Journal of Science: Advanced Materials and Devices 2 (2017) 470e475

Contents lists available at ScienceDirect

Journal of Science: Advanced Materials and Devices

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

Original Article

Effects of initial graphite particle size and shape on oxidation time in

graphene oxide prepared by Hummers' method
Seyyedeh Saadat Shojaeenezhad, Mansoor Farbod*, Iraj Kazeminezhad
Department of Physics, Faculty of Science, Shahid Chamran University of Ahvaz, Ahvaz, Islamic Republic of Iran

a r t i c l e i n f o a b s t r a c t

Article history: The effects of initial graphite particle size and shape on oxidation time of graphite prepared by Hummers'
Received 6 July 2017 method have been investigated. The oxidation was performed on three series of graphite particles, clod
Received in revised form powder with two different sizes of 18 and 6 mm, and flake shaped powder with an average particle size of
7 September 2017
25 mm. The samples were characterized by means of particle size analyzer, X-ray diffraction (XRD) and
Accepted 18 September 2017
Available online 27 September 2017
scanning electron microscopy (SEM). The ratio of XRD graphite oxide peak intensity to graphite peak
intensity was considered as an indicator of the oxidation degree. It was observed that the oxidation time
has a critical dependence on the initial graphite particle size and shape. While the oxidation of the clod
Keywords:
Graphene oxide
samples was completed in several days, the oxidation of flake powder was completed just in 2 h. These
Hummers method findings help researchers to save time by choosing the particle size and shape of initial graphite powders.
Particle shape © 2017 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
Oxidation time This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Particle size

1. Introduction oxide to graphene [5,6]. Hummers' method is a commonly used

Graphene is one of the carbon's allotropes with just one atom
thick in which the carbons are formed a honeycomb lattice of SP2
hybridization bonds [1]. Super electrical and thermal conductiv-
ities, high mechanical strength, high specific surface area and
interesting transport properties such as quantum Hall effect have
made graphene the most widely considered material, according to
the theoretical and experimental studies [2]. There are many re-
ports for producing graphene such as the micromechanical exfoli-
ation of graphite known as the “Scotch tape” or “peeling” method,
chemical vapor deposition, epitaxial growth techniques on non-
conductive surfaces like SiC and also the wet chemical methods [3].
Chemical methods are the most common ways of making gra-
phene due to their high yield production and control. In addition,
the final products of these methods are a colloidal suspension that
provides a possibility of subsequent modifications such as func-
tionalization [4]. Due to such features, the chemical methods are
still the best methods for many graphene-based applications.
Chemically produced graphene consists of three steps: graphite
oxidation, graphite oxide exfoliation and reduction of the graphene
* Corresponding author. Fax: þ98 6133331040.
E-mail addresses: s.shojaee1390@gmail.com (S.S. Shojaeenezhad), farbod_m@
scu.ac.ir (M. Farbod), I.Kazeminezhad@scu.ac.ir (I. Kazeminezhad).
Peer review under responsibility of Vietnam National University, Hanoi.
method for the oxidation of graphite. Various oxidation times have
been reported by different researchers. Hummers used flaky
graphite powders and oxidized graphite after half an hour [7]. Park
et al. [8] oxidized their graphite in 2 h, but they didn't describe
about the shape of the used graphite particles. Shahriary et al. [9]
spent 12 h for graphite oxidation but they also didn't present any
data about the shape of the used graphite particles. Wilson et al.
oxidized their samples in five days [10]. The lack of the used particle
shape's information has left an open question of what factor is
responsible for such discrepancy.
In this work, we present the effect of initial graphite particle size
and shape on oxidation time in graphene oxide prepared by
Hummers' method. This helps control the oxidation producer,
which can be useful in large scale production of graphite oxide.
2. Experimental
2.1. Materials
Experiments with three kinds of graphite powders with
different size distribution were performed. The first sample was the
graphite that was purchased from Samchun pure chemical Co., Ltd.
(Pyeongtaek, South Korea). The second sample was the same but
ball milled for 5 h, and the third sample was a flaky one that was
quite different in size and shape compared to the other two

