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Facile and safe graphene preparation on solution based platform

Article  in  Journal of Industrial and Engineering Chemistry · September 2014

DOI: 10.1016/j.jiec.2013.11.022

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 Journal of Industrial and Engineering Chemistry 20 (2014) 2883–2887

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Facile and safe graphene preparation on solution based platform

Fatima Tuz Johra, Jee-Wook Lee, Woo-Gwang Jung *
School of Advanced Materials Engineering, Kookmin University, Seoul 136-702, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Graphene has attracted increasing attention because of its interesting properties. In this study, graphene
Received 3 August 2013 was prepared from graphite by a very simple and easy process. The two-step protocol involves
Received in revised form 30 October 2013 conversion of graphite to graphene oxide (GO) by oxidation, and subsequent reduction of GO to
Accepted 4 November 2013
graphene. The structures and properties of the obtained GO and graphene were characterized via X-ray
Available online 12 November 2013
diffraction, and Raman, NMR, UV–vis absorption, and X-ray photoelectron spectroscopic techniques. The
morphologies of these products were observed via field emission scanning electron microscopy. The
Keywords:
preparation protocol is simple, easy, environmental friendly, i.e., nontoxic, and the yield of graphene is
Graphene
Improved Hummers’ method
high.
Hydrothermal ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Raman spectroscopy reserved.
ð-conjugation

1. Introduction
Graphene, a two-dimensional honeycomb sheet of sp2-hybrid-
ized carbon atoms, exhibits a number of extraordinary character-
istics, such as a large theoretical specific surface area
(2630 m2 g 1), high intrinsic mobility (200,000 cm2 v 1 s 1)
[1,2], high Young’s modulus (1.0 TPa) [3] and thermal conduc-
tivity (5000 Wm 1 K 1) [4], optical transmittance (97.7%) [5],
and good electrical conductivity [6]. These characteristics render
graphene popular and useful for applications such as transparent
conductive electrodes [7,8] and super-capacitors, among many
other potential applications. The thermal, mechanical, and
electrical properties of graphene are derived from long range ð-
conjugation.
Graphene can be obtained by various processes, including
chemical vapor deposition [9], micromechanical cleavage of
graphite [10], and exfoliation of graphite [11]. In this study, a
solution-based chemical process is utilized as a simple approach
for graphene generation. To address the poor carrier mobility of
solution-processed graphene, which is due to the presence of a
large number of defects [12], graphite flakes are utilized as the
starting material. Graphite consists of a stack of flat graphene
sheets and is inexpensive and readily available. The graphene
preparation protocol involves two steps, i.e., oxidation of graphite
to graphene oxide (GO) and subsequent reduction of graphene
oxide to graphene. In the initial step, graphite flakes are exfoliated
into single layers to facilitate graphene production. Graphene
* Corresponding author. Tel.: +82 2 910 4643; fax: +82 2 910 4320.
E-mail addresses: wgjung@kookmin.ac.kr, drwgjung@gmail.com (W.-G. Jung).
oxide was first prepared almost 150 years ago [13], and has found
application in the cost-effective, large-scale production of gra-
phene-based materials. Here, an improved Hummers’ method is
utilized to prepare graphene oxide, which offers the advantage of
simplicity, notwithstanding the longer time needed relative to the
Hummers’ and modified Hummers’ methods [14–16]. This method
utilizes two powerful acid mixtures as the oxidizing agent and
offers the advantages of high yield and environmental friendliness.
Treatment of graphite by this method retains the layered structure
of graphene oxide, whereas the interlayer spacing is larger than
that in graphite. The resulting graphene oxide contains epoxy and
hydroxyl groups and also a few carbonyl and carboxyl groups.
2. Experimental
High-purity graphite flakes (40 mm) were obtained from
Taewon Scientific Co., and potassium permanganate (KMnO4),
95% sulfuric acid (H2SO4), 85% phosphoric acid (H3PO4), 35–37%
hydrochloric acid (HCl), 30% hydrogen peroxide (H2O2), 25–30%
ammonia water (NH4OH), 99.9% ethanol (C2H5OH), and 99% ethyl
ether [(C2H5)2O] were obtained from Duksan reagents and
chemicals. A poly(tetrafluoroethylene) (PTFE) membrane filter
was purchased from the Pall Corporation.
Graphene oxide was prepared from graphite flakes via an
improved Hummers’ method [17]. A mixture of H2SO4 and H3PO4
(9:1 vol. equiv.) was added to a mixture of KMnO4 and graphite
flakes (3:1 wt. equiv.). Because of heat evolution from the
exothermic process, a delay (15–20 min) was introduced to bring
the temperature down to room temperature. The mixture was then
placed on a heating mantle at 50 8C, with constant stirring for 12 h.
After completion of the reaction, the mixture was cooled to room

