Research progress in methods and mechanisms of chemical reduction graphene oxide
GUO Jian-qiang1,2,3, LI Jiong-li1,2,3, LIANG Jia-feng1,2, LI Yue1,2, ZHU Qiao-si1,2, WANG Xu-dong1,2,3
1. AECC Beijing Institute of Aeronautical Materials, Beijing 100095, China;
2. Beijing Institute of Graphene Technology, Beijing 100094, China;
3. Beijing Engineering Research Centre of Graphene Application, Beijing 100095, China
Abstract：The mass production of graphene sheets is a prerequisite for exploiting the applications of graphene. A major focus of experimental research has been concentrated on the development of effective approaches to produce well-defined graphene in large scale. Due to its high yield and cost efficiency, chemical reduction of graphene oxide has been proofed to be one of the most feasible approaches to achieve this goal. Graphene consists almost entirely of sp2 hybridized carbon atoms, while graphene oxide additionally contains sp3 regions, oxygen functional groups and structural defects. The fundamental understanding of the mechanism of chemical reduction of graphene oxide is a key issue when preparing graphene materials via graphene oxide precursor. Although dozens of methods have been exploited to facilitate the chemical reduction of graphene, only few studies were focused on the reduction mechanism.The chemical reduction strategies of graphene oxide, and as well as their mechanisms were reviewed in this paper. It was suggested that the core issue of the reduction is how to clarify the removal of hydroxyl groups and the simultaneous restoration of a conjugated structure.
郭建强, 李炯利, 梁佳丰, 李岳, 朱巧思, 王旭东. 氧化石墨烯的化学还原方法与机理研究进展[J]. 材料工程, 2020, 48(7): 24-35.
GUO Jian-qiang, LI Jiong-li, LIANG Jia-feng, LI Yue, ZHU Qiao-si, WANG Xu-dong. Research progress in methods and mechanisms of chemical reduction graphene oxide. Journal of Materials Engineering, 2020, 48(7): 24-35.
[1] NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696):666-669.
[2] AVOURIS P, DIMITRAKOPOULOS C. Graphene:synthesis and applications[J]. Materials Today, 2012, 15(3):86-97.
[3] MOHAN V B, LAU K T, HUI D, et al. Graphene-based materials and their composites:a review on production, applications and product limitations[J]. Composites:Part B, 2018, 142:200-220.
[4] YANG Z F, TIAN J R, YIN Z F, et al. Carbon nanotube-and graphene-based nanomaterials and applications in high-voltage supercapacitor:a review[J]. Carbon, 2019, 141:467-480.
[5] GEIM A K, NOVOSELOV K S. The rise of graphene[J]. Nature Materials, 2007, 6(3):183-191.
[6] SUN D J, LUO Y F, DEBLIQUY M, et al. Graphene-enhanced metal oxide gas sensors at room temperature:a review[J]. Beilstein Journal of Nanotechnology, 2018, 9:2832-2844.
[7] BEITOLLAHI H, SAFAEI M, TAJIK S. Application of graphene and graphene oxide for modification of electrochemical sensors and biosensors:a review[J]. International Journal of Nano Dimension, 2019, 10(2):125-140.
[8] LERF A, HE H, FORSTER M, et al. Structure of graphite oxide revisited[J]. The Journal of Physical Chemistry:B, 1998, 102(23):4477-4482.
[9] CHUA C K, PUMERA M. Chemical reduction of graphene oxide:a synthetic chemistry viewpoint[J]. Chemical Society Reviews, 2014, 43(1):291-312.
[10] DE SILVA K K H, HUANG H H, JOSHI R K, et al. Chemical reduction of graphene oxide using green reductants[J]. Carbon, 2017, 119:190-199.
[11] PEI S F, CHENG H M. The reduction of graphene oxide[J]. Carbon, 2012, 50(9):3210-3228.
[12] BRODIE B C. On the atomic weight of graphite[M]. London:Philosophical Transactions of the Royal Society of London, 1859:249-259.
[13] STAUDENMAIER L. Method for the preparation of graphitic acid[J]. Ber Dtsch Chem Ges, 1898, 31:1481-1487.
[14] HOFMANN U, KÖNIG E. Untersuchungen über graphitoxyd[J]. Zeitschrift für Anorganische und Allgemeine Chemie, 1937, 234(4):311-336.
