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Procedia Engineering 184 (2017) 469 477

Advances in Material & Processing Technologies Conference

Synthesis of Graphene Oxide using Modified Hummers Method:

Solvent Influence
N.I. Zaabaa, K.L. Fooa,*, U. Hashima,d, S.J.Tanb,c, Wei-Wen Liua, C.H. Voona
a
Institute of Nano Electronic Engineering (INEE), Universiti Malaysia Perlis (UniMAP), 01000 Kangar, Perlis, Malaysia.
b
Faculty of Engineering Technology, Universiti Malaysia Perlis (UniMAP), Level 1, Block S@, Campus UniCITI Nature, Sungai Chuchuh, 02100
Padang Besar, Perlis, Malaysia.
c
Center of Excellence Geopolymer and Green Technology (CEGeoGTech). School of Material Engineering, Universiti Malaysia Perlis (UniMAP), 77
Pejabat Pos Besar, 01007, Kangar, Perlis, Malaysia.
d
School of Microelectronic Engineering (SoME), Universiti Malaysia Perlis (UniMAP), Perlis, Malaysia.

Abstract

The aim of this study is to study the influence of different solvents on the structure and electrical properties of graphene oxide.
GO was obtained from graphite flakes by using modified hummers method in which different from conventional hummers
method. In this method, the experiment was synthesized without sodium nitrate (NaNO 3) and ice bath, but carried out at room
temperature. Prepared GO powders were then dissolved into different solvents, namely acetone and ethanol. Then spin-coated
onto silicon wafer and IDE to produce acetone-GO (A-GO) and ethanol-GO (E-GO). SEM result shows that several square
micron GO were obtained. In addition, due to the large agglomerates and contact between the flakes in E-GO sample, current-
voltage pattern indicated the E-GO produced higher current flow than A-GO. Meanwhile, GO characterized using FTiR shows
that both samples contain several functional groups such as hydroxyl, epoxy, carboxyl and carbonyl. Besides that, due to the
lower diffraction peak of A-GO, XRD result shows the interlayer spacing of A-GO sample is slightly higher than E-GO sample.

2017Published
2017 The Authors. Published
by Elsevier Ltd.by Elsevier
This Ltd.access article under the CC BY-NC-ND license
is an open
Peer-review under responsibility of the organizing committee of the Advances in Material & Processing Technologies
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review under responsibility of the organizing committee of the Advances in Materials & Processing Technologies Conference
Conference.

Keywords: Graphene oxide; modified hummers method; electrical characteristic; structure characateristic; functional group

*
Corresponding author. Tel.: 04-9798580/81/82; fax: 04-9798578.

1877-7058 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review under responsibility of the organizing committee of the Advances in Materials & Processing Technologies Conference
doi:10.1016/j.proeng.2017.04.118
470 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477

E-mail address: klfoo@unimap.edu.my

1. Introduction

Single atomic plane layer of graphite called graphene[1]. Graphene can produce from graphite using by chemical
vapor deposition (CVD), mechanical or chemical method[2,3]. Through the discovery of graphene, many
researchers became interested to do research in this two-dimensional(2D) carbon, as to discover its properties,
characteristic and improve device in future[4]. Until now, graphene become hot topic and potential materials in huge
number of applications.As compared to other carbon materials, graphene contain higher mobility (200000cm 2 v-1 s-
1
)[5,6], young modulus (1TPa) [7] and thermal conductivity (4.84x103 to 5.30x103 W/mK)[8] which make it as a
potential material in sector transistor element and integrated circuit [9],storage energy[10], gas sensor[3] and bio
electronic sensor[11]. During the oxidation process, sp3 bonding are heavily interrupted and make electrical
conductivity of GO drastically decrease compare to graphene[12]. X. Huang et al[12] concluded based on their
experiment, the temperature of GO related with conductivity of GO. The preparation of GO can modified to produce
certain functionalized GO which has lower or higher conductivity properties than pristine graphene [13,14].