https://doi.org/10.1016/j.jsamd.2017.09.003
2468-2179/© 2017 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
 S.S. Shojaeenezhad et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 470e475
samples. The scanning electron microscopy (SEM) images of the
samples were shown in Fig. 1 and their particle size distribution
diagrams deduced from particle size analyzer can be observed in
Fig. 2. The average particle size of the first, second and third sam-
ples were 18, 6, and 25 mm, respectively.
Potassium permanganate (KMnO4) and sodium nitrate (NaNO3)
were purchased from Samchun pure chemical Co., Ltd. (Pyeong-
taek, South Korea). Sulfuric acid (H2SO4) and hydrochloric acid
(HCl) were obtained from Merck (Germany). Hydrogen peroxide
(H2O2) was purchased from Kian kaveh azma (Tehran, Iran). All the
chemicals were research grade and used without any purification.
Deionized water was used throughout the experiment.
2.2. Characterization
SEM images were taken with a Leo, 1455 VP scanning electron
microscope. The particle size distributions were obtained using an
analysette 22 NanoTec (FRITSCH) particle analyzer. The powder X-
ray diffraction (XRD) measurements were performed using a Phi-
lips PW1840 diffractometer with Cu Ka radiation of 1.5418 Å to
investigate the structural properties.
2.3. Preparation of graphene oxide
5 g graphite powder of the first sample and 2.5 g sodium nitrate
(NaNO3) were put in a mortar, ground and mixed thoroughly then
transferred into a beaker. 115 ml concentrated sulfuric acid (H2SO4)
was added slowly to the mixture and well stirred up with a mag-
netic stirrer. The temperature was kept below 5  C by immersing
the beaker in an ice-water bath and 15 g of potassium permanga-
nate (KMnO4) was slowly and continuously added to the solution.
The beaker was then transferred to a bath where the temperature
was maintained at 35  C for 3 days. On the fourth day, 75 ml of
Fig. 1. SEM images of the initial graphite a) the unmilled sample, b) the 5 h milled sample, c) the flake sample, and d) graphene oxide.
471
deionized water was added to 25 ml of the suspension and the
mixture was kept at this temperature for half an hour. The resulting
suspension was then further diluted with 230 ml of deionized
water at 40  C, afterward a 30% aqueous hydrogen peroxide (H2O2)
was added drop wised until the suspension's color changed to
yellow, indicating the end of the reaction. A 3% hydrochloric acid
(HCl) solution was used to wash the suspension and the mixture
was centrifuged at 4000 rpm. This procedure was repeated 5 times.
The remaining sediment (i.e., graphite oxide) was dried at 40  C for
48 h. The same procedure was repeated after 5, 10 and 20 days for
the sample 1.
The above steps were also performed at 1, 3, 5, 10 and 12 day
intervals for the second sample. For the third sample due to its
morphology all the oxidation process (35  C bath) was completed in
2 h and we didn't need to soak it for several days. The SEM image of
the graphene oxide is illustrated in Fig. 1d. From the figure, it is
clear that the graphene oxide sheets obtained by sonication of the
graphite oxide are in the form of thin, flexible and wrinkled sheets.
The XRD patterns were used to evaluate the oxidation of our
samples. Jeong et al. [11] have shown that the XRD pattern of
graphite (G) has a characteristic peak at 26 . This peak is transferred
to the range of 10 to 12 after oxidation of graphite. The distance
between graphite sheets is about 3.35 Å, which upon oxidation can
vary between 6 and 12 Å, depending on the oxidation time [4].
Figs. 3 and 4 show the XRD patterns of the first, second and third
samples before and after oxidation respectively. As can be observed
in these figures, the peaks at approximately 26 are the charac-
teristic peaks of the initial graphite samples and the ones at 10 are
the characteristic peaks of graphite oxide.
The intensity and position of the GO peak in the XRD pattern can
be used as an indication of the oxidation degree [12]. It has been
shown that when the partial oxidation of graphite occurs, the XRD
pattern included either the peaks predicted for graphite (G) or
472 S.S. Shojaeenezhad et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 470e475

Fig. 2. Particle size distribution diagrams for the a) unmilled sample, b) 5 h milled sample, and c) flake samples.

