Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Reduction of graphene oxide by Phyllanthus Emblica as a reducing agent

– A green approach for supercapacitor application
D.R. Madhuri a, K. Kavyashree a, Ashok R Lamani a,⇑, H.S. Jayanna a, G. Nagaraju b, Shridhar Mundinamani c
a
Department of PG Studies and Research in Physics, Kuvempu University, Jnana Sahyadri, Shankaraghatta, Shivamogga 577451, India
b
Department of Chemistry, Siddaganga Institute of Technology, Tumakuru 572103, India
c
Department of Physics, Siddaganga Institute of Technology, Tumakuru 572103, India

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

Article history: In recent days the green approach of preparing reduced graphene oxide using plant extracts has attracted
Available online xxxx more attention among the research fraternity over the orthodox way of using chemicals. The green
approach carries advantages like low cost and environmentally friendly nature. Here in this study, the
Keywords: reduction of graphene oxide is carried out using Phyllanthus Emblica, commonly known as amla. This
Graphene oxide fruit is grown in almost every part of the country, and is rich in vitamin C (478.56 mg/100 mL). The
Reduced graphene oxide advantage of using Vitamin C is, it is composed of only carbon, oxygen and hydrogen. Thus minimizing
Green approach
the risk of introducing heteroatoms in the reduced graphene oxide. Also here we have employed a
Phyllanthus Emblica
Supercapacitor
binder-free electrode for supercapacitor application. It is capable of delivering specific capacitance of
123.12 Fg
1 at the scan rate of 5 mVs
1. The characterization techniques performed here on the sample
are powder X-ray diffraction technique, FTIR spectra and Raman spectra which give clear information on
the reduction of graphene oxide. The morphology is studied by SEM images. Electrochemical studies
include cyclic voltammetry, galvanostatic charging-discharging and electrochemical impedance spec-
troscopy. All these studies illustrate that effective results are obtained from the green synthesis of
reduced graphene oxide using Phyllanthus Emblica and it is an efficient and environmentally friendly
method.
Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Web International Con-
ference on Accelerating Innovations in Material Science – 2020.

1. Introduction The capacitance of a device is mainly dependent on the charac-

In the system of the electricity grid, power supply and demand
must be equal at all the moment. Energy storage plays an essential
role in this balancing act and helps to create a more flexible and
reliable grid system. For this purpose, there are various types of
energy storage devices such as batteries, fuel cells, supercapacitors,
etc. Among all these, supercapacitors have the advantage of high
power density, better reversibility, long cycle life, and are much
safer than batteries [1,2]. Supercapacitors are constructed much
like a battery in which there are two electrodes immersed in an
electrolyte with an ion-permeable separator located between the
electrodes. In such devices, each electrode–electrolyte interface
represents a capacitor so that the complete cell can be considered
as two capacitors in series.
⇑ Corresponding author.
E-mail address: ashok1571972@gmail.com (A.R Lamani).
teristics of the electrode material, particularly, the surface area and
the pore size. Due to the high porosity, and correspondingly low
density, it is usually the volumetric capacitance of each electrode
that determines the energy density [3].
Carbon materials are considered as the best material in the
preparation of electrodes for supercapacitors because of their low
cost, functional properties, and commercial availability. There is a
wide range of carbon materials and their electrical property
depends on their structure. Graphite is one of the carbon allotropes
and is naturally found on the earth. Graphene is a two-dimensional
honeycomb structured single atomic layer of sp2 hybridized carbon
atoms. Theoretically, it has an extensive specific surface area
(2630 m2g
1), the thermal conductivity of around 5000 Wm-1K
1
[4], Young’s modulus ~ 1.0 TPa [5], 97.7% of optical transmittance,
and good electrical conductivity. Graphene provides the necessary
possible modification or functionalization of the carbon backbone
[6].

https://doi.org/10.1016/j.matpr.2021.06.173
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Web International Conference on Accelerating Innovations in Material Science – 2020.

