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Purification and Preparation of Graphite Oxide

from Natural Graphite
CONFERENCE PAPER OCTOBER 2014

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THE 4th INTERNATIONAL CONFERENCE ON THEORETICAL AND APPLIED PHYSICS (ICTAP-2014)

16-17 October 2014, Denpasar-Bali, Indonesia

Purification and Preparation of Graphite Oxide from

Natural Graphite
C. Panatarani1, a, I. M. Joni and N. Muthahhari
Lab. of Instrumentation System and Functional Material Processing, Physics Department, Padjadjaran University,
JL. Raya Bandung-Sumedang KM 21, Jatinangor, 45363, Jawa Barat, Indonesia.
a
c.panatarani@phys.unpad.ac.id
Abstract. Graphite oxide has attracted much interest as a possible route for preparation of natural graphite in the largescale production and manipulation of graphene as a material with extraordinary electronic properties. Graphite oxide
was prepared by modified Hummers method from purified natural graphite sample from West Kalimantan. We
demonstrated that natural graphite is well-purified by acid leaching method. The purified graphite was proceed for
intercalating process by modifying Hummers method. The modification is on the reaction time and temperature of the
intercalation process. The materials used in the intercalating process are H2SO4 and KMNO4. The purified natural
graphite is analyzed by carbon content based on Loss on Ignition test. The thermogravimetric analysis and the Fourier
transform infrared spectroscopy are performed to investigate the oxidation results of the obtained GO which is indicated
by the existence of functional groups. In addition, the X-ray diffraction and Energy dispersive X-ray spectroscopy are
also applied to characterize respectively for the crystal structure and elemental analysis. The results confirmed that
natural graphite samples with 68% carbon content was purified into 97.68 % carbon content. While the intercalation
process formed a formation of functionals groups in the obtained GO. The results show that the temperature and reaction
times have improved the efficiency of the oxidation process. It is concluded that these method could be considered as an
important route for large-scale production of graphene
Keywords: Natural Graphite, Acid Leaching Method, Modified Hummers Method, Graphite Oxide, Graphene.
PACS: 81.05 uf

INTRODUCTION
Graphite has been intensively studied not only
because it shows good properties in heat resistance and
electrical conductivity, and has been used as the
materials for high-efficient secondary batteries,
lubrication, etc, but also as a prime materials for
graphene fabrication. Graphene is the name given to a
flat monolayer of carbon atoms tightly packed into a
two-dimensional (2D) honeycomb lattice [1].
Besides an efficient processing methods, largescale production of graphene can be attained by the
abundant availability of raw graphite and Indonesia is
a country which is rich in natural resources such as oil,
gas, coal and various minerals, including graphite. So
the availability of raw materials is a great potential to
be utilized.
Production of graphene on a large scale is usually
performed by chemical methods, by oxidizing purified
graphite into graphite oxide (GO). GO is an
amphiphilic carbon material that is not conductive and
a precursor material of graphene which is can be
obtained by exfoliation of GO [2]. In the chemical
method, the quality and quantity of GO in maintaining
the structure of sp2 when the oxidation process is
crucial to success in producing graphene [3]. Because

the study was used raw natural graphite, this study

only focused on purification process to obtained a
graphite with good purity and see the effectiveness of
the modified Hummers method to the purified graphite
in obtaining GO.

EXPERIMENT
Experiments in this study include natural graphite
purification process using acid treatment and GO
synthesis by using modified Hummers method

Preparation of Graphite Purification and

Synthesis of Graphite Oxide
The sampel used is natural graphite from West
Kalimantan. Through the process of milling and
flotation, samples were obtained in the form of natural
graphite powder (NGP) with a particle size < 149 m.
Furthermore the samples were used for analysis of the
purity of graphite

THE 4th INTERNATIONAL CONFERENCE ON THEORETICAL AND APPLIED PHYSICS (ICTAP-2014)

16-17 October 2014, Denpasar-Bali, Indonesia

HF Leaching
Seperately, 5 grams of NGP washed in a solution
containing of 10, 20 and 30 % of HF (25 ml of each
solution) at each different temperature (room
temperature, 60-65 C and 90-95 C) for 2 hours. Then
the solids filtered and neutralized with distilled water
until its pH is 7. The process is done through the
process of stirring and vacuum filtration. Resulted
material dried at 100 C for 14 h and then the sample
used for analysis of the purity of graphite.