[15] HUMMERS Jr W S, OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society, 1958, 80(6):1334-1339.
[16] MARCANO D C, KOSYNKIN D V, BERLIN J M, et al. Improved synthesis of graphene oxide[J]. ACS Nano, 2010, 4(8):4806-4814.
[17] DIMIEV A M, TOUR J M. Mechanism of graphene oxide formation[J]. ACS Nano, 2014, 8(3):3060-3068.
[18] DIMIEV A, KOSYNKIN D V, ALEMANY L B, et al. Pristine graphite oxide[J]. Journal of the American Chemical Society, 2012, 134(5):2815-2822.
[19] KANG J H, KIM T, CHOI J, et al. Hidden second oxidation step of Hummers method[J]. Chemistry of Materials, 2016, 28(3):756-764.
[20] KRISHNAMOORTHY K, VEERAPANDIAN M, YUN K, et al. The chemical and structural analysis of graphene oxide with different degrees of oxidation[J].Carbon,2013,53:38-49.
[21] SZABÓ T, BERKESI O, FORGÓ P, et al. Evolution of surface functional groups in a series of progressively oxidized graphite oxides[J]. Chemistry of Materials, 2006, 18(11):2740-2749.
[22] VOIRY D, YANG J, KUPFERBERG J, et al. High-quality graphene via microwave reduction of solution-exfoliated graphene oxide[J]. Science, 2016, 353(6306):1413-1416.
[23] GÓMEZ-NAVARRO C, MEYER J C, SUNDARAM R S, et al. Atomic structure of reduced graphene oxide[J]. Nano Letters, 2010, 10(4):1144-1148.
[24] GAO W, ALEMANY L B, CI L, et al. New insights into the structure and reduction of graphite oxide[J]. Nature Chemistry, 2009, 1(5):403.
[25] ERICKSON K, ERNI R, LEE Z, et al. Determination of the local chemical structure of graphene oxide and reduced graphene oxide[J]. Advanced Materials, 2010, 22(40):4467-4472.
[26] ZHU Y W, MURALI S, CAI W W, et al. Graphene and graphene oxide:synthesis, properties, and applications[J]. Advanced Materials, 2010, 22(35):3906-3924.
[27] MAHANTA N K, ABRAMSON A R. Thermal conductivity of graphene and graphene oxide nanoplatelets[C]//13th InterSociety Conference on Thermal and Thermomechanical Phenomena in Electronic Systems, 2012:1-6.
[28] FEHER F. Handbook of preparative inorganic chemistry[M]. NY:Academic Press, 1963:418.
[29] STANKOVICH S, DIKIN D A, PINER R D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007, 45(7):1558-1565.
[30] LI D, MVLLER M B, GILJE S, et al. Processable aqueous dispersions of graphene nanosheets[J]. Nature Nanotechnology, 2008, 3:101.
[31] GAO X F, JANG J, NAGASE S. Hydrazine and thermal reduction of graphene oxide:reaction mechanisms, product structures, and reaction design[J]. Journal of Physical Chemistry:C, 2010, 114(2):832-842.
[32] STANKOVICH S, DIKIN D A, DOMMETT G H, et al. Graphene-based composite materials[J]. Nature, 2006, 442(7100):282.
[33] YUN J M, YEO J S, KIM J, et al. Solution-processable reduced graphene oxide as a novel alternative to PEDOT:PSS hole transport layers for highly efficient and stable polymer solar cells[J]. Advanced Materials, 2011, 23(42):4923-4928.
[34] FAN X B, PENG W C, LI Y, et al. Deoxygenation of exfoliated graphite oxide under alkaline conditions:a green route to graphene preparation[J]. Advanced Materials, 2008, 20(23):4490-4493.
[35] ZHOU X, ZHANG J, WU H, et al. Reducing graphene oxide via hydroxylamine:a simple and efficient route to graphene[J]. Journal of Physical Chemistry:C, 2011, 115(24):11957-11961.
[36] LIU S, TIAN J, WANG L, et al. A method for the production of reduced graphene oxide using benzylamine as a reducing and stabilizing agent and its subsequent decoration with Ag nanoparticles for enzymeless hydrogen peroxide detection[J]. Carbon, 2011, 49(10):3158-3164.
