Materials Research Bulletin 79 (2016) 41–51

Contents lists available at ScienceDirect

Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Studies on synthesis of reduced graphene oxide (RGO) via green route

and its electrical property
Sourav Sadhukhana,b , Tapas Kumar Ghosha,c , Dipak Ranad, Indranil Roya ,
Amartya Bhattacharyyaa , Gunjan Sarkara , Mukut Chakrabortyc,* ,
Dipankar Chattopadhyaya,*
a
Department of Polymer Science and Technology, University of Calcutta, 92 A.P.C. Road, Kolkata 700009, India
b
Department of Chemistry, Budge Budge Institute of Technology, Nischintapur, Budge Budge, Kolkata 700137, India
c
Department of Chemistry, West Bengal State University, Barasat, Kolkata 700126, India
d
Department of Chemical and Biological Engineering, Industrial Membrane Research Institute, University of Ottawa, 161 Louis Pasteur St., Ottawa, Ontario K1
N 6N5, Canada

A R T I C L E I N F O A B S T R A C T

Article history: An environmentally friendly method has been applied for the preparation of reduced graphene oxide
Received 29 October 2015 (RGO). This method was developed by using polyphenols that contained a phytoextract of Mangifera indica
Received in revised form 25 January 2016 L. along with Solanum tuberosum L. as reducing agents since they are non-toxic and naturally available.
Accepted 24 February 2016
The phytoextracts used in the production of RGO was set between 60 and 70
C. Graphene oxide (GO) was
Available online 27 February 2016
prepared by modified Hummer’s method as reported in earlier findings. Structural and morphological
studies demonstrate that the part of the oxygen functionalities in GO can be removed by following green
Keywords:
reduction. Characterizations of the resulting product have been done by X-ray diffraction, FTIR, UV–vis
A. Organic compounds
B. Optical properties
and Raman spectroscopy. FESEM, TEM, EDX spectrum, TGA, DLS and Zeta potential measurements of the
C. X-ray diffraction samples have also been carried out to study the morphological, thermal and surface charge
C. Raman spectroscopy characteristics. Electrical conductivity was also measured to check the extent of reduction of GO to RGO.
D. Electrical properties ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Graphene is a two dimensional nanostructure with single layer
carbon atoms firmly packed into a honey comb crystal lattice [1].
Due to graphene’s unique mechanical, thermal, catalytic, electrical
and optical properties [1], it has attracted tremendous attention in
recent years [2–5]. Graphene has the ability to be used in a wide
range of fields including bio-sensing [6], drug delivery [7], catalysis
[8] and energy storage [9]. This is why it can be used in a wide
range of applications such as nano-electronics [10], Li-ion batteries
[4], thin-film transistors [11] and solar cells [12,13]. Generally the
production of individual graphene sheets in bulk quantity proves
to be a significant challenge but the problem can be solved by the
chemical reduction [14–17] (using hydrazine, di-methyl hydrazine,
hydroquinone, sodium borohydride etc.) of graphene oxide (GO).
The reason being is that it has a low cost of production of reduced
graphene oxide (RGO) however, the reducing chemicals are either
non-environmentally friendly, poisonous or both. The presence of
* Corresponding authors.
E-mail address: dipankar.chattopadhyay@gmail.com (D. Chattopadhyay).
trace amounts of such toxic agents could have detrimental effect,
especially for bio-related applications [18,19]. Even in the case of
metal/hydrochloric acid reduction of GO, metal particles may
remain as impurities and tendency of p-p stacking between
chemically reduced GO sheets may form irreversible aggregation
[20]. In this context, the employment of green technology for the
reduction of GO have been reported to overcome the above
problem.
Alternatively few other methods for the preparation of RGO
such as the exfoliation of GO under strong alkaline conditions and
lower temperature, chemical vapor deposition (CVD) [21],
synthesis using biomolecules as reducing agents such as ascorbic
acid [22,23], amino acid [24], sodium citrate [25], glucose [26],
bovine serum albumin [27] etc. have also been reported. However,
flash photo reduction [28], hydrothermal dehydration [16] and
solvothermal reduction [29] processes lead to irreversible
aggregation due to strong Vander Waals forces between
RGO sheets which hamper its processibility. To avoid these
difficulties, various surface modifications of GO have been
introduced using small organic molecules, biomolecules and
polymers or surfactants such as poly(N-vinyl-2-pyrrolidone)
[30] and poly(sodium-4-styrene sulfonate) [15], etc. in order to