Gradual Leaching
200 grams of NGP is leached in its best conditions
correspond to HF leaching results and re-leached in
solutions of 30 % HF at room temperature for 24 hours
and 20 % H2SO4 for 3 hours, respectively. Then the
solids filtered and neutralized (pH 7) with distilled
water. The process is done through the process of
stirring and vacuum filtration. Resulted material called
leached graphite powder (LGP), dried at 100 C for
14 h and then the sample used for analysis of the
purity of graphite.

Thermal test conducted by thermogravimetric

analysis (TGA) in nitrogen atmosphere with heating
rate of 10 C/min from 30 to 900 C.
Elemental analysis was conducted by using the
Energy-Dispersive spectrometers& JED AnalysStation
2300.

RESULTS AND DISCUSSION

Purity of Graphite Sample
Based on the data of elements that presented in
Table 1, we determined the type of acid that used for
the leaching process for NGP. Silicon as the main
impurities can be effectively reduced by using HF.
Figure 1(a) shows the effect of HF concentration at
different temperatures in increasing the carbon content
of the samples NGP. The significant increased of
carbon content of purified NGP, meaning that leaching
using HF as the finishing process is very necessary.

100

Room Temperature

60-65 C

90-95 C

(a)

25

35

90

80

70

60
0

10

15

20

30

HF%

120

Gradual Leaching

(b)

110
100
C%

In conditions of low temperature, 10 grams LGP

(97.68% purity, ~ 37 m) were mixed and stirred with
230 ml of concentrated H2SO4, and 5 grams of NaNO3
for 60 minutes in the ice bath. 30 grams of KMnO 4
was added slowly to the solution for 2 hours to keep
the temperature did not exceed 20 C. The solution
was continuously stirred for 1 hour. The solution was
heated to a temperature of 35 C and continuously
stirred for 1 hour. Then, the solution is heated to a
temperature of 45 C without stirring for 1 hour. Add
dropwise 460 ml of distilled water for 15 minutes to
keep the reaction temperature did not exceed 98 C.
Finally, oxidation reactions was terminated with the
addition of 1.4 l of distilled water and 100 ml of 30%
H2O2. The solid obtained was washed repeatedly with
a solution of 5% HCl and distilled water and then
dried at 60 C for 12 hours.

C%

Synthesis of Graphite Oxide

90
80
70

Characterizations

60
0

Loss-on-ignition test of NGP and LGP were

obtained by using Ney Vulcan D-130 furnace with a
heating rate of 30 C/min from 30 C to 1000 C.
XRD patterns of NGP, LGP and GO were obtained
by using PANalytical X'Pert diffractometer with CuK radiation source = 1.5406 .

10

15
20
Acid%

25

30

35

FIGURE 1. (a) Effect of HF concentration on upgrading the

carbon content in different temperature conditions. (b)
Gradual leaching of HF 20 vol.% (T = 60-65C, t = 2 h), HF
30 vol.% (T = Room Temperature, t = 24 h), and H2SO4 20
vol.% (T = Room Temperature, t = 3 h).

THE 4th INTERNATIONAL CONFERENCE ON THEORETICAL AND APPLIED PHYSICS (ICTAP-2014)

16-17 October 2014, Denpasar-Bali, Indonesia

7000

to the increasing of carbon content (see Figure 1).

Nevertheless, at room temperature, the higher the
concentration of HF, the higher the carbon content
obtained. Based on these, to get better results then we
also done the repeated leaching which the result is
shown in Figure 1(b). The final result obtained
graphite sample (LGP) has 97.68% of carbon content.

NG

5000

LGP

4000
3000

Crystal Structure of NGP and LGP

2000

GO

1000
0
0

20

40

60

80

100

2 (deg)

FIGURE 2. XRD spectra of NGP, LGP and GO

Purified NGP with the highest purity (93.84%) level

was obtained at the conditions of temperature of 60-65
C with concentration of 20 % of HF solutions. This
result indicated that the temperature is very influential
to the effectiveness of HF. Moreover, use a high
concentration of HF is not always directly proportional
TABLE 1. Element Contains of NGP
Element
Carbon
Oxygen
Magnesium
Aluminum
Silicon
Potassium
Calcium
Titanium
Iron
Copper

The crystal structure of the graphite that would be

used to synthesize GO is very important to be analyzed
first, because GO is a material in the intermediate
phase between graphite and graphene, where graphene
as the ultimate goal can be obtained only by
exfoliation of GO that maintain its crystal structure of
graphite through chemical method. However, in this
study the calculation of the degree of crystallinity
based on the data shown in Figure 2 shows the degree
of crystallinity of samples LGP which is quite low that
is 27.12%. The calculation of the degree of
crystallinity was performed using X'Pert Highscore.