Graphite oxide can be exfoliated using any organic solvent to form GO and produce different form dispersion
with different long-term stability and thickness of single layer GO. Four type of organic solvent such as DMF,
NMP, THF, and ethylene glycol can form single layer of GO sheet same when used water [15]. According to T.
Kavinkumar et al[16],due to containing more sp3 but less sp2 carbon atom, GO become a nonconductive element.
Defect of sp3 bonding and various oxygen functional groups that attached on basal planes and edges can be
generated during intercalating with organic solvent. Therefore, S. Ray et al[17] declare that due to sp3 bonding
feature, the functional group on the GO surface might affect the conductivity of GO. Due to elimination/removal of
oxygen functional group, electrical conductivities of GO increased[18]. However, by oxidation of graphene, O.
Moradi et al complete the improvement on conductivity of graphene oxide from 0.005 S/m to 0.14 S/m by using
conductive-meter in aqueous solution at 35oC [14]. From statement above shows that graphene consists of high
young modulus. On the other hand, due to oxygen functional group of GO, monolayer GO only consists of low
young modulus (207.6 23.4Gpa) [7,18]. Similar to electrical conductivity, thermal conductivity of GO is lower
than graphene due to functional group and presence of defect[20]. It can be concluded that functional group might
affect the electrical and thermal conductivity of GO. Therefore, graphene and GO are rapidly increased attraction
by the researchers in various fields[21]. After discovered on graphene and GO, many potential applications are
under development and proposed, such as biosensor[22],gas sensor [23] and supercapacitor [24]. Besides that, GO
functionalized with epoxy, hydroxyl, carboxyl, and carbonyl group play an important role for interacting with gas
molecule[23], DNA[25], and enzyme[26]. Based on H. Hsu et al [27], interlayer spacing of GO increasing due to
oxygen functional group make GO high specific surface area, high mesopore volume, and certain level of electrical
conductivity. Interdigitated electrode (IDE) currently used onto molecular [28], gas[18], acoustic and MEMS [29]
sensor. Variety sensor has been optimized by synthesis material onto IDE.

British chemist B.C. Brodie was the first researcher that discover properties of graphite oxide[30]. Since then,
graphite oxide became popular among researcher because of interesting in unique properties of graphite oxide. Due
to limitation of data, research about graphite oxide still currently on going on by researchers from all around the
world. In Brodie method, ratio of 1:3 of graphite and potassium chlorate (KClO 3) were mixed and reacted with
fuming nitric acid (HNO3) in 3 or 4 days with 60oC [30]. In year 1898, L. Staundenmaier improved the work of
Brodies method by exchange two-third of fuming HNO3 to sulfuric acid (H2SO4) and used multiple aliquot of
KClO3 the reaction occurs[31]. However, it caused hazard because of addition of KClO3 which caused continued
explosion and took four days for this reaction[32]. After 40 years, L. Staundenmaier discover new method, which
was more practical and simplified. Since it doesnt need repeat 4 times of oxidations process[33]. After that, chemist
Hummer and Offeman introduced their method that currently often used by the researches to produce graphite oxide
in 1958[34]. In this method, 100g of graphite powder, 50g of sodium nitrate (NaNO3), 2.3-liter sulfuric acid and
300g potassium permanganate (KMnO4) were used in oxidation process. In hummers method, KMnO 4 used to
replace KClO3 to avoid spontaneous explosion during oxidation process while NaNO 3 replaced fuming HNO3 to
 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477 471

eliminate fog acid produced. This process takes just in few hours to produce high quality of GO. Besides that,
Hummers method produce more amount of oxygen than the Brodies method [35]. However, hummers method
still have flaws [36], whereby it produce toxic gas such as NO2 and N2O4 [33].

GO and graphite oxide can be produced by similar in chemical process but different in its structure[37]. Graphite
oxide can be described as group of layers graphene oxide[38]. Furthermore, exfoliation of graphite oxide would
produce single layer sheet of graphite oxide which call GO[39]. Many thermal and mechanical methods exist to
exfoliate graphite oxide to GO, but sonication graphite oxide into wafer or organic media is common method used
because of faster than other method. The older method is rapidly heat graphite oxide hundred degrees in inert
atmosphere[2]. This method caused explosive thermal reduction of material, large amount of CO2 and H2O between
spaces of graphite layers[40].

Marcano et al [41] had completed the study on different between hummers method, modified hummers method
and improved hummers method without NaNO3. As we know, oxidation using NaNO3 would emit toxic gasses.
Therefore, improved hummers method replaced the use of NaNO 3 with H2SO4, H3PO4 and double the amount
KMnO4. In addition, his improved hummers method gives other advantages such as more hydrophilic carbon
material, equivalent conductivity and no toxic gasses emitted and finally attract in large producing GO[41].