Fig. 3. XRD patterns of the samples before oxidation (PG) and after different oxidation times: a) the first sample (18 mm) and b) the second sample (6 mm).

graphite oxide (GO). The intensities of GO peaks increase with

increasing the oxidation process while the G peak disappears in the
case of the complete oxidation [13].
In this study, the ratio of GO peak intensity to G peak intensity
(IGO/IG) was used to evaluate degrees of oxidation. Some features of
the XRD patterns of the first and second samples are presented in
Tables 1 and 2, respectively.
As can be seen from the XRD patterns and the data presented in
the tables, the peak intensity of GO has increased by increasing the
oxidation time, showing that the oxidation degree has increased by
increasing the oxidation time. The ratio of IGO/IG for the first and
second samples is plotted as a function of time in Fig. 5, indicating
that the degree of oxidation increases with increasing the oxidation

Table 1
Some characteristics of the first sample deduced from the XRD patterns.

Time 3 days 5 days 10 days 20 days

IGO/IG 0.16 0.82 1.55 1.92

GO interlayer distance (Å) 8.66 8.35 8.16 7.66
Fig. 4. XRD patterns of the flake sample before oxidation (PG) and after 2 h oxidation.
 S.S. Shojaeenezhad et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 470e475 473

Table 2 time for both samples. The ratio of IGO/IG for the bigger clod parti-
Some characteristics of the second sample deduced from the XRD patterns. cles reaches to 1.92 after 20 days oxidation but for smaller particles
Time 1 day 3 days 5 days 10 days 20 days reaches to 2.3 after the same time of oxidation, which means the
IGO/IG 0.22 0.31 1.1 1.8 2.3
smaller particles were oxidized in a shorter time.
GO interlayer distance (Å) 7.61 7.58 7.45 7.16 6.91 Unlike the first two samples, the third sample (flaky one) was
oxidized in just 2 h. It could be due to the fact that the flaky samples
had a lesser thickness and a higher effective surface area. If the
thickness of a particle is lesser, the acid diffusion between its layers
is completed in a shorter time. On the other words, a more effective
surface area provides a better access to acids and oxidizing agents
to diffuse and thus the oxidation is completed faster. For the big
clod particles, there are always some core graphitic parts that even
with a longer period (20 days) remain unoxidized.
Also the GO interlayer distances of the first and second samples
are shown in Fig. 6. It can be observed from the figure, for both
samples by increasing the soaking dwelling time of the samples in
acid, the interlayer distances decreased, which was unexpected.
The peak position of GO in the XRD patterns is another indi-
cator for determining the degree of oxidation. The oxygen func-
tional groups are located at the edges and surfaces of the GO
sheets, which make the GO highly hydrophilic. Upon oxidation, as
the solution pH was increased by washing and removing the salts
and acids, it was changed from acidic to neutral and thus the
surface oxygen functional groups became negatively charged. The
Fig. 5. Degree of oxidation of the first (18 mm) and second sample (6 mm). electrostatic repulsion induced by the negative surface charges of
GO sheets then caused the formation of a stable colloidal graphene
oxide exfoliated sheets solution [14]. Fig. 7 shows a schematic of
the processes.
As mentioned above, in our experiment, despite our expectation
that upon oxidation, the peak of GO should move to lower angles, it
was observed that the GO peaks of the first and second samples had
moved to the higher angles with increasing the oxidation time. This
means that the interlayer distance has decreased with increasing
the degree of oxidation (Fig. 6). Such a decrease was more pro-
nounced for the second sample with smaller particle size. This
result apparently was in contradiction with our expectation and
with the results of previous studies [13,15].
It seemed that during the drying process of GO solution,
restacking of the graphene oxide layers could occur and the GO
crystals could form again. The more the degree of oxidation, the
more the hydrophilic of the GO would be and so the more water
molecules could be trapped in between the sheets during drying,
resulting in a larger interlayer distance. Due to the long oxidation
time, the acids and oxidizing agents broke the graphene oxide
Fig. 6. GO interlayer distance of the first sample (unmilled) and the second sample sheets into sheets with smaller lateral size [16]. Such an effect had
(milled for 5 h). also been observed in carbon nanotubes [17,18].