http://dx.doi.org/10.1016/j.materresbull.2016.02.039
0025-5408/ ã 2016 Elsevier Ltd. All rights reserved.
42 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
improve the dispersibility of RGO sheets and prevent them from
aggregation. Various phytoextracts such as carrot roots [31], green
tea [32], bacteria (Escherichia coli) [33], C. sinensis peel (Orange), S.
aromaticum (Cloves), S. oleracea (Spinach), R. damascene (Rose), P.
serrulata (Cherry) etc. [60] have also been used to produce RGO.
Although the degree of reduction through green methods is lower
than that of the chemical methods, they are widely accepted in
biological and biomedical fields. But some of the reported green
methods suffer from limitations of high time consumption (e.g.
48–72 h) [19], relatively poor stability [25,34] and poor solubility
(e.g. 0.1 mg/ml) [23] which may not be propitious to obtain a large
quantity of RGO in order to store them for a long time.
In this present work we have used two different types of
aqueous phytoextracts such as Mangifera indica L. (mango) leaves
extract and Solanum tuberosum L. (potato) extract as reducing
agents, which are commonly available, eco-friendly, non-hazard-
ous and have low environmental impacts [31]. These phytoextracts
contain many phenolic compounds (Fig. 1) such as caffeic acid,
chlorogenic acid, gallic acid, protocatechuic acid, salicylic acid, vanillic
acid [35,36,55,56,57] etc. and have a large number of hydroxyl
groups, which endow them in having mild reducing properties
[58,59]. This helps in the partial removal of the oxygen containing
functionalities from GO during reduction in order to restore
electronic conjugation in RGO. The presence of these phytoextracts
will also help to prevent the extensive agglomeration in an
aqueous dispersion of the resulting RGO through electrostatic
Fig. 1. Some Phenol derivatives in Mangifera indica L. and Solanum tuberosum L extracts as reported earlier [55–57].
repulsion interactions of the negative charge densities of many
carboxylic groups. The green synthesized RGO is highly dispersible
in water.
2. Experimental
2.1. Materials
Graphite Micro-850 was received as gift from the Asbury
Graphite Mills, Inc., Asbury, Warren Country, NJ. Potassium
permanganate (KMnO4 purified), hydrogen peroxide (30% H2O2),
sodium nitrate (NaNO3, extra pure), concentrate sulphuric acid
(98% H2SO4, GR grade) were purchased from Sigma Aldrich, Merck
and S.D. Fine Chemicals, India. The fresh potatoes were purchased
from the local market and were used within 30 min of chopping.
The fresh mango leaves were collected from a mango garden.
2.2. Preparation of graphene oxide (GO)
The graphene oxide was synthesized from natural graphite
powder by the modified Hummer’s method [37,38,51,52]. Graphite
powder (1 g) and NaNO3 (1 g) were added into 50 ml 98%
concentrated H2SO4 under vigorous stirring in a conical flask
placed in an ice bath. After some time, the whole mass was
converted to black slurry. Then KMnO4 (6 g) was slowly added into
the slurry maintaining the reaction temperature below 20
C.
 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
After 4 h, the whole system was taken out from the ice bath and
diluted with 100 ml water and then stirred for 2 h at 70–80
C. To
control the pH of the reaction medium and also to terminate the
reaction, 200 ml of hot water (60
C) followed by 20 ml H2O2 were
added to the above reaction mixture which resulted in a color
change from brownish black to bright yellow. The resultant
mixture was washed several times with distilled water and the
residue was subjected to centrifugation several times. To get the
pure graphite oxide powder the GO slurry was then collected and
dried in a hot air oven at 60
C for 24 h.
2.3. Preparation of different phytoextracts
2.3.1. Mangifera indica L. (mango) leaves extract
Fresh mango leaves (collected from a garden) were washed
with hot water then dried under sunlight and finally was set in a
hot air oven at 100
C. Then they were placed in a grinder in order
to be changed into a fine powder form. Then sufficient quantities of
this dry powder were taken in a conical flask and 100 ml Millipore
water was added followed by stirring at 50
C for 1 h by a magnetic
stirrer until it was thoroughly mixed. Then the mixture was
allowed to settle down at room temperature and after centrifuga-
tion the liquid extract was collected from decanting the upper
portion of the mixture. This was followed by filtration through a
Whatman 42 filter paper and the filtrate was collected as extract.
2.3.2. Solanum tuberosum L. (potato) extract
Fresh potatoes (collected from the local market) were thinly
sliced and then washed with warm distilled water. Then this thinly
sliced potato was taken in 100 ml Millipore water and grinded well
in a grinder to form a paste. Then the resultant mixture was
centrifuged several times and the supernatant liquid was collected
as the extract and the residual portion was rejected.
2.4. Reduction of GO by different phytoextract
