Chemical and structural properties of reduced graphene oxide—dependence on the reducing agent
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Abstract
Abstract Graphene oxide (GO) prepared from graphite powder using a modified Hummers method and reduced graphene oxide (rGO) obtained from GO using different reductants, i.e., sodium borohydride, hydrazine, formaldehyde, sodium hydroxide and L-ascorbic acid, were investigated using transmission electron microscopy, X-ray diffraction, Raman, infrared and electron spectroscopic methods. The GO and rGOs’ stacking nanostructure (flake) size (height x diameter), interlayer distance, average number of layers, distance between defects, elementary composition, content of oxygen groups, C sp3 and vacancy defects were determined. Different reductants applied to GO led to modification of carbon to oxygen ratio, carbon lattice (vacancy) and C sp3 defects with various in-depth distribution of C sp3 due to oxygen group reduction proceeding as competing processes at different rates between interstitial layers and in planes. The reduction using sodium borohydride and hydrazine in contrary to other reductants results in a larger content of vacancy defects than in GO. The thinnest flakes rGO obtained using sodium borohydride reductant exhibits the largest content of vacancy, C sp3 defects and hydroxyl group accompanied by the smallest content of epoxy, carboxyl and carbonyl groups due to a mechanism of carbonyl and carboxyl group reduction to hydroxyl groups. This rGO similar diameter to GO seems to result from a predominant reduction rate between the interstitial layers. The thicker flakes of a smaller diameter than in GO are obtained in rGOs prepared using remaining reductants and result from a higher rate of reduction of in plane defects.
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Research context
OpenAlex topics: Graphene research and applications · Graphene and Nanomaterials Applications · Fiber-reinforced polymer composites
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References (57)
Show source-provided references
1. Pei S, Cheng H-M (2012) The reduction of graphene oxide. Carbon 50:3210–322810.1016/j.carbon.2011.11.010 ↗
2. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2012) The chemistry of graphene oxide. Chem Soc Rev 39:228–24010.1039/B917103G ↗
3. Chua CK, Pumera M (2014) Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. Chem Soc Rev 43:291–31210.1039/C3CS60303B ↗
4. Obata S, Tanaka H, Saiki E (2013) Electrical and spectroscopic investigations on the reduction mechanism of graphene oxide. Carbon 55:126–13210.1016/j.carbon.2012.12.018 ↗
5. Stobinski L, Lesiak B, Malolepszy A, Mazurkiewicz M, Mierzwa B, Zemek J, Jiricek P, Bieloshapka I (2014) Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods. J Electron Spectros Re Phenom 195:145–15410.1016/j.elspec.2014.07.003 ↗
6. Ren P-G, Yan D-X, Ji X, Che T, Li Z-M (2011) Temperature dependence of graphene oxide reduced by hydrazine hydrate. Nanotechnology 22:055705–05570810.1088/0957-4484/22/5/055705 ↗
7. Guo H, Peng M, Zhu Z, Sun L (2013) Preparation of reduced graphene oxide by infrared irradiation induced photothermal reduction. Nanoscale 5:9040–904810.1039/c3nr02805d ↗
8. Malard LM, Pimenta MA, Dresselhaus G, Dresselhaus MS (2009) Raman spectroscopy in graphene. Phys Rep 473:51–8710.1016/j.physrep.2009.02.003 ↗
9. Niyogi S, Bekyarova E, Itkis ME, Zhang H, Shepperd K, Hicks L, Sprinkle M, Berger C, Lau CN, de Heer WA, Conrad EH, Haddon RC (2010) Spectroscopy of covalently functionalised graphene. Nano Lett 10:4061–406610.1021/nl1021128 ↗
10. Qi Z, Zhu X, Jin H, Zhang T, Kong X, Ruoff RS, Qiao Z, Ji H (2018) Rapid identification of the layer number of large-area-graphene on copper. Chem Matter 30:2067–207310.1021/acs.chemmater.7b05377 ↗
11. Szirmai P, Márkus BG, Chacón-Torres JC, Eckerlein P, Edelthalhammer K, Englert JM, Mundloch U, Hirsch A, Hauke F, Náfrádi B, Forró L, Kramberger C, Pichler T, Simon F (2019) Characterizing the maximum number of layers in chemically exfoliated graphene. Scientific Reports 9:19480–1951010.1038/s41598-019-55784-6 ↗
12. Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 61(20):14095–1410710.1103/PhysRevB.61.14095 ↗
13. Tunistra F, Koenig JL (1970) Raman spectrum of graphite. J Chem Phys 53:1126–113010.1063/1.1674108 ↗
14. Lan Y, Zondode M, Deng H, Yan J-A, Ndaw M, Lisfi A, Wang Ch, Pan Y-L (2018) Basic Concepts and recent advances of crystallographic orientation determination of graphene by Raman spectroscopy. Crystals 8:375–42810.3390/cryst8100375 ↗