Fig. 7. Schematic illustration of chemical methods for producing stable aqueous solution of graphene oxide, 1) Oxidation of graphite to GO with larger interlayer distance, 2)
Exfoliation of GO in water and formation of graphene oxide solution.
474 S.S. Shojaeenezhad et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 470e475
Fig. 8. Mechanisms for production of graphene quantum dots: Cutting GO using a modified Hummers method.
Fig. 9. Schematic of the stacking process of graphene oxide sheets on top of each other
and forming the GO crystals, a) sheets with larger lateral size, b) sheets with smaller
lateral size.
At long oxidation time, the degree of oxidation is thus increased,
but the lateral size of the sheets becomes smaller. This fragmen-
tation is developed so that most of the oxygen functional groups are
located at the edges of the sheets (Fig. 8) [19] so the sheets can get
closer.
It has also demonstrated that if more functional groups are
created on the GO sheets' surfaces, the sheets would be rougher
[20]. In fact by decreasing the GO flack's surface area with respect to
the surface edges, the softness and flexibility of the surfaces
decrease [21]. Therefore, the GO sheets with larger lateral size and
thus with more functional groups are expected to have a rougher
and more wrinkled surface. As a result, in the process of drying and
stacking, the sheets with smaller lateral size and rougher surface
seem to exhibit better stacking and lower interlayer distance, while
the rough and wrinkled surface causes the GO sheets with larger
lateral size not to stack well together and thus to have a higher
interlayer distance. Fig. 9 demonstrates such a process schemati-
cally. One can say that there is an optimal oxidation time in Ham-
mers' method, which depends on the size and morphology of the
graphite particles. In lesser time, the oxidation is not completed
and in the longer time the dimension of the graphene oxide flakes
will be less.
3. Conclusion
The oxidation of graphite using the Hummers method was
performed for three samples with different particle sizes and
shapes. It was found that the appropriate oxidation time for
graphite depended on the size and shape of the initial particles.
While the oxidation of the clod samples was completed in several
days, the oxidation of flake powder was completed just within 2 h.
Thus, the oxidation time could be decreased by reducing the par-
ticle size (e.g. by grinding). This means that the small and flakey
particles are more suitable for large scale GO preparation. By
increasing the oxidation time, the GO peaks were also observed to
move to larger angles indicating that the distance between the
layers has reduced. In addition, it was observed that the graphene
oxide sheets were divided into smaller parts so that most of the
functional groups located on the edges and the sheets were smaller
and smoother. The smoother surface allowed the sheets to be
placed at a smaller distance apart in the process of drying, and thus
there would be less distance between the sheets.
Acknowledgments
The authors would like to acknowledge Shahid Chamran Uni-
versity of Ahvaz for the financial support of this work.
References
[1] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. 6 (2015) 183.
[2] Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Graphene and
graphene oxide: synthesis, properties, and applications, Adv. Mater. 22 (2010)