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.11.022
2884 F.T. Johra et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 2883–2887
temperature and poured onto ice [400 mL of deionized (DI) water
were used to make the ice] with 30% H2O2 (3 mL). The solution
was then sieved using a testing sieve and the filtrate was
centrifuged (4000 rpm, 4 h). The supernatant was then discarded,
and the remaining solid was sequentially washed with water, 30%
HCl, and ethanol (twice in each case); for each wash, the mixture
was sifted through the sieve and the filtrate was then centrifuged
(4000 rpm, 4 h) using a Mega 17R small, high-speed, refrigerated
centrifuge machine, and the supernatant was decanted. After the
multiple washing treatments, the remaining materials were
coagulated using ethyl ether and then filtered through a PTFE
membrane with a micropore size of 0.2 mm, followed by drying in
vacuum.
Graphene oxide was placed in a beaker and sonicated with DI
water (0.1 mg mL 1) for 5 min, using an ultrasonicator. NH4OH (2–
4 mL) were added to adjust the pH to 11. The mixture was
transferred to a Teflon-lined stainless-steel autoclave and placed in
an oven at 180 8C for 6 h. After completion of the reaction, this
solution was centrifuged (4000 rpm, 4 h), and the obtained
materials were washed with DI water and ethanol (twice in each
case) to remove impurities. Finally, the obtained material was
collected by vacuum filtration and dried in vacuum.
The obtained products were dispersed in water by sonication
and spin coated onto a SiO2/Si wafer (Piranha cleaned) for field
emission scanning electron microscopy (FE-SEM) analysis. The
FE-SEM images were obtained by analysis of the sample using a
JEOL JSM5410 instrument. The obtained graphene was examined
via transmission electron microscopy (TEM, JEOL JEM1210).
Atomic force microscopy (AFM, XE-100, Park system) was used
to determine the graphene thickness. X-ray diffraction (XRD)
analyses were performed on a Rigaku D-max 2500 instrument
(Japan), using Cu Ka radiation, under a voltage of 40 kV and a
current of 200 mA. The refraction data of the finely powdered
samples were recorded for 2u angles between 3 and 558. Raman
spectra were recorded between 500 and 3000 cm 1 on a Horiba
Jobin Yvon LabRam Aramis Raman spectrometer, using a
514.5 nm Ar laser at 0.5 mW power. The laser spot size was
around 1 mm. NMR analysis was performed on a Bruker AVANCE
III 500 MHz spectrophotometer. UV–vis spectral measurements
were acquired using a Perkin Elmer Precisely Lambda 35 UV/VIS
Spectrometer. An ultrasonicated suspension of the product in
water was used for this analysis. The ultrasonication was
performed using an Ulsso Hitechs Sonosmasher ULH-700S at
19.82 kHz. X-ray photoelectron spectroscopy (XPS) was per-
formed using an ESCA2000 instrument with an Al Ka X-ray source
(1486.6 eV) under 10 10 torr vacuum pressure. The pass energy
was set at 50 eV for wide and 20 eV for narrow scanning. The X-ray
take off angle was fixed at 568.
3. Results and discussion
In the first step, graphite was converted to graphene oxide by
reaction of a potassium permanganate, sulfuric acid, and
phosphoric acid mixture. As mentioned, the treated graphite
contains a number of oxygen containing groups, and is thus readily
dispersed in water, i.e., GO acts as an oxygenated graphene layer.
Based on the physical appearance of graphite, GO and graphene,
they could be separated. Graphite was grey in color whereas the
GO was brownish, and graphene had a very dark color. The mass of
each of these species was another distinguishing feature. GO
contained a large quantity of water, thus the mass was increased
relative to that of graphite. However, after reduction, the mass was
low compared to that of GO because of the loss of oxygen during
the reduction process. Approximately 50 mg of grey-colored
graphite yielded 100 mg of GO, which, upon reduction, yielded
