   Stroyuk, A.L., et al. (2012) Photochemical Reduction of Graphene Oxide in Colloidal Solution. Theoretical and Experimental Chemistry, 48, 2-13.

[69]   Krishnamoorthy, K., Veerapandian, M., Kim, G.-S. and Jae Kim, S. (2012) A One Step Hydrothermal Approach for the Improved Synthesis of Graphene Nanosheets. Current Nanoscience, 8, 934-938.

[70]   Dai, Z., Wang, K., Li, L. and Zhang, T. (2013) Synthesis of Nitrogen-Doped Graphene with Microwave. International Journal of Electrochemical Science, 8, 9384-9389.

[71]   Chua, C.K. and Pumera, M. (2014) Chemical Reduction of Graphene Oxide: A Synthetic Chemistry Viewpoint. Chemical Society Reviews, 43, 291-312.

[72]   Jimenez-Cervantes, E., López-Barroso, J., Martínez-Hernández, A.L. and Velasco-Santos, C. (2016) Graphene-Based Materials Functionalization with Natural Polymeric Biomolecules. Recent Advances in Graphene Research, 257-298.

[73]   Choucair, M., Thordarson, P. and Stride, J.A. (2009) Gram-Scale Production of Graphene Based on Solvothermal Synthesis and Sonication. Nature Nanotechnology, 4, 30-33.

[74]   Van Bommel, A.J., Crombeen, J.E. and Van Tooren A. (1975) LEED and Auger Electron Observations of the SiC(0001) Surface. Surface Science, 48, 463-472.

[75]   Berger, C., et al. (2004) Ultrathin Epitaxial Graphite: 2D Electron Gas Properties and a Route toward Graphene-Based Nanoelectronics. The Journal of Physical Chemistry B, 108, 19912-19916.

[76]   De Heer, W.A., et al. (2007) Epitaxial Graphene. Solid State Communications, 143, 92-100.

[77]   Juang, Z.-Y., et al. (2009) Synthesis of Graphene on Silicon Carbide Substrates at Low Temperature. Carbon, 47, 2026-2031.

[78]   Guo, S., Dong, S. and Wang, E. (2010) Three-Dimensional Pt-On-Pd Bimetallic Nanodendrites Supported on Graphene Nanosheet: Facile Synthesis and Used as an Advanced Nanoelectrocatalyst for Methanol Oxidation. ACS Nano, 4, 547-555.

[79]   Sutter, P.W., Flege, J.-I. and Sutter, E.A. (2008) Epitaxial Graphene on Ruthenium. Nature Materials, 7, 406-411.

[80]   Coraux, J., N’Diaye, A.T., Busse, C. and Michely, T. (2008) Structural Coherency of Graphene on Ir(111). Nano Letters, 8, 565-570.

[81]   Karu, A.E. and Beer, M. (1966) Pyrolytic Formation of Highly Crystalline Graphite Films. Journal of Applied Physics, 37, 2179-2181.

[82]   Perdereau, J. and Rhead, G.E. (1971) LEED Studies of Adsorption on Vicinal Copper Surfaces. Surface Science, 24, 555-571.

[83]   Eizenberg, M. and Blakely, J.M. (1979) Carbon Monolayer Phase Condensation on Ni(111). Surface Science, 82, 228-236.

[84]   Somani, P.R., Somani, S.P. and Umeno, M. (2006) Planer Nano-Graphenes from Camphor by CVD. Chemical Physics Letters, 430, 56-59.

[85]   Obraztsov, A.N., Obraztsova, E.A., Tyurnina, A.V. and Zolotukhin, A.A. (2007) Chemical Vapor Deposition of Thin Graphite Films of Nanometer Thickness. Carbon, 45, 2017-2021.

[86]   Li, X., et al. (2009) Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils. Science, 324, 1312-1314.

[87]   Lee, J., Zheng, X., Roberts, R.C. and Feng, P.X.L. (2015) Scanning Electron Microscopy Characterization of Structural Features in Suspended and Non-Suspended Graphene by Customized CVD Growth. Diamond and Related Materials, 54, 64-73.

[88]   Shang, N.G., et al. (2008) Catalyst-Free Efficient Growth, Orientation and Biosensing Properties of Multilayer Graphene Nanoflake Films with Sharp Edge Planes. Advanced Functional Materials, 18, 3506-3514.