Please cite this article as: D.R. Madhuri, K. Kavyashree, Ashok R Lamani et al., Reduction of graphene oxide by Phyllanthus Emblica as a reducing agent – A
green approach for supercapacitor application, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.06.173
D.R. Madhuri, K. Kavyashree, Ashok R Lamani et al.
Graphene oxide (GO) is an exciting material because of its low
cost and easy conversion from GO to graphene. GO contains oxygen
molecules in between carbon layers. It is then reduced to separate
carbon layers into a single layer or few-layer graphene. The Chem-
ical method is the popular method of reduction of GO. The reduc-
ing agents which are commonly used are hydrazine, borohydrides,
and hydroquinones. But the main drawback of this method is that
the chemicals used here are hazardous, highly toxic, corrosive and
combustible. Hence these are not promising for reduction of GO. To
avoid the use of toxic and environmentally harmful reducing
agents, green synthesis to reduce GO is of interest. Clove, cinna-
mon, spinach, carrot root, caffeine, baking soda, etc are used as
reducing agents [7–14].
Phyllanthus Emblica is commonly known as gooseberry has
medicinal value and nutritional reasons to build up lost mental
and physical strength [15]. These are due to the strong antioxidant
property associated with amla fruit. This antioxidant activity is due
to the high content of vitamin C or ascorbic acid present in it. Fruit
juice of amla contains the highest amount of vitamin C
(478.56 mg/100 mL) compared to lime, apple, grapes and pomegra-
nate [16]. Studies suggest that the other components of amla are
sugar, Gallic acid, Flavonoids and polyphenolic compounds. The
ascorbic acid acts as a redox buffer; it reduces and then neutralizes
reactive oxygen species. Using this amla fruit extract as a reducing
agent, we have successfully prepared reduced graphene oxide
(rGO).
2. Experimental
Modified Hummer’s method is implemented to synthesize GO
and the reducing agent used here was amla extract. Fresh fruits
of amla were washed cleanly, the pulp was ground into very small
pieces and DI water was added to it and kept it in a round-
bottomed (RB) flask. The above mixture was kept in a reflux system
for 4 h, filtered the juice using a muslin cloth, transferred it to a
beaker, and kept on a hot plate overnight to get it in a powdered
form. The prepared powder was then poured into DI water (1 mg
in 10 mL DI water) and stirred well until the well-dispersed solu-
tion was formed.
50 mg of GO powder is dispersed in 50 mL of DI water, ultrason-
icated for a period of 40 min. This suspension was thoroughly
mixed with amla extract solution and then kept it on a heating
mantle for 30 min then it was washed with DI water, dried, and
stored.
3. Mechanism
Though amla contains many constituents in it, vitamin C or
ascorbic acid plays a major role in the reduction process. The main
functional groups of GO are hydroxyl, epoxy and carbonyl. The
reaction of the epoxy group with polyhydroxy functional groups
of ascorbic acid leads to ring-opening reaction of the epoxy group.
Propagated by ring expansion due to condensation with loss of
water molecules. Further rearrangement to cause deoxygenation
of GO. Again the condensation is responsible for ring formation
in the case of a hydroxyl group. Then ring cleavage leads to the for-
mation of graphene moiety and eases the green reduction [12]. The
oxidized form of ascorbic acid might form the P - P stacking
between rGO sheets and thereby preventing the agglomeration.
4. Results and discussion
X-ray diffraction studies were employed to investigate the
structure of the prepared sample and to calculate the d-spacing
value. Fig. 1a shows the XRD pattern of GO and rGO. Diffraction
2
Materials Today: Proceedings xxx (xxxx) xxx
peaks corresponding to GO appear at 9.6° and 42.3° (pdf number:
44–558). The characteristic peak of GO is 2h  10° (001 reflection).