In a typical experiment 0.025 g of GO powder was mixed with
25 ml de-ionized water and ultra-sonicate for 1 h at room
temperature to make a stable GO dispersion (1 mg/ml). On the
other hand, 25 ml of raw extract (Mangifera indica L.) was mixed
with this disperse solution of GO (keeping GO, phytoextracts
volume ratio 1:1) and again magnetically stirred (650 rpm) for 12 h
at 60
C. The reaction mixture was heated at 70–80
C under
Fig. 2. Preparation scheme of RGO using phytoextracts.
43
refluxed conditions in an oil bath for 8 h. It was found that the
colour of GO dispersion changes from brownish yellow to dark
black. Finally, the mixture was allowed to cool at room tempera-
ture, then centrifuged and finally the product was collected after
repeated washings with warm water followed by acetone. The RGO
obtained was dried subsequently in vacuum desiccators at room
temperature for 48 h (Fig. 2). A similar experimental protocol was
followed for the other extract (Solanum tuberosum L.) and the same
colour change for the GO dispersion was observed. This indicates
that phytoextracts played an important role in the reduction of GO
to RGO (Fig. 3). The as prepared RGOs were marked as RGO-1 and
RGO-2.
3. Characterizations
The X-ray diffraction(XRD) analysis of GO and RGO were
performed at room temperature by a X-PERT-PRO Pan analytical
diffractometer using Cu Ka (l = 1.5406 nm) as an X-ray source at a
generator voltage of 40 kV and current of 30 mA. The scanning rate
was 1
/min. From the XRD data, the interlayer spacing of GO and
RGO were calculated using Bragg’s law as follows:
l
d¼ ð1Þ
2 sin u
Raman spectroscopy is highly sensitive to the electronic
structure and has proven to be an essential tool for the
characterization of carbon-based materials, especially C¼C double
bonds that lead to high Raman intensities. It can be a useful tool to
characterize GO and its reduced form by green reduction [1]. The
Raman spectra was monitored using 1.96 eV (633 nm) line of a He-
Ne laser in HORIBA-JOBIN-YVON Lab RAM HR 800 instrument by
placing the sample solution into a semi-micro stopper cuvette with
an exposure time of 1 s.
Fourier transform infra-red (FTIR) spectroscopy was done to
confirm the formation of GO and RGO. It was also used to identify
the characteristic peaks of oxygen containing groups of GO such as
epoxy, carbonyl, hydroxides etc. and the removal of these oxygen-
functional groups in case of RGO after green reduction. An FTIR
spectrum was performed in a PerkinElmer spectrum Express
Version 1.03.00 instrument in the range of 500–4000 cm1.
The UV visible spectrometer was also used to verify the
formation of stable GO and RGO suspension because the
absorbance at the characteristic peak was in a linear relationship
44 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
Fig. 3. Proposed reaction mechanism for green reduction of GO by phytochemicals.
with the concentration on the basis of Beer’s law, if a homogeneous
solution was formed. This was done in Agilent 8453 Spectropho-
tometer, USA, with wave lengths in the 175–500 nm ranges.
Zeta-potential measurements were carried out to study the
surface charge as well as the stability of GO and RGO. The
measurements were performed using a Zetasizer Nano-
ZS90 System (Malvern Inc.).
Thermo-gravimetric analysis (TGA) of nanocomposites films
with GO were carried out in a Mettler-Toledo TGA/SDTA
851 thermal analyzer in a dynamic atmosphere of nitrogen (flow
rate = 30 cm3 min1). The samples were heated in an alumina
crucible at a rate of 10
C/min over a temperature range of 50–
800
C.
Field emission scanning electron microscopy (FESEM) was used
at different magnifications to observe the surface morphology of
the GO and RGO samples. Before testing, the samples were coated
with a thin layer of gold to avoid electrical charging during
examination. FESEM study was performed in a Zeiss Auriga
instrument.
The morphology of synthesized samples were characterized
using a transmission electron microscope (TEM, JEOL-JEM-
2100 with a 200 kV accelerating voltage). Samples for TEM analysis
were prepared by drying a droplet of material suspension on a
carbon coated copper grid. Energy dispersive X-ray (EDX) analysis
was done by field emission scanning electron microscopy (FESEM-
JEOL).
Electrical conductivity of GO and RGO samples were measured
using pellets having a thickness of 0.1 cm and a diameter of 0.5 cm
by an Ecopia HNS 5300.
4. Results and discussion
4.1. XRD analysis
To characterize the crystal structure, XRD analysis of the
exfoliated GO, Mangifera indica L. leaf extract reduced RGO-1 and
the Solanum tuberosum L. extract reduced RGO-2 were studied. The
diffraction peak of GO was found to be at 10.36
(0 0 2) with layer to
layer distance (d-spacing) of 0.85 nm (Fig. 4). Pristine graphite
exhibits the basal reflection (0 0 2) peak at 2u = 26.6
(d spacing
0.335 nm) [27]. The increase in d-spacing is due to the formation of
oxygen containing functional groups between the layers of the
graphite. However, the broad peaks at 2u = 21.87
and 2u = 21.86