[89]   Zhu, M., et al. (2007) A Mechanism for Carbon Nanosheet Formation. Carbon, 45, 2229-2234.

[90]   Obraztsov, A.N., Zolotukhin, A.A., Ustinov, A.O., Volkov, A.P., Svirko, Y. and Jefimovs, K. (2003) DC Discharge Plasma Studies for Nanostructured Carbon CVD. Diamond and Related Materials, 12, 917-920.

[91]   Wang, J.J., et al. (2004) Free-Standing Subnanometer Graphite Sheets. Applied Physics Letters, 85, 1265-1267.

[92]   Jǎsek, O., Synek, P., Zajíckováa, L., Elíǎs, M. and Kudrle, V. (2010) Synthesis of carbon Nanostructures by Plasma Enhanced Chemical Vapour Deposition at Atmospheric Pressure. Journal of Electrical Engineering, 61, 311-313.

[93]   Yuan, G.D., et al. (2009) Graphene Sheets via Microwave Chemical Vapor Deposition. Chemical Physics Letters, 467, 361-364.

[94]   Lee, D.H., Lee, J.A., Lee, W.J., Choi, D.S., Lee, W.J. and Kim, S.O. (2010) Facile Fabrication and Field Emission of Metal-Particle-Decorated Vertical N-Doped Carbon Nanotube/Graphene Hybrid Films. The Journal of Physical Chemistry C, 114, 21184-21189.

[95]   Subrahmanyam, K.S., Panchakarla, L.S., Govindaraj, A. and Rao, C.N.R. (2009) Simple Method of Preparing Graphene Flakes by an Arc-Discharge Method. The Journal of Physical Chemistry C, 113, 4257-4259.

[96]   Subrahmanyam, K.S., Vivekchand, S.R.C., Govindaraj, A. and Rao, C.N.R. (2008) A Study of Graphenes Prepared by Different Methods: Characterization, Properties and Solubilization. Journal of Materials Chemistry, 18, 1517-1523.

[97]   Panchakarla, L.S., et al. (2009) Synthesis, Structure, and Properties of Boron- and Nitrogen-Doped Graphene. Advanced Materials, 21, 4726-4730.

[98]   Ci, L., et al. (2010) Atomic Layers of Hybridized Boron Nitride and Graphene Domains. Nature Materials, 9, 430-435.

[99]   Park, J.S., Reina, A., Saito, R., Kong, J., Dresselhaus, G. and Dresselhaus, M.S. (2009) G’ Band Raman Spectra of Single, Double and Triple Layer Graphene. Carbon, 47, 1303-1310.

[100]   Novoselov, K.S., et al. (2005) Two-Dimensional Atomic Crystals. Proceedings of the National Academy of Sciences, 102, 10451-10453.

[101]   Luican, A., Li, G. and Andrei, E.Y. (2009) Scanning Tunneling Microscopy and Spectroscopy of Graphene Layers on Graphite. Solid State Communications, 149, 1151-1156.

[102]   Zhang, Y.J., Small, P., Pontius, W.V. and Kim, P. (2005) Fabrication and Electric-Field-Dependent Transport Measurements of Mesoscopic Graphite Devices, Applied Physics Letters, 86, Article ID: 073104.

[103]   Huang, P.Y., et al. (2011) Grains and Grain Boundaries in Single-Layer Graphene Atomic Patchwork Quilts. Nature, 469, 389-392.

[104]   Wang, Y.Y., et al. (2008) Raman Studies of Monolayer Graphene: The Substrate Effect. The Journal of Physical Chemistry C, 112, 10637-10640.

[105]   Chandrasekhar, P. (2018) Conducting Polymers, Fundamentals and Applications. Cham: Springer International Publishing, Boston.

[106]   Ding, X., Liu, H. and Fan, Y. (2015) Graphene-Based Materials in Regenerative Medicine. Advanced Healthcare Materials, 4, 1451-1468.

[107]   Torrisi, F., et al. (2012) Inkjet-Printed Graphene Electronics. ACS Nano, 6, 2992-3006.

[108]   Sun, Y., Wu, Q. and Shi, G. (2011) Graphene Based New Energy Materials. Energy and Environmental Science, 4, 1113-1132.