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

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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

method for the oxidation of graphite. Various oxidation times have
Graphene is one of the carbon's allotropes with just one atom been reported by different researchers. Hummers used flaky
thick in which the carbons are formed a honeycomb lattice of SP2 graphite powders and oxidized graphite after half an hour [7]. Park
hybridization bonds [1]. Super electrical and thermal conductiv- et al. [8] oxidized their graphite in 2 h, but they didn't describe
ities, high mechanical strength, high specific surface area and about the shape of the used graphite particles. Shahriary et al. [9]
interesting transport properties such as quantum Hall effect have spent 12 h for graphite oxidation but they also didn't present any
made graphene the most widely considered material, according to data about the shape of the used graphite particles. Wilson et al.
the theoretical and experimental studies [2]. There are many re- oxidized their samples in five days [10]. The lack of the used particle
ports for producing graphene such as the micromechanical exfoli- shape's information has left an open question of what factor is
ation of graphite known as the “Scotch tape” or “peeling” method, responsible for such discrepancy.
chemical vapor deposition, epitaxial growth techniques on non- In this work, we present the effect of initial graphite particle size
conductive surfaces like SiC and also the wet chemical methods [3]. and shape on oxidation time in graphene oxide prepared by
Chemical methods are the most common ways of making gra- Hummers' method. This helps control the oxidation producer,
phene due to their high yield production and control. In addition, which can be useful in large scale production of graphite oxide.
the final products of these methods are a colloidal suspension that
provides a possibility of subsequent modifications such as func- 2. Experimental
tionalization [4]. Due to such features, the chemical methods are
still the best methods for many graphene-based applications. 2.1. Materials
Chemically produced graphene consists of three steps: graphite
oxidation, graphite oxide exfoliation and reduction of the graphene 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.
* Corresponding author. Fax: þ98 6133331040.
E-mail addresses: [email protected] (S.S. Shojaeenezhad), farbod_m@
(Pyeongtaek, South Korea). The second sample was the same but
scu.ac.ir (M. Farbod), [email protected] (I. Kazeminezhad). ball milled for 5 h, and the third sample was a flaky one that was
Peer review under responsibility of Vietnam National University, Hanoi. 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 471

samples. The scanning electron microscopy (SEM) images of the deionized water was added to 25 ml of the suspension and the
samples were shown in Fig. 1 and their particle size distribution mixture was kept at this temperature for half an hour. The resulting
diagrams deduced from particle size analyzer can be observed in suspension was then further diluted with 230 ml of deionized
Fig. 2. The average particle size of the first, second and third sam- water at 40  C, afterward a 30% aqueous hydrogen peroxide (H2O2)
ples were 18, 6, and 25 mm, respectively. was added drop wised until the suspension's color changed to
Potassium permanganate (KMnO4) and sodium nitrate (NaNO3) yellow, indicating the end of the reaction. A 3% hydrochloric acid
were purchased from Samchun pure chemical Co., Ltd. (Pyeong- (HCl) solution was used to wash the suspension and the mixture
taek, South Korea). Sulfuric acid (H2SO4) and hydrochloric acid was centrifuged at 4000 rpm. This procedure was repeated 5 times.
(HCl) were obtained from Merck (Germany). Hydrogen peroxide The remaining sediment (i.e., graphite oxide) was dried at 40  C for
(H2O2) was purchased from Kian kaveh azma (Tehran, Iran). All the 48 h. The same procedure was repeated after 5, 10 and 20 days for
chemicals were research grade and used without any purification. the sample 1.
Deionized water was used throughout the experiment. 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
2.2. Characterization 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
SEM images were taken with a Leo, 1455 VP scanning electron the graphene oxide is illustrated in Fig. 1d. From the figure, it is
microscope. The particle size distributions were obtained using an clear that the graphene oxide sheets obtained by sonication of the
analysette 22 NanoTec (FRITSCH) particle analyzer. The powder X- graphite oxide are in the form of thin, flexible and wrinkled sheets.
ray diffraction (XRD) measurements were performed using a Phi- The XRD patterns were used to evaluate the oxidation of our
lips PW1840 diffractometer with Cu Ka radiation of 1.5418 Å to samples. Jeong et al. [11] have shown that the XRD pattern of
investigate the structural properties. 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
2.3. Preparation of graphene oxide between graphite sheets is about 3.35 Å, which upon oxidation can
vary between 6 and 12 Å, depending on the oxidation time [4].
5 g graphite powder of the first sample and 2.5 g sodium nitrate Figs. 3 and 4 show the XRD patterns of the first, second and third
(NaNO3) were put in a mortar, ground and mixed thoroughly then samples before and after oxidation respectively. As can be observed
transferred into a beaker. 115 ml concentrated sulfuric acid (H2SO4) in these figures, the peaks at approximately 26 are the charac-
was added slowly to the mixture and well stirred up with a mag- teristic peaks of the initial graphite samples and the ones at 10 are
netic stirrer. The temperature was kept below 5  C by immersing the characteristic peaks of graphite oxide.
the beaker in an ice-water bath and 15 g of potassium permanga- The intensity and position of the GO peak in the XRD pattern can
nate (KMnO4) was slowly and continuously added to the solution. be used as an indication of the oxidation degree [12]. It has been
The beaker was then transferred to a bath where the temperature shown that when the partial oxidation of graphite occurs, the XRD
was maintained at 35  C for 3 days. On the fourth day, 75 ml of pattern included either the peaks predicted for graphite (G) or

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.
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.

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
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 The authors would like to acknowledge Shahid Chamran Uni-
lateral size. versity of Ahvaz for the financial support of this work.

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