One step synthesis of graphene oxide under low-temperature and its microwave reduction
YUWEN Chao1,2,3, LIU Bing-guo1,2,3, ZHANG Li-bo1,2,3, GUO Sheng-hui1,2,3, PENG Jin-hui1,2,3
1. Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China;
2. Yunnan Provincial Key Laboratory of Intensification Metallurgy, Kunming 650093, China;
3. The Key Laboratory of Unconventional Metallurgy(Ministry of Education), Kunming University of Science and Technology, Kunming 650093, China
Abstract：The graphene oxide was prepared via one step under low-temperature with natural flake graphite as raw material. Factors affecting oxidation degree and layer spacing of graphene oxide were discussed in the process of low-temperature oxidation, such as the dosage of oxidant and oxidation time in system. The results indicate that high C-O bond and low defect structure (ID:IG=0.63) graphene oxide with the carbon and oxygen atom ratio of 1.98 can be prepared in the condition of the potassium permanganate with natural flake graphite mass ratio of 1:3, oxidation temperature of 0℃, oxidation time of 48h.This way avoids the increase of graphene oxide defects in the process of Hummers preparation due to the formation of CO2, which leads to the hexagon fracture and the absence of carbon atoms. After microwave reduction, the reduced graphene oxide with low defect is obtained, which the distance between defects(LD)is 12nm,the defect density(nD) is 2.21×1011cm-2 and the ratio of ID:IG is only 0.85 (ΓG=32.1cm-1).
[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] GÓMEZ N C,WEITZ R T,BITTNER A M,et al. Electronic transport properties of individual chemically reduced graphene oxide sheets[J]. Nano Letters,2007,7(11):3499-3503.
[3] PRASHER R. Graphene spreads the heat[J]. Science,2010,328(5975):185-186.
[4] NOVOSELOV K S,FALKO V I,COLOMBO L,et al. A roadmap for graphene[J]. Nature,2012,490(7419):192-200.
[5] ZHU Y, MURAL S,CAI W,et al. Graphene-based materials:graphene and graphene oxide:synthesis, properties, and applications[J]. Advanced Materials,2010,22(35):3906-3924.
[6] GEIM A K. Graphene:status and prospects[J]. Science,2009,324(5934):1530-1534.
[7] TUNG V C,ALLEN M J,YANG Y,et al. High-throughput solution processing of large-scale graphene[J]. Nature Nano-technology,2009,4(1):25-29.
[8] HE D,SHEN L,ZHANG X,et al. An efficient and eco-friendly solution-chemical route for preparation of ultrastable reduced graphene oxide suspensions[J]. AICHE Journal,2014,60(8):2757-2764.
[9] DIMIEV A,KOSYNKIN D V,ALEMANY L B,et al. Pristine graphite oxide[J]. Journal American Chemical Society,2012,134(5):2815-2822.
[10] EIGLER S,ENZELBERGER H M,GRIMM S,et al. Wet chemical synthesis of graphene[J]. Advanced Materials,2013,25(26):3583-3587.
[11] EIGLER S,DOTZER C, HIESCH A,et al. Visualization of defect densities in reduced graphene oxide[J]. Carbon,2012,50(10):3666-3673.
[12] HASHIMOTO A,SUENAGAK,GLOTER A,et al. Direct evidence for atomic defects in graphene layers[J]. Nature,2004, 430(7002):870-873.
[13] PEI S, CENG H M. The reduction of graphene oxide[J]. Carbon,2012,50(9):3210-3218.
[14] MAO S,PU H,CHEN J. Graphene oxide and its reduction:modeling and experimental progress[J]. Cheminform,2012,43(22):2643-2662.
[15] EIGLER S,DOTZER C,HIRSCH A,et al. Formation and decomposition of CO2 intercalated graphene oxide[J]. Chemistry of Materials,2012,24(7):1276-1282.
[16] FERRARI A C,ROBERTSON J. Interpretation of Raman spectra of disordered and amorphous carbon[J]. Physical Review B Condensed Matter,2000,61(20):14095-14107.
[17] YU V B,RYBAKOV K I,SEMENOV V E. High-temperature microwave processing of materials[J]. Journal of Physics D Applied Physics,2001,34(13):55-75.
[18] JU H M,HUH S H,CHOI S H,et al. Structures of thermally and chemically reduced graphene[J]. Materials Letters,2010,64(3):357-360.
[19] MOON I K,LEE J,RUOFF R S,et al. Reduced graphene oxide by chemical graphitization[J]. Nature Communications,2010,1(6):73-79.
[20] YAMAGUCHI H,EDA G,MATTEVI C,et al. Highly uniform 300mm wafer-scale deposition of single and multilayered che-mically derived graphene thin films[J]. ACS Nano,2010,4(1):524-528.
[21] VORIY D,YANG J, KUPFERBER J,et al. High-quality graphene via microwave reduction of solution-exfoliated graph-ene oxide[J]. Science,2016,353(6303):1413-1416.
[22] 王培草,孙红娟,彭同江,等. 氧化程度对氧化石墨烯a-b轴结构及电学性能的影响[J]. 无机化学学报,2015,31(2):275-281. WANG P C,SUN H J,PENG T J,et al. Influence of oxidation degrees on the a-b structures and conductivity of graphene oxide sample[J]. Chinese Journal of Inorganic Chemistry,2015,31(2):275-281.
[23] SZABÓ T,TOMBÁCA E,ILLÉS E,et al. Enhanced acidity and pH-dependent surface charge characterization of successively oxidized graphite oxides[J]. Carbon,2006,44(3):537-545.
[24] BASKO D M. Theory of resonant multiphonon Raman scattering in graphene[J]. Physics,2008,78(12):1884-1898.
[25] FERRARI A C,ROBERTSON J. Resonant Raman spectroscopy of disordered,amorphous,and diamondlike carbon[J]. Physical Review B Condensed Matter,2001,64(7):075414.
[26] MARTINS F E H,MOUTINBO M V O,STAVALE F,et al. Evolution of the Raman spectra from single-,few-,and many-layer graphene with increasing disorder[J]. Physical Review B,2010,82(12):4079-4085.
[27] CHEN W,YAN L,BANGGAL P R. Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves[J]. Carbon,2010,48(4):1146-1152.
[28] NOVOSELOV K S,JIANG D,SCHEDIN F,et al. Two-dimensional atomic crystals[J]. Proceeding of the National Academy Sciences of the United States of America,2005,102(30):10451-10455.
2019, Vol. 47 