[37] AMARNATH C A, HONG C E, KIM N H, et al. Efficient synthesis of graphene sheets using pyrrole as a reducing agent[J]. Carbon, 2011, 49(11):3497-3502.
[38] CHEN Y, ZHANG X, YU P, et al. Stable dispersions of graphene and highly conducting graphene films:a new approach to creating colloids of graphene monolayers[J]. Chemical Communications, 2009,30:4527-4529.
[39] LEI Z, LU L, ZHAO X. The electrocapacitive properties of graphene oxide reduced by urea[J]. Energy & Environmental Science, 2012, 5(4):6391-6399.
[40] SU P, GUO H L, TIAN L, et al. An efficient method of producing stable graphene suspensions with less toxicity using dimethyl ketoxime[J]. Carbon, 2012, 50(15):5351-5358.
[41] SHEN X, JIANG L, JI Z, et al. Stable aqueous dispersions of graphene prepared with hexamethylenetetramine as a reductant[J]. Journal of Colloid and Interface Science, 2011, 354(2):493-497.
[42] CHE J, SHEN L, XIAO Y. A new approach to fabricate graphene nanosheets in organic medium:combination of reduction and dispersion[J]. Journal of Materials Chemistry, 2010, 20(9):1722-1727.
[43] GAO J, LIU F, LIU Y L, et al. Environment-friendly method to produce graphene that employs vitamin C and amino acid[J]. Chemistry of Materials, 2010, 22(7):2213-2218.
[44] CHEN D, LI L, GUO L. An environment-friendly preparation of reduced graphene oxide nanosheets via amino acid[J]. Nanotechnology, 2011, 22(32):325601.
[45] BOSE S, KUILA T, MISHRA A K, et al. Dual role of glycine as a chemical functionalizer and a reducing agent in the preparation of graphene:an environmentally friendly method[J]. Journal of Materials Chemistry, 2012, 22(19):9696-9703.
[46] MA J, WANG X, LIU Y, et al. Reduction of graphene oxide with l-lysine to prepare reduced graphene oxide stabilized with polysaccharide polyelectrolyte[J]. Journal of Materials Chemistry:A, 2013, 1(6):2192-2201.
[47] TRAN D N H, KABIRI S, LOSIC D. A green approach for the reduction of graphene oxide nanosheets using non-aromatic amino acids[J]. Carbon, 2014, 76:193-202.
[48] WANG J, SALIHI E C, ŠILLER L. Green reduction of graphene oxide using alanine[J]. Materials Science and Engineering:C, 2017, 72:1-6.
[49] PHAM T A, KIM J S, KIM J S, et al. One-step reduction of graphene oxide with L-glutathione[J]. Colloids and Surfaces:A, 2011, 384(1/3):543-548.
[50] XU L Q, YANG W J, NEOH K G, et al. Dopamine-induced reduction and functionalization of graphene oxide nanosheets[J]. Macromolecules, 2010, 43(20):8336-8339.
[51] MOON I K, LEE J, RUOFF R S, et al. Reduced graphene oxide by chemical graphitization[J]. Nature Communications, 2010, 1:6.
[52] PEI S, ZHAO J, DU J, et al. Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids[J]. Carbon, 2010, 48(15):4466-4474.
[53] CHEN W, YAN L, BANGAL P R. Chemical reduction of graphene oxide to graphene by sulfur-containing compounds[J]. Journal of Physical Chemistry:C, 2010, 114(47):19885-19890.
[54] SU Y, GAO X, ZHAO J. Reaction mechanisms of graphene oxide chemical reduction by sulfur-containing compounds[J]. Carbon, 2014, 67:146-155.
[55] NAKAGAWA K, MINAMI K. Reduction of organic compounds with thiourea dioxide Ⅰ reduction of ketones to secondary alcohols[J]. Tetrahedron Letters, 1972, 13(5):343-346.
[56] CHUA C K, AMBROSI A, PUMERA M. Graphene oxide reduction by standard industrial reducing agent:thiourea dioxide[J]. Journal of Materials Chemistry, 2012, 22:11054-11061.
[57] WANG Y, SUN L, FUGETSU B. Thiourea dioxide as a green reductant for the mass production of solution-based graphene[J]. Bulletin of the Chemical Society of Japan, 2012, 85(12):1339-1344.