52 mg of graphene.
Fig. 1. XRD patterns of graphite, graphene oxide and graphene.
Fig. 1 shows the XRD patterns of graphite, graphene oxide, and
graphene. In the XRD pattern of GO obtained via the improved
Hummers’ method, the (0 0 1) crystal plane of GO was evident,
with a spacing of 8.33 Å, which is typical for GO. The spacing was
3.36 Å for graphite. The increased distance in the former was due to
the introduction of a number of oxygen-containing groups on the
edge of each layer, which increased the distance between the
layers. After hydrothermal treatment of GO, the spacing again
decreased to 3.70 Å, which is still slightly higher than that of
graphite. This suggests the presence of some remaining oxygen
functional groups in the prepared graphene. From the observed
peak broadening, it is inferred that the stacking of graphene was
not well ordered.
To evaluate the degree of exfoliation of the GO into graphene, an
aqueous suspension of both GO and graphene was spin coated onto
a Si/SiO2 substrate and inspected by means of FE-SEM. The SEM
image in Fig. 2(a) shows that GO flakes were distributed on the
substrate. From the FE-SEM image, the average size of GO was
estimated at 500 nm. Graphene flakes of various sizes are
observed in the SEM image in Fig. 2(b), derived from overlapping
with each other as a result of the three spin-coating cycles.
Ultrasonication (700 W) for a long time (1 h) may reduce the size of
the graphene flakes. The average size of the prepared graphene was
ca. 200–500 nm. Transmission electron microscopy (TEM) is also a
very important tool for investigating the quality of exfoliated
graphene. Fig. 2(c) shows the TEM image of a graphene sheet,
acquired by dropping a small quantity of the graphene dispersion
on a holey carbon grid, followed by drying. A very thin film of
graphene is observed in this image.
AFM, an effective method for determination of the thickness of
graphene, confirmed that the resulting graphene sheets deposited
on the Si/SiO2 were flat and had a thickness of around 1.0–1.5 nm
(Fig. 2(d)). Given that the pristine graphene sheet is flat with a
well-known van der Waals thickness of 3.70 Å, and the XRD
analysis demonstrated that the inter-sheet distance was around
3.70 Å, the data suggest that the hydrothermally treated graphene
consists of two to four layers. The size and shape of the graphene
produced in this method varied, as confirmed by the AFM data.
The prepared GO and graphene were characterized from their
Raman spectra (Fig. 3), which allow for consideration of the
conjugated and carbon–carbon double bonds, which lead to high-
intensity peaks in the Raman spectrum. The typical Raman
spectrum of GO is characterized by a G band at ca. 1605 cm 1,
which corresponds to the E2g phonon of the sp2 C atoms, and a D
band at 1353 cm 1, which corresponds to the breathing mode of k-
point phonons of A1g symmetry. Here, the G band of graphene was
 F.T. Johra et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 2883–2887
Fig. 2. (a) FE-SEM image of graphene oxide, (b) FE-SEM image of graphene, (c) TEM image of graphene, and (d) AFM image of graphene.
observed at 1600 cm 1, which is slightly shifted from the position
of that of GO. The D band is an indication of disorder, which may
arise from certain defects such as vacancies, grain boundaries
[18,19], and amorphous carbon species [20]. The intensity ratio of
these two bands indicates the quality of the product. The band
intensity ratio, Id/Ig, decreased to 0.96 in the case of graphene from
the ratio of 1.00 for GO. This difference indicates the repair of
defects by recovery of the aromatic structures. Lee and co-workers
[21] reported an increase in the Id/Ig ratio of reduced graphene
oxide treated with hydroiodic acid and acetic acid, indicating that
the reduction process altered the structure of GO with a large