appeared when the GO is reduced to RGO-1 and RGO-2 by the
different phytoextracts at 60–70
C for 8 h [32] respectively. The
disappearance of 0 0 2 reflection peak of GO and the appearance of
a broad band in RGOs is due to the removal of some of oxygen
functionalities during reduction from GO and the formation of a
S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51 45

Fig. 4. XRD pattern of GO, RGO-1 and RGO-2.

Fig. 5. Raman spectra of GO, RGO-1 and RGO-2.

46 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51

few layers of graphene. It is also observed that the peak intensities 4.3. FTIR analysis
of RGO-1 to RGO-2 were found almost the same and indicating to
some extent of equal reducing capabilities of both phytoextracts. Fig. 6 shows the Fourier Transform Infrared (FTIR) spectra of
pure GO, RGO-1 and RGO-2 samples to evaluate de-oxidation of GO
by Mangifera indica L. leaf extract and Solanum tuberosum L. extract.
4.2. Raman spectra analysis
The spectra of GO clearly shows the FTIR peaks corresponding to
the oxygen functionalities such as the C¼O stretching vibration
Raman spectroscopy is an essential tool for the characterization
peak at 1720 cm1, C¼O bending vibration peak at 1628 cm1,
of carbon-based materials, especially C¼C bonds that leads to high
OH deformation peak at 1407 cm1, OH vibration peak at
Raman intensities. Raman scattering is strongly dependent upon
3400 cm1, C O (epoxy) stretching vibration peak at 1229 cm1,
electronic structure, hence it can be a useful tool to recognize the
COH (alkoxy) stretching peak at 1072 cm1, respectively [42,43].
single layer characteristics of GO [50] and its reduced form after
After 8 h the reduction of GO by different phytoextracts the peak
green reduction. Raman spectra of GO, RGO-1 and RGO-2 are
belonging to carbonyl (C¼O) group disappeared completely (e.g.,
shown in Fig. 5 and the spectrum of GO was found to be
1720 cm1) and OH deformation peak at 1407 cm1 decreases
significantly changed after reduction. Raman spectra is generally
significantly from RGO-1 to RGO-2. The two peaks at 1628 and
characterized by two main features: The G vibration mode, owing
3434 cm1for RGO-1, and 1569 and 3364 cm1 for RGO-2 are due to
to the first-order scattering of E2g phonons by sp2 carbon of GO,
in plane C¼C skeleton vibrations and the O H stretching
RGO-1 and RGO-2 were observed at 1578, 1594 and 1585 cm1
vibration, respectively. The presence of another two new peaks
while the D vibration band arising from the breathing mode of j-
at 2914 cm1, 2840 cm1 for RGO-1 and 2865 cm1 2781 cm1 for
point phonons of A1g symmetry [39,44] appeared at 1336, 1352 and
RGO-2 are probably due to the absorption of phytoextracts
1342 cm1 respectively. After the reduction of GO, the intensity
containing phenolic compounds at the surface of the RGOs [39].
ratio of the D band to the G band (ID/IG) is increased significantly.
This observation implies that the FTIR spectra of RGOs are almost
ID/IG is 0.846 for GO whereas for RGO-1 and RGO-2 ID/IG are
identical with that of the hydrazine reduced RGO as reported in
1.024 and 1.066, respectively. This implies that the intensity of the
early findings [41]. Then it is quite obvious that the oxygen
D-band has increased due to the removal of oxygen moieties and
functionalities in GO could be removed by plant phytoextracts via
restoration of sp2-carbon cluster during reduction [15,39,44],
the green route.
hence the higher intensity of the D band suggested the presence of
a more isolated graphene domain in RGOs in comparison to GO. GO
4.4. UV-spectroscopy-optical analysis
has different types of functional groups which prevent the stacking
of graphene layers but after reduction, due to the decrease of such
UV–visible spectroscopy was used to confirm the reduction of
functional groups, a few graphene layers are stacking and can lead
oxygen functionalities in GO by the aqueous phytoextract. It refers
to the formation of multilayer RGOs [40].
to the optical absorption spectroscopy (OAS) in the ultraviolet-

Fig. 6. FTIR spectrum of GO, RGO-1 and RGO-2.