3906.
[3] X. Lu, M. Yu, H. Huang, R.S. Ruoff, Tailoring graphite with the goal of achieving
single sheets, Nanotechnology 10 (1999) 269.
[4] S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nat.
Nanotechnol. 4 (2009) 217.
[5] S. Stankovich, R.D. Piner, X. Chen, N. Wu, S.T. Nguyen, R.S. Ruoff, Stable
aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated
graphite oxide in the presence of poly (sodium 4-styrenesulfonate), J. Mater.
Chem. 16 (2006) 155.
[6] I. Jung, M. Pelton, R. Piner, D.A. Dikin, S. Stankovich, S. Watcharotone,
M. Hausner, R.S. Ruoff, Simple approach for high-contrast optical imaging and
characterization of graphene-based sheets, Nano Lett. 7 (2007) 3569.
[7] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc.
80 (1958) 1339.
[8] S. Park, J. An, R.D. Piner, I. Jung, D. Yang, A. Velamakanni, S.T. Nguyen,
R.S. Ruoff, Aqueous suspension and characterization of chemically modified
graphene sheets, Chem. Mater. 20 (2008) 6592.
[9] L. Shahriary, A.A. Athawale, Graphene oxide synthesized by using modified
Hummers approach, IJREEE 02 (2014) 58.
[10] N.R. Wilson, P.A. Pandey, R. Beanland, R.J. Young, I.A. Kinloch, L. Gong, Z. Liu,
K. Suenaga, J.P. Rourke, S.J. York, J. Sloan, Graphene oxide: structural analysis
and application as a highly transparent support for electron microscopy, Acs
Nano 3 (2009) 2547.
[11] H.K. Jeong, H.J. Noh, J.Y. Kim, M.H. Jin, C.Y. Park, Y.H. Lee, X-ray absorption
spectroscopy of graphite oxide, EPL 8 (2008) 67004.
[12] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev,
L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, Acs
Nano 4 (2010) 4806.
[13] A.G. Bannov, A.A. Timofeeva, V.V. Shinkarev, K.D. Dyukova, A.V. Ukhina,
E.A. Maksimovskii, S.I. Yusin, Synthesis and studies of properties of graphite
oxide and thermally expanded graphite, Prot. Met. Phys. Chem. 50 (2014) 183.
 S.S. Shojaeenezhad et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 470e475
[14] D. Li, M.B. Müller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous dis-
persions of graphene nanosheets, Nat. Nanotechnol. 3 (2008) 101.
[15] A. Ganguly, S. Sharma, P. Papakonstantinou, J. Hamilton, Probing the thermal
deoxygenation of graphene oxide using high resolution in situ X-ray based
spectroscopies, J. Phys. Chem. C 115 (2011) 17009.
[16] L. Zhang, J. Liang, Y. Huang, Y. Ma, Y. Wang, Y. Chen, Size-controlled synthesis
of graphene oxide sheets on a large scale using chemical exfoliation, Carbon
47 (2009) 3365.
[17] D.V. Kosynkin, A.L. Higginbotham, A. Sinitskii, J.R. Lomeda, A. Dimiev,
B.K. Price, J.M. Tour, Longitudinal unzipping of carbon nanotubes to form
graphene nanoribbons, Nature 458 (2009) 872.
475
[18] J. Li, K.N. Kudin, M.J. Mcllister, R.K. Prud'homme, I.A. Aksay, R. Car, Oxygen-
driven unzipping of graphitic materials, Phys. Rev. Lett. 96 (2006) 176101.
[19] T. Fan, W. Zeng, W. Tang, C. Yuan, S. Tong, K. Cai, Y. Liu, W. Huang, Y. Min,
A.J. Epstein, Controllable size-selective method to prepare graphene quantum
dots from graphene oxide, Nanoscale Res. Lett. 10 (2015) 1.
[20] K.A. Mkhoyan, A.W. Contryman, J. Silcox, D.A. Stewart, G. Eda, C. Mattevi,
S. Miller, M. Chhowalla, Atomic and electronic structure of graphene-oxide,
Nano Lett. 9 (2009) 1058.
[21] K. Krishnamoorthy, M. Veerapandian, K. Yun, S.J. Kim, The chemical and
structural analysis of graphene oxide with different degrees of oxidation,
Carbon 53 (2013) 38.