15. Venezuela P, Lazzeri M, Mauri F (2011) Theory of double-resonant Raman spectra in graphene: Intensity and line-shape of defect-induced and two-phonon bands. Phys Rev B 84:035433–03551210.1103/PhysRevB.84.035433 ↗
16. Casiraghi C, Pisana S, Novoselov KS, Geim AK, Ferrari AC (2007) Raman fingerprint of charged impurities in graphene. Appl Phys Lett 91:233108–3p10.1063/1.2818692 ↗
17. Eckmann A, Felten A, Mishchenko A, Britnell L, Krupke R, Novoselov KS, Casiraghi C (2012) Probing nature of defects in graphene by Raman spectroscopy. Nano Lett 12:3925–393010.1021/nl300901a ↗
18. Lucchese MM, Stavale F, Martin Ferreire EH, Vilani C, Moutinho MVO, Capaz RB, Achete CA, Jorio A (2010) Quantifying ion-induced defects and Raman relaxation length in graphene. Carbon 48:1592–159710.1016/j.carbon.2009.12.057 ↗
19. Cançado LG, Jorio A, Martins Ferreira EH, Sravale F, Achete CA, Capaz RB, Moutinho MVO, Lombardo A, Kulmala TS, Ferrari AC (2011) Quantifying defects in graphene via Raman Spectroscopy at different excitation energies. Nano Lett 11:3190–319610.1021/nl201432g ↗
20. Jablonski A, Powell CJ (2004) Information depth for elastic-peak electron spectroscopy. Surf Sci 551:106–12410.1016/j.susc.2003.12.036 ↗
21. Jablonski A, Powell CJ (2009) Practical expressions for the mean escape depth, the information depth, and the effective attenuation length in Auger-electron spectroscopy and X-ray photoelectron spectroscopy. J Vac Sci Technol A 27:253–26110.1116/1.3071947 ↗
22. Standard E 673–01, Annual Book of ASTM Standards 2002, ASTM International, West Conshohocken, PA, 2002, vol 3.06, p. 755.
23. ISO 18115, Surface Chemical Analysis – Vocabulary, International Organization for Standarization, Geneva, 2001.
24. Shinotsuka H, Tanuma S, Powell CJ, Penn DR (2015) Calculations of electron inelastic mean free paths. X. Data for 41 elemental solids over the 50 eV to 200 keV range with the relativistic full Penn algorithm. Surf Interface Anal 47:871–88810.1002/sia.5789 ↗
25. Xu M, Fujita D, Gao J, Hanagata N (2010) Auger electron spectroscopy: A rational method for determining thickness of graphene films. ACS Nano 4:2937–294510.1021/nn100276w ↗
26. Jablonski A, Zemek J (2009) Overlayer thickness determination by XPS using the multiline approach. Surf Interface Anal 41:193–20410.1002/sia.3005 ↗
27. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:311–33610.1021/ja01539a017 ↗
28. Kövér L, Varga D, Cserny I, Tóth J, Tökési K (1992) Some applications of high-energy, high-resolution Auger-electron spectroscopy using Bremsstrahlung radiation. Surf Interface Anal 19:9–1510.1002/sia.740190106 ↗
29. Pan Q, Chung C-C, He N, Jones JN, Gao W (2016) Accelerated thermal decomposition of graphene oxide films in air via in situ X-ray diffraction analysis. J Phys Chem C 120:14984–1499010.1021/acs.jpcc.6b05031 ↗
30. Yuan R, Yuan J, Wu Y, Chen L, Zhou H, Chen J (2017) Efficient synthesis of graphene oxide and the mechanisms of oxidation and exfoliation. Appl Surf Sci 416:868–87710.1016/j.apsusc.2017.04.181 ↗
31. Rezania B, Severin N, Talyzin AV, Rabe JP (2014) Hydration of bilayered graphene oxide. Nano Lett 14(7):3993–399810.1021/nl5013689 ↗
32. Calliari L, Fanczenko S, Filippi M (2007) Plasmon features in electron energy loss spectra from carbon materials. Carbon 45:1410–141810.1016/j.carbon.2007.03.034 ↗
33. Eberlein JT, Bangert U, Nair RR, Jones R, Gass M, Bleloch AL, Novoselov AS, Geim A, Briddon PR (2008) Plasmon spectroscopy of free-standing graphene films. Phys Rev B: Condens Matter 77:233406–23341410.1103/PhysRevB.77.233406 ↗
34. Johari P, Shenoy VB (2011) Modulating optical properties of graphene oxide: Role of prominent functional groups. ACS Nano 5:7640–764710.1021/nn202732t ↗
35. Xu Z, Bando Y, Liu L, Wang W, Bai X, Golberg D (2011) Electrical conductivity, chemistry, and bonding alternations under graphene oxide to graphene transition as revealed by in situ TEM. ACS Nano 5:4401–440610.1021/nn103200t ↗
36. Mkhoyan KA, Contryman AW, Silcox J, Stewart DA, Eda G, Mattevi C, Miller S, Chhowalla M (2009) Atomic and electronic structure of graphene-oxide. Nano Lett 9:1058–106310.1021/nl8034256 ↗
37. Gass MH, Bangert U, Bleloch AL, Wang P, Nair RR, Geim AK (2008) Free-standing graphene at atomic resolution. Nature Nanotechnol 3:676–68110.1038/nnano.2008.280 ↗
38. Touggard S, Background analysis of XPS/AES QUASES Simple Backgrounds, ver. 2.2, 1999–2001 Tougaard Inc.
39. Mohai M (2004) MultiQuant XPS multimodel XPS quantification software. Surf Interface Anal 36:828–83210.1002/sia.1775 ↗
40. Mohai M, Multimodel of X-ray photoelectron spectroscopy quantification program for 32-bit Windows, XPSMuliQuant, ver. 7, 1999–2001.