quantity of structural defects. Based on this information, it can be
deduced that the product prepared herein contains fewer defects
than the reported one. Two other bands were observed at 2700 and
2900 cm 1. For monolayer graphene, there is a sharp peak at ca.
2700 cm 1. The band at 2700 cm 1 is known as the 2D band, which
is an indicator of the number of graphene layers. Here, the band is
Fig. 3. Raman spectra of graphene oxide and graphene.
2885
observed to be broadened, attributed to the fact that the prepared
graphene contains few layers with some defects. Another band,
known as the S3 band (2900 cm 1), is a second-order peak derived
from the D–G peak combination. The intensity ratio of S3 relative
to 2D is proportional to the reduction in defects. This reduction is
accompanied by a lower oxygen content in graphene [22]. The
intensities of both peaks increased in the case of graphene
compared to those of GO, indicating better graphitization [21].
The NMR spectrum of GO presented in Fig. 4 shows a resonance
centered at 130 ppm, corresponding to the unoxidized sp2 carbon
(C55C); the 59 ppm resonance results from epoxidation (C–O–C)
[23], and that at 167 ppm is attributed to the carbonyl carbon
(C55O) [24]. Another peak near 68 ppm (revealed after deconvolu-
tion) indicated the presence of hydroxyl groups. After reduction,
the peaks at 59, 68, and 167 ppm disappeared, and the peak at
130 ppm was shifted to 117 ppm as a result of the change in the
chemical environment of the sp2 carbons [25]. This peak was
Fig. 4. NMR spectra of graphene oxide and graphene.
2886 F.T. Johra et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 2883–2887
Fig. 5. UV spectra of graphene oxide and graphene.
slightly broadened by the chemical distribution, corresponding to
variations in the carbon atom environments.
The absorption peak at 235 nm in the UV–vis spectrum of GO
corresponds to p–p* transitions of the remaining sp2 C5 5C bonds,
which were shifted to longer wavelength (265 nm) after reduction
of GO to graphene (Fig. 5). The reduction of GO to graphene
increased the p-conjugation (or, in other words, restored the p-
conjugation network) [26]. As the p-conjugation increases, less
energy is required for the transition, which corresponds to the
observed shift of the absorption to the longer wavelength region.
Fig. 6 shows the C 1s XPS spectra for GO and graphene. After
deconvolution, it is clearly evident from Fig. 6 that the C 1s
spectrum of GO contains three peaks at 284.6, 286.6, and 288.5 eV,
corresponding to the sp2 carbon, the epoxide, and the carboxyl
functional groups, respectively [27]. There was one additional peak
in the case of graphene at 287.5 eV, corresponding to the C5 5O
bond. The XPS spectrum of graphene obtained after the hydro-
thermal reduction was characterized by a highly intense band at
284.6 eV, the intensity of which is almost twice that of GO; the
intensities of the bands corresponding to the carboxyl, epoxide, or
other functional groups were decreased compared to those of GO,
that is, the relative percentage of C55C bonds was increased and
Fig. 6. XPS spectra of graphene oxide and graphene.
that of the C–O bonds decreased in graphene, confirming the
reduction of GO. The XPS spectrum of graphene did not contain any
elements other than C and O, indicating the absence of impurities.
From the above discussion, it is clear that quite a good quality of
graphene can be prepared very easily. This method needs very
simple setup, that is, an autoclave for the graphene preparation,
and the handling of setup is quite easier than using some
complicated instruments. This process is also environmental
friendly, because no other chemical has been used without water.
Some work has been reported that the synthesis of graphene by
reduction with the hydrazine [25], which is quite harmful for the
environment, as well as the health. Moreover, there is no evolution