Weight %
2.577
2.372
0.123
0.177
0.392
0.150
0.130
0.000
0.336
0.000

Weight %
68.456
25.667
0.062
0.846
4.294
0.195
0.138
0.000
0.340
0.000

Chemical Structure of GO
Because the functional groups of GO decomposed
by heat, the thermal stability of functional groups of
GO can be identified through TGA. Figure 3 shows a
decreased in the mass of the GO samples that are fairly
consistent and depleted at temperatures below 900 C
and a decreased in the LGP sample mass has been
depleted before it reaches the temperature of 625 C.
A sharp decrease in the mass about 25-30 wt% in the
sample GO, occurs in the temperature range between
40-100 C is due to unstable functional groups of
carboxyl and carbonyl that are located on the edge of
GO sheets. However, relatively we can observe that
the GO sample has a good thermal stability because its
ability in maintaining its mass above 20 wt% at
temperatures above 800 C due to the bonding of the

Atomic %
75.942
21.376
0.034
0418
2.037
0.066
0.046
0.000
0.081
0.000

epoxy and hydroxyl functional groups that bind stably

between the sheets in GO [3].
120
100

Weight (%)

Intensity (counts)

6000

LGP

80

GO

60
40

20
0

200

400
600
Temperature ( C)

FIGURE 3. TGA spectra of LGP and GO.

800

1000

THE 4th INTERNATIONAL CONFERENCE ON THEORETICAL AND APPLIED PHYSICS (ICTAP-2014)

16-17 October 2014, Denpasar-Bali, Indonesia

0.9

819.7
1082.0

1634.5

0.7
0.6
0.5
0.4

3418.1

0.3

Transmittance (%)

0.8

GO

synthesized GO and can not be exfoliated into

graphene layer. However, the TGA and FTIR data
showed that the synthesized GO samples showed the
formation of functional groups that are thermally
stable and even able to maintain its mass exceeds the
mass of LGP.

CONCLUSION

0.2

LGP
400

1000

1600
2200
2800
Wavenumber (cm-1)

0.1
3400

0
4000

FIGURE 4. FTIR spectra of LGP and GO

FTIR spectra were used for further investigations

of the chemical structure of the GO samples. Peaks at
Figure 4 shows the formation of functional groups that
exist in the GO samples. Peak of 3418.1 cm-1 due to
the vibration of the hydroxyl group, indicating the
presence of adsorbed water molecules and OH
functional group. Peak of 1634.5 cm-1 indicated the
formation of aromatic ring due to the stretch vibration
of C = C. Peaks of 1082 cm-1 and 819,7 cm-1 indicated
the formation of ester and aromatic ring due to the
vibration of C H respectively [4].
The small amount of functional groups that are
formed when compared to the ideal GO [5] showed
that the oxidation rate is still low. This is reinforced by
the value of carbon to oxygen atoms ratio through the
investigation results of EDS at Table 2 which is about
3,19, whereas according to Hummers [6] the ideal
ratio of carbon to oxygen atoms in a graphite oxide is
2.1-2.9. In addition, the XRD spectra in Figure 2 also
did not indicated any changes in the interlayer distance
of GO samples due to the disappearance of peaks in
the range between 12 -13 at 2 axis [7].
TABLE 2. Element Contains of GO
Element
Weight%
Carbon
69.367
Oxygen
28.913
Magnesium
0.000
Aluminum
0.447
Silicon
0.664
Potassium
0.192
Calcium
0.092
Titanium
0.166
Iron
0.157
Copper
0.000

Atomic%
75.630
23.666
0.000
0.217
0.310
0.064
0.030
0.045
0.037
0.000

Based on the analysis of crystal and chemical

structure that have been presented, it can be concluded
that the graphite samples used in this study is an
amorphous graphite and it resulting to an unoptimal

This study reveals that the impurity contained in

the NGP can be effectively reduced by acid leaching
treatment of 20% HF solution at temperature of 6065 C. This method used a lower acid concentration
and temperature when compared to the previous
similiar study [8]. XRD spectra showed that the NGP
has a low degree of crystallinity and resulted no
change of the interlayer distance of GO, indicated by
the disappearance of peak between 12 - 13 at 2 axis.
Modified Hummers method in this study can
effectively oxidized the NGP into GO with formation
of some thermally stable functional groups. Therefore,
by using the same methods and selecting graphite
samples with a good crystalline structure may result to
graphite oxide that can be exfoliated so that will allow
the production of graphene.

ACKNOWLEDGMENTS
Acknowledgments should be positioned at the end
of the paper before the reference section. The text of
the acknowledgments is in 10 point font.

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