[58] MA Q, SONG J, JIN C, et al. A rapid and easy approach for the reduction of graphene oxide by formamidinesulfinic acid[J]. Carbon, 2013, 54:36-41.
[59] CHUA C K, PUMERA M. Selective removal of hydroxyl groups from graphene oxide[J]. Chemistry-A European Journal, 2013, 19(6):2005-2011.
[60] MELLON M, MANGADLAO J, ADVINCULA R, et al. The pH dependent reactions of graphene oxide with small molecule thiols[J]. RSC Advances, 2018, 8(33):18388-18395.
[61] DREYER D R, MURALI S, ZHU Y, et al. Reduction of graphite oxide using alcohols[J]. Journal of Materials Chemistry, 2011, 21(10):3443-3447.
[62] ZHANG J, YANG H, SHEN G, et al. Reduction of graphene oxide via L-ascorbic acid[J]. Chemical Communications, 2010, 46(7):1112-1114.
[63] FERNANDEZ-MERINO M J, GUARDIA L, PAREDES J I, et al. Vitamin C is an ideal substitute for hydrazine in the reduction of graphene oxide suspensions[J]. Journal of Physical Chemistry:C, 2010, 114(14):6426-6432.
[64] ZHU C, GUO S, FANG Y, et al. Reducing sugar:new functional molecules for the green synthesis of graphene nanosheets[J]. ACS Nano, 2010, 4(4):2429-2437.
[65] LI B, JIN X, LIN J, et al. Green reduction of graphene oxide by sugarcane bagasse extract and its application for the removal of cadmium in aqueous solution[J]. Journal of Cleaner Production, 2018, 189:128-134.
[66] WANG G, YANG J, PARK J, et al. Facile synthesis and characterization of graphene nanosheets[J]. The Journal of Physical Chemistry:C, 2008, 112(22):8192-8195.
[67] LI J, XIAO G, CHEN C, et al. Superior dispersions of reduced graphene oxide synthesized by using gallic acid as a reductant and stabilizer[J]. Journal of Materials Chemistry:A, 2013, 1(4):1481-1487.
[68] WANG Y, SHI Z, YIN J. Facile synthesis of soluble graphene via a green reduction of graphene oxide in tea solution and its biocomposites[J]. ACS Applied Materials & Interfaces, 2011, 3(4):1127-1133.
[69] SHIN H J, KIM K K, BENAYAD A, et al. Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance[J]. Advanced Functional Materials, 2009, 19(12):1987-1992.
[70] SI Y, SAMULSKI E T. Synthesis of water soluble graphene[J]. Nano Letters, 2008, 8(6):1679-1682.
[71] MUSZYNSKI R, SEGER B, KAMAT P V. Decorating graphene sheets with gold nanoparticles[J]. Journal of Physical Chemistry:C, 2008, 112(14):5263-5266.
[72] GUEX L G, SACCHI B, PEUVOT K F, et al. Experimental review:chemical reduction of graphene oxide (GO) to reduced graphene oxide (rGO) by aqueous chemistry[J]. Nanoscale, 2017, 9(27):9562-9571.
[73] CHUA C K, PUMERA M. Reduction of graphene oxide with substituted borohydrides[J]. Journal of Materials Chemistry:A, 2013, 1(5):1892-1898.
[74] PHAM V H, HUR S H, KIM E J, et al. Highly efficient reduction of graphene oxide using ammonia borane[J]. Chemical Communications, 2013, 49(59):6665-6667.
[75] AMBROSI A, CHUA C K, BONANNI A, et al. Lithium aluminum hydride as reducing agent for chemically reduced graphene oxides[J]. Chemistry of Materials, 2012, 24(12):2292-2298.
[76] KANG S S, ZHUANG J Y, KANG S H, et al. Synthesis of high-quality graphene with enhanced electrochemical properties by two-step reduction method[J]. Ceramics International, 2019,45(18):23954-23965.
[77] FAN Z, WANG K, WEI T, et al. An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder[J]. Carbon, 2010, 48(5):1686-1689.
[78] FAN Z J, KAI W, YAN J, et al. Facile synthesis of graphene nanosheets via Fe reduction of exfoliated graphite oxide[J]. ACS Nano, 2010, 5(1):191-198.