The calculated d-spacing of GO is 9.286 nm. The prepared GO was
reduced by amla extract. The diffraction peak for rGO is shifted
from ~ 10° to 26° and d-spacing is reduced to 3.41 nm. This
decrease in d-spacing is due to the removal of oxygen-containing
functional groups between the graphite layers. This peak (2h 
26°) is close to the diffraction pattern of graphite. The appearance
of a broad peak reveals the formation of highly organized few-
layered graphene. The interlayer spacing of the graphene sheet
has a structure similar to that of graphite [17].
The functional group of GO and rGO is studied using FT-IR. Fig. 1b
shows the FT-IR spectra of both GO and rGO. It can be seen that there
is a broad peak at 3426 cm
1 which is due to the presence of O–H
stretching vibration in the hydroxyl group. This peak can also be
found in the rGO spectrum with relatively low intensity. This indi-
cates that the partial removal of the hydroxyl group. Small peaks
at ~ 2900 cm
1 indicate the C–H stretching of heterocyclic com-
pounds. Strong bond at 1623 cm
1 attributes to carbonyl groups in
the molecule. The presence of a peak at 1110 cm
1 indicates the
C–O stretching. The FT-IR spectrum of rGO is quite similar to that
of GO, but it can be seen that the intensity of all the peaks is
decreased. No new bands can be observed after the reduction of
GO. This indicates that amla and its derivatives are completely
removed by the washing of rGO. From these observations, one can
see that most of the oxygen-containing groups GO nanosheets are
removed in the reduction process using amla as a reducing agent.
Raman spectra of GO and rGO are depicted in Fig. 2. The D band
and G band of GO and rGO are appearing at 1347 and 1590 cm
1
respectively. The D band appears due to the structural defects
and disorder, whereas the G band corresponds to E2g mode formed
from the first-order Raman scattering of SP2 carbon atoms. ID/IG
ratio of GO is found to be 0.956 and that of rGO is 1.08. This
increase in the ID/IG ratio after reduction with amla indicates the
disordered domains during the reduction of GO [18]. This change
in the value of ID/IG ratio is in good agreement with the observa-
tions reported for other reducing agents too [10,18–20]. It can be
seen that the 2D band of rGO shifted to 2828 cm
1 in comparison
with GO at 2811 cm
1.
The morphological studies are characterized by SEM. Fig. 3a
shows the SEM image of GO. From these figures, it can be seen that
GO has wrinkled surface morphology. It consists of randomly
aggregated crumpled sheets closely associated with each other.
The wrinkled GO sheets are loosely connected to each other.
Fig. 3b corresponds to rGO, the curl of rGO is significantly reduced
but there is a still wrinkle on the surface. Few layers of rGO are
stacked together. Borders of sheets are partially folded, which sig-
nificantly reduces the total surface energy of the sheets [21]. On
the other hand, the heaping of individual sheets through different
self-assembly techniques develops the surface morphology. This
difference in morphology assures the change in the structure after
reduction.
The electrochemical performance of GO and rGO for superca-
pacitor are studied using cyclic voltammetry (CV), galvanostatic
charging-discharging curve and electrochemical impedance spec-
troscopy (Nyquist plot) in two electrode system. Electrodes are
prepared by pasting the active material on the Whatman filter
paper of dimension 1 cm  1 cm. Whatman filter paper with a
slightly higher dimension was used as a separator.
CV studies of the electrode are carried out in 1 M NaOH solution
and 1 M KCl solution as electrolyte at different scan rates shown in
Fig. 4a and b. The specific capacitance values are calculated by CV
curves using the formula,
R
IdV
Cs ¼ Fg
1 :
2mSDV
D.R. Madhuri, K. Kavyashree, Ashok R Lamani et al. Materials Today: Proceedings xxx (xxxx) xxx