2. Experimental procedure

2.1 Preparation of graphene oxide by a modified hummers method

In typical procedure, graphene oxide (GO) was produced using modified hummers method from pure graphite
powder. In this method, 27 ml of sulfuric acid (H 2SO4) and 3 ml of phosphoric acid (H3PO4) (volume ratio 9:1) were
mixed and stirred for several minutes. Then 0.225 g of graphite powder was added into mixing solution under
stirring condition. 1.32 g of potassium permanganate (KMnO4) was then added slowly into the solution. This
mixture was stirred for 6 hours until the solution became dark green. To eliminate excess of KMnO 4, 0.675 ml of
hydrogen peroxide (H2O2) was dropped slowly and stirred for 10 minutes. The exothermic reaction occurred and let
it to cool down. 10 ml of hydrochloric acid (HCl) and 30ml of deionized water (DIW) was added and centrifuged
using Eppendorf Centrifuge 5430R at 5000 rpm for 7 minutes. Then, the supernatant was decanted away and the
residuals was then rewashed again with HCl and DIW for 3 times. The washed GO solution was dried using oven at
90 C for 24 hours to produce the powder of GO.

2.2 Preparation of graphene oxide solution

To produce acetone graphene oxide (A-GO) and ethanol graphene oxide (E-GO) samples,1 mg of GO were
dissolve in 1 ml of acetone/ethanol solution (volume ratio 1:1) under ultrasonic for 1 hour. 100 l of A-GO/E-GO
solution were then dropped on silicon wafer and spin at 2000 rpm for 20 second. The coated sample were then
heated on the hot-plate with 80 C for 10 minutes. This step was repeated for 10 times. Same coating process was
done on interdigitated electrode (IDE) sample, which was mainly for electrical properties study.

Figure 1: Schematic illustration of IDE functional by GO

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2.3 Characterization of acetone and ethanol graphene oxide

The morphologies of sample were observed by SEM model Jeol JSM-6010LV at the magnification of 500 X and
10 kX with accelerating voltage of 20 kV. Meanwhile, XRD Siemens Diffractometer Model D-5000 using Cu K
radiation (=0.14406n) source in /2 mode was used to investigate the composition of specimens. Measurements
were made with fast duration scan 5/min from 10 - 80. FTIR (Perkin-Elmer spectrum 65 FT-IR) was used to scan
the samples from 650 to 4000 cm-1. Electrical characterization was conducted using Keithley 6487 picoammeter,
where the IDE electrodes were connected using 2 point probes in purpose for electrical conductivity differences
between A-GO and E-GO. The difference of electrical conductivity is defined by biasing 2 V through the IDE
coated GO and graphically illustrated.

3. Result and discussion

3.1 SEM

Figure 2: SEM image of the samples (a) A-GO; (b) E-GO

The morphology of both samples were determined by SEM. Fig. 2 shows the distribution of GO on the device at
500 X magnification. The working distance is approximately 10 mm at high vacuum mode with 20 kV. From the
image shown in Fig. 2, GO dissolved in acetone (A-GO) shows comprehensive extensive spread on the silicon
surface, while E-GO sample looks clustered on the entire surface. This phenomenon might due to the GO was fully
dissolved in acetone but partially dissolved in ethanol solvent. After sonication, GO fully dissolved in acetone while,
ethanol act as non-solvent

Figure 3: SEM image of the samples (a) A-GO; (b) E-GO

 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477 473

Fig. 3 shows on same samples but at higher magnification (10 kX). The similar result was founded by Li et. al
[42]. Besides that, morphology of E-GO structure appeared in large agglomerates but A-GO seemed to be scattered
on silicon wafer. These might further affect the flow of current through the IDEs fingers.

3.2 XRD

In this analysis, XRD was used to determine the crystal structure and verify the interlayer spacing of A-GO and
E-GO. The XRD pattern of A-GO and E-Go are presented in Fig. 4. The peak for both A-GO and E-GO samples
shown in Fig. 4 is slightly different. Whereby the A-GO sample exhibits peak at 11.7o meanwhile E-GO sample at
12.3o. Both results show the diffraction peak at ~10 o due to (002) plane of GO[43]. The interlayer spacing of GO can
be calculated according to the bragg law [44]:

(1)

where n is the diffraction series and is the X-ray wavelength. Interlayer spacing () of A-GO and E-GO was
0.75nm and 0.71nm by Bragg equation. Both interlayer spacing slightly different although same GO used but
different solution used. Increasing of interlayer spacing because of intercalated functional group of oxygen and
water molecule into carbon layer structure[45]. Besides that, it is also related to the weaker van der waals bonding
formed by epoxyl, hydroxyl, carbonyl and carboxyl group on the basal planes[46]. Usually, interlayer spacing d of
graphene oxide is at the range of 0.6-1.0nm and it controlled on the degree of oxidation of graphite and amount of
water molecules intercalated into interlayer spacing[47]. According to the literature, once the graphite is oxidized
and become GO, the XRD peak should shift from ~26 o to ~11o. However, there is no sharp peak appeared in the
XRD result shown in Fig. 4 but gives a very broad range from ~10 o to ~25o. This might due to the graphite was
incompletely oxidized using this method.