[79] LIU P, HUANG Y, WANG L. A facile synthesis of reduced graphene oxide with Zn powder under acidic condition[J]. Materials Letters, 2013, 91:125-128.
[80] DEY R S, HAJRA S, SAHU R K, et al. A rapid room temperature chemical route for the synthesis of graphene:metal-mediated reduction of graphene oxide[J]. Chemical Communications, 2012, 48(12):1787-1789.
[81] KUMAR N A, GAMBARELLI S, DUCLAIROIR F, et al. Synthesis of high quality reduced graphene oxide nanosheets free of paramagnetic metallic impurities[J]. Journal of Materials Chemistry:A, 2013, 1(8):2789-2794.
[82] PHAM V H, PHAM H D, DANG T T, et al. Chemical reduction of an aqueous suspension of graphene oxide by nascent hydrogen[J]. Journal of Materials Chemistry, 2012, 22(21):10530-10536.
[83] LIU Y, LI Y, ZHONG M, et al. A green and ultrafast approach to the synthesis of scalable graphene nanosheets with Zn powder for electrochemical energy storage[J]. Journal of Materials Chemistry, 2011, 21(39):15449-15455.
[84] FENG H, CHENG R, ZHAO X, et al. A low-temperature method to produce highly reduced graphene oxide[J]. Nature Communications, 2013, 4:1539.
[85] ENG A Y S, SOFER Z, HUBER Š, et al. Hydrogenated graphenes by Birch reduction:influence of electron and proton sources on hydrogenation efficiency, magnetism, and electrochemistry[J]. Chemistry-A European Journal, 2015, 21(47):16828-16838.
[86] SALAS E C, SUN Z, LÜTTGE A, et al. Reduction of graphene oxide via bacterial respiration[J]. ACS Nano, 2010, 4(8):4852-4856.
[87] AKHAVAN O, GHADERI E. Escherichia coli bacteria reduce graphene oxide to bactericidal graphene in a self-limiting manner[J]. Carbon, 2012, 50(5):1853-1860.
[88] KHANRA P, KUILA T, KIM N H, et al. Simultaneous bio-functionalization and reduction of graphene oxide by baker's yeast[J]. Chemical Engineering Journal, 2012, 183:526-533.
[89] LIU J, FU S, YUAN B, et al. Toward a universal "adhesive nanosheet" for the assembly of multiple nanoparticles based on a protein-induced reduction/decoration of graphene oxide[J]. Journal of the American Chemical Society, 2010, 132(21):7279-7281.
[90] ESFANDIAR A, AKHAVAN O, IRAJIZAD A. Melatonin as a powerful bio-antioxidant for reduction of graphene oxide[J]. Journal of Materials Chemistry, 2011, 21(29):10907-10914.
[91] KARTICK B, SRIVASTAVA S. Green synthesis of graphene[J]. Journal of Nanoscience and Nanotechnology, 2013, 13(6):4320-4324.
[92] HAGHIGHI B, TABRIZI M A. Green-synthesis of reduced graphene oxide nanosheets using rose water and a survey on their characteristics and applications[J]. RSC Advances, 2013, 3(32):13365-13371.
[93] KUILA T, BOSE S, KHANRA P, et al. A green approach for the reduction of graphene oxide by wild carrot root[J]. Carbon, 2012, 50(3):914-921.
[94] TAVAKOLI F, SALAVATI-NIASARI M, MOHANDES F. Green synthesis and characterization of graphene nanosheets[J]. Materials Research Bulletin, 2015, 63:51-57.
[95] BO Z, SHUAI X, MAO S, et al. Green preparation of reduced graphene oxide for sensing and energy storage applications[J]. Scientific Reports, 2014, 4:4684.
[96] MUTHOOSAMY K, BAI R G, ABUBAKAR I B, et al. Exceedingly biocompatible and thin-layered reduced graphene oxide nanosheets using an eco-friendly mushroom extract strategy[J]. International Journal of Nanomedicine, 2015, 10:1505-1519.
[97] THAKUR S, KARAK N. Green reduction of graphene oxide by aqueous phytoextracts[J]. Carbon, 2012, 50(14):5331-5339.
2020, Vol. 48 