a b
(001)

rGO

Transmittance (%)
Intensity (a.u)

(002)
GO

2852.44
2925.2
GO
rGO

3426.66

1623.46

1110.13

611.7
10 20 30 40 50 60 70 80 90
4000 3500 3000 2500 2000 1500 1000 500
2 Theta (Degree) -1
Wave number (cm )

Fig. 1. (a) XRD pattern of synthesized GO and rGO; (b) FT-IR spectra synthesized GO and rGO.

D capacitance values are calculated at the scan rates 120, 100, 50,
G
25, 10 and 5 mVs
1 and it is found to be 3.906, 4.968, 23.47, 44.5,
97.5 and 123.12, Fg
1 respectively. For 1 M KCl electrolyte, it is cal-
culated for the scan rates 120, 100, 50 and 10 mVs
1 and is found to
be 0.61, 1.423, 1.532 and 7.79 Fg
1 respectively. As the scan rate
increases, the number of ions adsorbed on the surface of the elec-
trode decreases. As a result, the specific capacitance of the material
decreases. All the obtained values of specific capacitance (Cs) of rGO
Intensity (a.u.,)

2D are tabulated below inTable 1

500 1000 1500 2000
Raman Shift (cm-1)
Fig. 2. Raman spectra of GO and rGO.
where I is oxidation or reduction current, m is the mass of active
material on the surface of the electrode, DV is the potential window
and S is the scan rate. The specific capacitance value of rGO is
obtained at different scan rates for 1 M NaOH and 1 M KCl
electrolyte solution. For 1 M NaOH electrolyte, the specific
rGO Among these two electrolytes, the specific capacitance of rGO is
higher for NaOH than that of KCl. This is because the ionic radius of
Na+ ion is smaller than the ionic radius of K+ ion. The ionic radius
plays an important role here. Low ionic radius enhances the
GO diffusion of ions into the electrode. Also, it has enough time to
remove the surrounded water molecules and interact with the
electrode material. Subsequently, the mobility of OH– ion
2500 3000 3500 4000
(20.6  10-5 cm2 s
1 v-1) is greater than the mobility of cl- ion
(7.91  10-5 cm2 s
1 v-1) [22]. One more information is taken from
CV curve. Fig. 4a and b exhibiting quasi-rectangular shapes with no
redox peaks. It says that the carbon materials belong to double layer
capacitor electrode materials, which deliver rectangular CV curve.
The galvanostatic charge–discharge curve is plotted at the cur-
rent density of 1 Ag
1 which is shown in Fig. 4c. The specific capac-
itance is calculated according to the formula Cs = It / mDt. Where I
is the current of charge/discharge, t is the discharging time, m is
the mass of active material and Dt is the discharging time. The
calculated specific capacitance of rGO is 131 Fg
1.

a b

Fig. 3. SEM images of (a) GO; (b) rGO.

3
D.R. Madhuri, K. Kavyashree, Ashok R Lamani et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 1 Fig. 4d shows the Nyquist plot rGO. It demonstrates the behav-
Specific capacitance values of rGO at different scan rates in 1 M NaOH and 1 M KCl ior of the electrode. A nearly vertical straight line is observed at a
electrolyte solutions.
low-frequency region which indicates the good capacitive behavior
Scan rate Cs in 1 M NaOH electrolyte Cs in 1 M KCl electrolyte of electrodes. At the high-frequency region, the semicircular arc is
(mVs
1) (F/g) (F/g) ascribed to the double-layer capacitance, parallelly charge transfer
120 3.9 0.611 resistance at the contact interface between electrode and elec-
100 4.96 1.423 trolyte solution. The impedance spectra is analyzed by fitting an
50 23.47 1.532
10 97.5 7.79
equivalent circuit using Z-view software. The component marked
with Rs is combinational resistance, which is the sum of the inter-
nal resistance of electrolyte and the contact resistance at the active
material. Rct is the charge transfer resistance, Cdl is the double layer
capacitor and W is the Warburg impedance. The fitted values of Rs,

a 120mV/s
b
120 mV/s
0.012 0.000015
100mV/s 100 mV/s
50mV/s 10 mV/s
25mV/s 50 mV/s
0.010 0.000010
10mV/s
5mV/s
0.008
0.000005
Current (A)

0.006
0.000000

0.004 Current (A)

-0.000005

0.002

-0.000010
0.0 0

0 0.0 0.5 1.0 1.5 2.0 2.5 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Potential (V) Potential (V)

c
3.0 1 A/g

2.5

2.0

1.5
Potential (V)

1.0

0.5

0.0
0 100 200 300 400 500 600 700
Time (sec)

e
120

110

100
Retention (%)

90

80

70

60
0 200 400 600 800 1000
No. of cycles

Fig. 4. Electrochemical performance of rGO in two-electrode system (a) CV curves of rGO in 1 M NaOH electrolyte; (b) CV of rGO in 1 M KCl electrolyte; (c) Charging-
discharging curve of rGO (d) Nyquist plot and equivalent circuit of rGO; (e) Cycling performance at 120 mVs
1 scan rate.