of any kind of gas or side product during this process. This method
ensures the recovering of aromatic structures in graphene.
4. Summary
Graphene oxide and graphene were synthesized very easily via
the solution-based process presented herein. The obtained
graphene contains a few layers with an intense D band in the
Raman spectra (indicative of defects), which may be caused by the
ultrasonication required for proper suspension using the solution-
based process. This may affect the quality of graphene, which is one
of the disadvantages of the solution-based process. Further
improvement in the quality can be achieved by changing the
solvent during the reduction. The preparation of graphene oxide
and graphene using this technique offers the advantage of
simplicity, without harmful environmental effects.
Acknowledgements
This study was supported by the ERC (Center for Materials and
Processes of Self Assembly) program of MOST/KOSEF ((R11-2005-
048-00000-0) and the Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science, and Technology (KRF-2011-
0024104).
References
[1] K.I. Bolotin, K.J. Sikes, Z. Jiang, M. Klima, G. Fudenberg, J. Hone, P. Kim, H.L. Stormer,
Solid State Commun. 146 (2008) 351.
[2] S.V. Morozov, K.S. Novoselov, M.I. Katsnelson, F. Schedin, D.C. Elias, J.A. Jaszczak,
A.K. Geim, Phys. Rev. Lett. 100 (2008) 016602.
[3] C. Lee, X.D. Wei, J.W. Kysar, J. Hone, Science 321 (2008) 385.
[4] A.A. Balandin, S. Ghosh, W.Z. Bao, I. Calizo, D. Teweldebrhan, F. Miao, C.N. Lau,
Nano Lett. 8 (2008) 902.
[5] R.R. Nair, A.N. Grigorenko, K.S. Novoselov, T.J. Booth, T. Stauber, N.M.R. Peres, A.K.
Geim, Science 320 (2008) 1308.
[6] A.K. Geim, K.S. Novoselov, Nat. Mater. 6 (2007) 183.
[7] W. Cai, Y. Zhu, X. Li, R.D. Piner, R.S. Ruoff, Appl. Phys. Lett. 95 (2009) 123115.
[8] X. Li, Y. Zhu, W. Cai, M. Borysiak, B. Han, D. Chen, R.D. Piner, L. Colombo, R.S. Ruoff,
Nano Lett. 9 (2009) 4359.
[9] G. Nandamuri, S. Roumimov, R. Solanki, Nanotechnology 21 (2010) 145604.
[10] D. Jiang, F. Schedin, T.J. Booth, V.V. Khotkevich, S.V. Morozov, A.K. Geim, Proc. Natl.
Acad. Sci. 102 (30) (2005) 10451.
[11] L.M. Viculis, J.J. Mack, O.M. Mayer, H.T. Hahn, R.B. Kaner, J. Mater. Chem. 15 (2005)
974.
[12] J.J. Palacios, J.F. Rossier, Phys. Rev. B 77 (2008) 195428.
[13] S. Park, R.S. Ruoff, Nat. Nanotechnol. 4 (2009) 217.
[14] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.B.
Alemany, W. Lu, J.M. Tour, ACS Nano 4 (2010) 4806.
[15] W. Hummers Jr., R.E. Offeman, J. Am. Chem. Soc. 80 (1958) 1339.
[16] T. Chen, B. Zeng, J.L. Liu, J.H. Dong, X.Q. Liu, Z. Wu, X.Z. Yang, Z.M. Li, J. Phys.: Conf.
Ser. 188 (2009) 012051.
[17] F.T. Johra, M.-J. Lee, W.-G. Jung, J. Sol–Gel Sci. Technol. 66 (2013) 481.
[18] F. Tuinstra, J.L. Koenig, J. Chem. Phys. 53 (1970) 1126.
[19] (a) A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S.
Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Phys. Rev. Lett. 97 (2006)
(1874) 01;
(b) A.C. Ferrari, J. Robertson, Phys. Rev. B 61 (2000) (1409) 5.
[20] R. Schonfelder, M.H. Rummeli, W. Gruner, M. Loffler, J. Acker, V. Hoffmann, T.
Gemming, B. Buchner, T. Pichler, Nanotechnology 18 (2007) 375601.
 F.T. Johra et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 2883–2887 2887

[21] I.K. Moon, J. Lee, R.S. Ruoff, H. Lee, Nat. Commun. 1 (2010), Article number 73 (doi:
10.1038/ncomms1067).
[22] H. Wang, J.T. Robinson, X. Li, H. Dai, J. Am. Chem. Soc. 131 (2009) 9910.
[23] H. He, J. Klinowski, M. Forster, A. Lerf, Chem. Phys. Lett. 287 (1998) 53.
[24] Y. Si, E.T. Samilski, Nanoletters 8 (2008) 1679.
[25] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu,
S.T. Nguyen, R.S. Ruoff, Carbon 45 (2007) 1558.
[26] Y. Zhow, Q. Bao, L.A. Ling Gtang, Y. Zhong, K.P. Loh, Chem. Mater. 21 (2009) 2950.
[27] S. Park, J. An, I. Jung, R.D. Piner, S.J. An, X. Li, A. Velamakanni, R.S. Ruoff, Nano Lett. 9
(2009) 1597.

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