Facile synthesis of graphene from graphite using ascorbic acid as reducing agent

Eko Andrijanto, Shoerya Shoelarta, Gatot Subiyanto, and Sadur Rifki

Citation: AIP Conference Proceedings 1725, 020003 (2016); doi: 10.1063/1.4945457

View online: http://dx.doi.org/10.1063/1.4945457
View Table of Contents: http://scitation.aip.org/content/aip/proceeding/aipcp/1725?ver=pdfcov
Published by the AIP Publishing

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 Facile Synthesis of Graphene from Graphite Using
Ascorbic Acid as Reducing Agent
Eko Andrijanto, Shoerya Shoelarta, Gatot Subiyanto, Sadur Rifki
Chemical Engineering Department, Bandung State Polytechnic
Email: andrijanto.2002@gmail.com

Abstract. Graphene has attracted a tremendous attention in recent years due to its unique properties such as mechanical,
thermal, optical and electrical properties. However, a large scale production of this material is still an issue and subjected to
intense research efforts. Here, we show a simple and green approach of the graphene synthesis from graphene oxide using
ascorbic acid as reduction agent. A facile synthesis of graphene (rGO) through chemical oxidation of graphite into graphene
oxide (GO) was described using modified Hummers method (Improved Tour Method/ITM). The ITM method does not
produce toxic gas and the temperature of the oxidation is easily controlled using ice bath. The synthesized of graphene oxide
was highly soluble and stable in water. The reduction of graphene oxide into graphene was performed using ascorbic acid
(AA) in mild condition. The combined ITM method and green reduction using ascorbic acid open the avenue of replacing
hydrazine in the reduction of graphite oxide into graphene and may be very important step for bulk production of graphene.

INTRODUCTION
Graphene is monolayer carbon atom with a two dimentional honeycomb lattice that are bonded together by
weak van der Walls force to form graphite. Graphene has been a subject of intense research efforts due to
remarkable properties such as conductive, transparent, flexible and has high tensile stregth which is 200 times
stronger than steel [1]. Potential applications of graphene are very huge from electronics [2], composite
materials [3], solar cell [4], gas sensors [5], drug delivery [6] and supercapacitor [7].

To date, several methods have been known for graphene synthesis including mechanical exfoliation
[2], chemical exfoliation [8], chemical synthesis [9], liquid phase exfoliation [10] and chemical vapour
deposition [11]. The most common use to produce graphene is chemical method (Hummers method). This
method basically uses graphite as starting material. The graphite is oxidized by treatment with KMnO4 and
NaNO3 in concetrated H2SO4 and further being reduced using reducing agent to form graphene [12]. This
Hummers method involve the production of heat and toxic gases NO2 and N2O4 which is known as being toxic
chemicals.

Recently, Tour et al reported the method of producing graphene in large scale by treatment of graphite
with KMnO4 and mixture of H2SO4/H3PO4 with weight ratio of 9:1. This method is called “improved method”
or “Improved Tour Method/TIM”[13]. The advantages of this improved method are simpler procedure, no toxic
gases being produced and higher yield. This method is attractive for large scale production of graphene (rGO)
[13]. The Hummers method is basically producing graphene oxide (GO) and then reducing the graphene oxide
with reducing agent such as including hydrazine, sodium borohydrate, hydrochloric acid and many more. Some
of the reducing agents are consider green such as melatonine, polyphenol of green tea and ascorbic acid.

In present study, we proposed the use of both techniques to produce rGO (reduced graphene oxides).
The combined method is to use Improved Method to produce graphene oxide (GO) and the reducing the GO by
adding ascorbic acid (AA) as know green reducing agent [14].This new approach is open a way to produce
graphene in large scale, easy and green method.

MATERIALS AND METHODS

Materials

Natural graphite powder 100 mesh was purchased from local supplier . All chemical reagents , H2SO4, H3PO4
and H2O2 were analytical grades and purchased from Sigma Aldrich. Ascorbic acid was pharmaceutical grade
and pruchased from local supplier (Bratachem).