4
D.R. Madhuri, K. Kavyashree, Ashok R Lamani et al.
Rct and Cdl are found to be 300 X, 759 X and 19.744 lF
respectively.
Another crucial parameter for supercapacitors is cycle stability
which is shown in Fig. 4e. The cyclic stability of the prepared sam-
ple is tested over 1000 cycles at the scan rate of 120 mVs
1. From
the above shown graph, it can be seen that only 11% loss of specific
capacitance at the end of 1000 cycles.
5. Conclusion
In summery rGO was successfully synthesized by a non-toxic
and environmentally friendly reducing agent. XRD studies give
the structural information of the prepared sample, d spacing of
both GO and rGO ensures the removal of oxygen functional groups.
The functional groups were identified using the FT-IR spectrum.
Raman spectra showed an increase in the ID/IG ratio after the
reduction of GO. This indicates the deformation in the rGO plane.
SEM exhibited the morphological structure of nanosheets. CV stud-
ies were carried out at different scan rates under aqueous 1 M
NaOH electrolyte solution and the specific capacitance of rGO
was obtained as 123.12 Fg
1 at a scan rate 5mVs
1. The Nyquist
plot indicates the capacitive behavior. All these results suggest that
amla extract is a good reducing agent for the reduction of GO.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors thank SIT Tumakuru for carrying out this research
work and providing lab facilities that are having projects under
DST Nanomission. Govt. of India.
Materials Today: Proceedings xxx (xxxx) xxx
References
[1] B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and
Technological Applications, Plenum Publishers, New York, 1999.
[2] A. Balducci, R. Dugas, P. Taberna, P. Simon, D. Plee, M. Mastragostino, S.J.
Passerini, J. Power Sources 165 (2007) 922–927.
[3] A. Burke, M. Arulepp, Batteries Supercaps, 2001, p. 576 (2001) 2–5.
[4] A.A. Balandin, S. Ghosh, W.Z. Bao, I. Calizo, D. Teweldebrhan, F. Miao, C.N. La,
Nano Lett. 902 (2008) 8.
[5] C. Lee, X.D. Wei, J.W. Kysar, J. Hone, Science 321 (2008) 385.
[6] D.W. Boukhvalov, M.I. Katsnelson, J. Phys. Condens. Matter 21 (2009) 344205.
[7] D. Suresh, Udayabhanu, H. Nagabhushana, S.C. Sharma, Mater. Lett 142 (2015)
4–6.
[8] D. Suresh, P.C. Nethravathi, H. Udayabhanu, S.C.S. Nagabhushana, Ceram. Int.
41 (2015) 4810–4813.
[9] T. Kuila, S. Bose, P. Khanra, Ananta Kumar Mishra, Nam Hoon Kim, Joong Hee
Lee, Carbon 50 (2012) 914–921.
[10] V.u. Thu Ha Thi, T.T.T. Tran, H.N.T. Le, P.H.T. Nguyen, Ngoc Quynh Bui, Nadine
Essayem, Bull. Mater. Sci. 38 (2015) 667–671.
[11] M.T.H. Aunkora, I.M. Mahbubula, R. Saidurb, H.S.C. Metselaar, RSC Adv. (2015)
1–32.
[12] S. Thakur, N. Karak, CARBON 50 (2012) 5331–5339.
[13] Z. Khosroshahi, M. Kharaziha, F. Karimzadeh, A. Allafchian, AIP Conf. Proc.
1920 (2018) 020032.
[14] C.M.J. Fernandez-Merino, L. Guardia, J.I. Paredes, S. Villar-Rodil, P. Solıs-
Fernandez, A. Martınez-Alonso, J.M.D. Tascon, J. Phys. Chem. C 114 (2010)
6426–6432.
[15] P. Goel, D. Agarwal, Int. Medico-Legal Rep. J. 3 (2020) 104–107.
[16] B.C. Variya, A.K. Bakrania, S.S. Patel, Pharmacol. Res. 111 (2016) 180–200.
[17] S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A.
Stach, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Nature 442 (2006) 282–286.
[18] A.C. Ferrari, Solid State Commun. 143 (2007) 47–57.
[19] S. Park, J. An, J.R. Potts, A. Velamakanni, S. Murali, R.S. Ruoff, Carbon 49 (2011)
3019–3023.
[20] D.N.H. Tran, S. Kabiri, D. Losic, Carbon 76 (2014) 193–202.
[21] T.V. Khai, D.S. Kwak, Y.J. Kwon, H.Y. Cho, T.N. Huan, H. Chung, H. Ham, C. Lee,
N.V. Dan, N.T. Tung, Chem. Eng. 232 (2013) 346–355.
[22] KalimuthuVijaya Sankar, Ramakrishnan Kalai Selvan, Carbon 90 (2015) 260–
273.