41. Scofield H (1976) Hartree-Slater Subshell Photoionization Cross-sections at 1254 and 1487 eV. J Electron Spectrosc Relat Phenom 8:129–13710.1016/0368-2048(76)80015-1 ↗
42. Kovtun A, Jones D, Dell’Elce S, Treossi E, Liscio A, Palermo V (2019) Accurate chemical analysis of oxygenated graphene-based materials using X-ray photoelectron spectroscopy. Carbon 143:268–27510.1016/j.carbon.2018.11.012 ↗
43. Kwok RWM, XPS peak fitting program for WIN95/98 XPSPEAK, ver. 4.1, Department of Chemistry, The Chinese University of Hong Kong, XPSPEAK4.1.
44. Estrade-Szwarckopf (2004) XPS photoemission in carbonaceous materials: A “defect” peak beside the graphitic asymmetric peak. Carbon 42:1713–172110.1016/j.carbon.2004.03.005 ↗
45. Butenko YV, Krishnamurthy S, Chakraborty AK, Kuznetsov VL, Dhanak VR, Hunt MC, Šiller L (2005) Photoemission study of onionlike carbons produced by annealing nanodiamonds. Phys Rev B 71:075420–10p10.1103/PhysRevB.71.075420 ↗
46. Lesiak B, Kövér L, Tóth J, Zemek J, Jiricek P, Kromka A, Rangam N (2018) C sp2/sp3 hybridisations in carbon nanomaterials – XPS and (X)AES study. Appl Surf Sci 452:223–23110.1016/j.apsusc.2018.04.269 ↗
47. Lesiak B, Stobinski L, Malolepszy A, Mazurkiewicz M, Kövér L, Tóth J (2014) Preparation of graphene oxide and characterisation using electron spectroscopy. J Electron Spectrosc Rel Phenom 193:92–9910.1016/j.elspec.2014.03.015 ↗
48. Barinov A, Malcioglu OB, Fabris S, Gregoratti ST, Dalmiglio L, Kiskinova M (2009) Initial stages of oxidation of graphitic surfaces: Photoemission study and density functional theory calculations. J Phys Chem C 113:9009–901310.1021/jp902051d ↗
49. Shim SH, Kim KT, Lee JU, Jo WH (2012) Facile method to functionalize graphene oxide and its application to poly(ethylene terephthalate)/graphene composite. ACS Appl Mater Interfaces 4:4184–419110.1021/am300906z ↗
50. Fujimoto A, Yamada Y, Koinuma M, Sata S (2016) Origins of sp3C peaks in C1s X-ray photoelectron spectra of carbon materials. Anal Chem 88:6110–611410.1021/acs.analchem.6b01327 ↗
51. Yanga Sh, Li L, Xiao T, Zheng D, Zhang Y (2016) Role of surface chemistry in modified ACF (activated carbon fiber)-catalyzed peroxymonosulfate oxidation. Appl Surf Sci 383:142–15010.1016/j.apsusc.2016.04.163 ↗
52. Hong S, Deng Sh, Yao X, Wang B, Wang Y, Huang J, Yu G (2016) Bromate removal from water by polypyrrole tailored activated carbon. J Col Interface Sci 467:10–1610.1016/j.jcis.2016.01.001 ↗
53. Winter B, Aziz EF, Hergenhahn U, Faubel M, Hertel IV (2007) Hydrogen bonds in liquid water studied by electron spectroscopy. J Chem Phys 126:124504–12450610.1063/1.2710792 ↗
54. Yamamoto S, Bluhm H, Andersson K, Ketteler G, Ogasawara H, Salmeron M, Nilsson A (2008) In situ x-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions. J Phys: Condend Matter 20:184025-14p
55. Lascovich C, Scaglione S (1994) Comparison among XAES, PEELS and XPS techniques for evaluation of Sp2 percentage in a-C:H. Appl Surf Sci 78:17–2310.1016/0169-4332(94)90026-4 ↗
56. Si Y-C, Samulski T (2008) Synthesis of water soluble graphene. Nano Lett 8(6):1679–168210.1021/nl080604h ↗
57. Susi T, Kaukonen M, Havu P, Ljungberg MP, Ayala P, Kauppinen EI (2014) Core level binding energies of functionalized and defective graphene. Beilstein J Nanotechnol 5:121–13210.3762/bjnano.5.12 ↗