The 3rd International Conference on Advanced Materials Science and Technology (ICAMST 2015)
AIP Conf. Proc. 1725, 020003-1–020003-4; doi: 10.1063/1.4945457
Published by AIP Publishing. 978-0-7354-1372-6/$30.00

020003-1
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 GO Synthesis

Graphene oxide (GO) was prepared using Improved Tour Method (ITM) (Tour et al, 2010) which is described
previously [13]. The described method, a mixture of concentrated H2SO4 and H3PO4 with volume ratio of 9:1
(360 ml : 40 ml) was added to a mixture of graphite (3 g, 1 wt equiv) and KMnO 4 (18 g, 6 wt equiv) in 1000 ml
beaker glass and cooled under ice bath to keep the reaction at low temperature and avoid any gas evolved during
the oxidation stage. The mixture was then heated at 50 oC and stirred for 12 h. The reaction was cooled to room
temperature and then poured onto crushed ice ( approx. 400 ml) in 2000 ml beaker glass. The 30% H2O2 (3 ml)
was then added to the mixture and stirred homogenously. DI water (1200 ml) was then added into the solution
and left for 24 h and the slurry was settled down at bottom of the beaker. The supernatant was decanted away
and the remaining solid was added with DI water (1200 ml) and the procedure was repeated three times. The
final solid as a slurry was then dried at room temperature for 3 days to obtain the solid GO and further drying in
an oven if necessary.

Reduced Graphene Oxide (rGO) Synthesis

In this procedure, graphene was synthesised from graphite oxide as explained in the previous section. The
graphene (rGO) was synthesized from graphite oxide (GO) by using ascorbic acid as reductant [14]. A mixture
of GO solution 50 ml (0.1 mg/ml) and 0.1 M ascorbic acid with volume ratio 1:1 was mixed and heated at 70 oC
on heating plate and stirred for 30 min, and the color of the solution changed from bownish yellow to black. The
product was centrifuged at 10000 rpm and supernatant was decanted away and the remaining solid (rGO) was
washed with ethanol and water three times and dried at 120 oC in oven.

Characterizations

The characterization of graphite, GO and rGO was performed by using FTIR and UV-VIS. The reduction effect
of ascorbic acid on GO was observed on Fourier Transform Infra Red Spectroscopy. The reduction was also
monitored using UV-Vis (Shimadzu UV-1800) spectrophotometer. Measurement of GO concentration was
performed by using gravimetic method.

RESULTS AND DISCUSSIONS

FTIR Analysis

Figure 1 shows the FTIR spectra of GO (graphene oxide) and rGO (reduced graphene oxide/graphene). The GO
(graphene oxide) spectrum as shown in Fig.1 shows the peak at 1066 cm-1 is attributed as C-O streching. The
peak at 1288 cm-1 is confirmed as C-O-C bending and C-OH bending is observed at 1587 cm-1. The carbonyl
groups are also shown at 1724 cm-1 as C=O stretching and a broad peak at 3448 cm-1 is attributed as O-H
stretching vibration of the C-OH groups and water content in the material.

FIGURE 1. FTIR spectra of GO (graphene oxide) and rGO (reduced graphene oxide).

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 The rGO peaks show the reduction oxygen-containing groups on GO by ascorbic acid (AA). These peaks were
confirmed by the removal and the reduction of the intensity of the peaks as shown in Fig.1. The peaks in 1066,
1288 and 1724, 3448 cm-1 disapeared and decreased dramatically, this is an indication of the removal of
oxygen-containing functional groups in GO. These rGO spectra observations confirmed that most oxygen-
containing functional groups in the GO were removed although some residual oxygen-functionalities on GO still
present on the rGO surface with weaker intensity after the reduction. The peak at 1605 cm-1 in rGO shows
strong band, this suggests the recovery of sp2 lattice.

UV-Vis Analysis

The graphene oxide (GO) and reduced graphene (rGO) were confirmed by UV-Vis spectroscopy. The spectra
of both materials in water show adsorption peaks at 230 nm. The reduction of GO by ascorbic acid shifted the
rGO peak to higher adsorption 270 nm. This higher absorption peak shows that the aromatic conjugation of
graphene sheets is re-established after the reduction and also confirming that the GO is being reduced into rGO.
Recovery of the electronic conjugation in rGO is very important and this contribute to the properties rGO. The
previous work ( ) confirmed that the ratio of ascorbic acid (AA) and GO determined the speed of reaction and
optimizing the reduction capability. However, the variation of AA and GO ratio was not studied in this work.

FIGURE 2. UV-Vis spectra of GO (graphene oxide) and rGO (reduced graphene oxide).

CONCLUSIONS
In summary, graphene was successfully synthesized through the reduction of graphite oxide (GO) by using
ascorbic acid (AA) as reduction agent. The Improved Tour Method offers large scale production of GO in easy
and more controlled condition. The graphene product was very high yield compared with other methods. The
graphene product was confirmed by using FTIR and UV-VIS spectroscopy and showed the evidence of
graphene oxide and graphene. The ascorbic acid is able to compete in term of reducing capability with other
reducing agent such as hydrazine which is mostly toxic and expensive.

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 ACKNOWLEDGEMENTS
Authors thank the Research and Technology Higher Education Ministry of Indonesia and The
Bandung State Polytechnic for their financial support through the project.

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