Figure 4: XRD pattern of A-GO and E-GO

474 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477

Figure 5: FTiR spectrum of E-GO and A-GO

3.3 FTIR

Fig. 5 shows the FTiR spectra of A-GO and E-GO samples. FTiR used to investigate the bonding interactions in
both samples. The result indicates that both A-GO and E-GO consist of carbonyl C=O, aromatic C=C, carboxyl C-
O, epoxy C-O-C and hydroxyl O-H, whereby peak at 3250cm-1 and 3125cm-1 are corresponding to the O-H
(hydroxyl) groups[48]. The band in between 2800cm-1 and 3200cm-1 represent the hydroxyl group in GO network,
which reduce the intensity after a sulfanilic acid treatment[49]. The band between 3000cm-1 and 3800cm-1 represent
as hydroxyl , as those reported in previous work[50,51]. While peak at ~2300cm-1 is corresponded to the peak for
absorbed CO2 molecules[52]. On the other hand, broad peak 1418.6 cm-1 and 858.23 cm-1 are corresponded to C=C
bond (aromatic group)[46,52,53]. T. Sakthivel et al declared as C-O (carbonyl and carboxyl moities) group at band
~1568cm-1 [55]. Besides that, band between 1106.3cm-1 and 1005.2 cm-1 is corresponded to C-O-C (epoxy)
groups[53]. All the peak shows the functional group existed in A-GO and E-GO samples. It can assume graphite
powder successfully oxidizing with concentration acid with KMnO 4.
 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477 475

3.4 I-V

Figure 6: The I-V curve of the two sample

Interdigitated electrode (IDE) was used for electrical test. The total saiz of IDE is 7x4 mm and consists 10
fingers. The width and length each finger are 0.1 mm and 3.75 mm, respectively. The spacing between 2 fingers is
100 m. The electrical test were carried out using picoammeter/voltage source unit at room temperature. Current
versus voltage (I-V) analysis was done in the range form 0V to 2V. Fig. 6 shown that a very weak current singal
occur. The ultra low current show in Fig. 6 indicated that produced GO just act like an insulator. This might due to
the sp2 bonded graphitic structure was distrupted by the electronegative oxygen in oxygen functional group[56]. Fig.
6 also shows that current flow for A-GO is weaker than E-GO, which indicated that E-GO performs conductivity.
However, current-voltage pattern indicated that the conductivities of GO are slightly different between two samples.
E-GO has higher current flow than A-GO because of the contact between the flakes GO as shown at SEM.

4. Conclusion

We applied improved hummers method in our experiment as to produce graphene oxide, and different from
conventional hummer method because synthesis graphene oxide without using NaNO 3. It shows that, NaNO3 does
not affect the synthesis method to produce graphene oxide. Without using NaNO 3 still produce same characteristic
of GO. This method can decrease coast and free toxic gases. Ethanol and acetone used to perform liquid medium of
GO. Ethanol and acetone slightly affect the result of the synthesis of GO. Ethanol has advantages more than acetone
in form of conductivity of electrical and solubility of GO. Conductivity of sample effected through morphology of
GO. These finding is confirmed by the SEM, XRD result, FTIR spectre and I-V curves. Morphology of E-GO
structure appeared in large agglomerates but A-GO seemed to be scattered on silicon wafer. E-GO has higher
current flow than A-GO because of the contact between the flakes GO as shown at SEM. In FTIR spectre both
sample contain several functional groups such as hydroxyl, epoxy, carboxyl and carbonyl. Besides that, due to the
lower diffraction peak of A-GO, XRD result shows the interlayer spacing of A-GO sample is slightly higher than E-
GO sample.

Acknowledgements

The authors are grateful to the Department of Higher Education, Ministry of Higher Education, Malaysia for
funding this research through the Fundamental Research Grant Scheme (FRGS) with the grant number 9003-00465.
The author also would like to acknowledge all the team members in Institute of Nano Electronic Engineering
(INEE), Universiti Malaysia Perlis (UniMAP) for their guidance and help.
476 N.I. Zaaba et al. / Procedia Engineering 184 (2017) 469 477

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