 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51 47

Fig. 7. UV absorption spectra of GO, RGO-1 and RGO-2.

visible spectral region of the electromagnetic spectrum. Fig. 7
represents the optical absorption spectra of graphene oxide (when
dispersed in water). As shown in Fig. 7 the absorption peak of GO
dispersion is located at 239 nm with a shoulder peak at 300 nm,
due to the p ! p* transition of aromatic C¼C bonds and n ! p*
transition of C¼O bonds [39,40,51,52]. After de-oxidation by
different phytoextract, the absorption peak of the p ! p* transition
becomes red shifted to 259 nm for RGO-1 and 265 nm for RGO-2.
This observation attributed to the fact that due to the excitation of
p-Plasmon [41], the oxygen functionalities on the GO surface are
removed and aromatic conjugated sp2 cluster might be restored in
RGOs. The absorption spectrum of hydrazine reduced RGO shows
the corresponding peak at 268 nm [40]. Therefore it is quite clear
that, though the aqueous phytoextracts are milder reducing agent

Fig. 8. Zeta potential and DLS of GO and different RGOs.

48 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
Fig. 9. Thermal analysis of GO and two different RGOs.
in comparison with chemical reducing agent, they are well capable
to partially remove the oxygen functionalities from the GO surface.
4.5. Zeta potential and DLS study
The Zeta potential measurement of GO and RGOs in an aqueous
solution have been carried out in a dynamic light scattering
instrument to inspect the surface charge characteristics (Fig. 8).
The average zeta potential [51] value of GO is 20.46 mV which is
due to the presence of carboxyl and epoxy groups [45] with
negative charge densities at the surface of GO. This value becomes
more negative with 23.5 mV for RGO-1 and 25.61 mV for RGO-
2 after the reduction using different phytoextracts. The increasing
trend of the zeta potential value might be due to the function-
alization of RGOs during partial reduction and hence possessed
more surface negative charge densities than GO. This leads to the
stable dispersion of RGOs in an aqueous solution by the
electrostatic repulsion interaction with water molecules [46,53].
The aqueous dispersion of GO and RGOs in water (1 mg/ml)
were characterized by DLS after prolonged sonication. It was found
that the average hydrodynamic diameter (AHD) of GO was
270.5  10.6 nm and after reduction by different phytoextracts it
becomes 150.4  26.1 nm for RGO-1 and 124.7  18.1 nm for RGO-
2 under the same experimental conditions. Both the results are
relatively lower than that of GO. As described in earlier findings
[54], most of the graphene based materials are not spherical
particles and the model derived diameters are not their real sizes.
Therefore, the data in our case cannot be taken to evaluate the
actual sizes of the 2-D structures and could only be used to reflect
the trend of changes in the graphene size [46]. After the reduction
Fig. 10. FESEM images of GO, RGO-1 and RGO-2.
process the size of the RGOs particles are roughly 1.8 and 2.1 times
smaller than the GO.
4.6. Thermal (TGA) study
Thermal stability was used to assess the quality of RGOs. TGA
plots of GO, RGO-1 and RGO-2 in nitrogen atmosphere are shown
in Fig. 9. It is evident that graphene oxide exhibits a significant
weight loss of 5–15% (at 25–135
C), 40–45% (at 250–350
C) and
50–65% (at 350–600
C) which are attributed to the loss of
absorbed water molecules, degradation of oxygenated functional
groups with the loss of CO, CO2, water vapor and oxidation of
residual matter. Pure GO exhibits two degradation steps, the first
commencing at 180
C, due to the loss of hydroxyl, epoxy
functional groups. The second degradation step (at 350–600
C)
involves the pyrolysis of the remaining oxygen-containing groups
as well as the burning of ring carbon [47–49]. In contrast, the RGOs
show high stability at a higher temperature increasing from RGO-1
to RGO-2. The total weight loss for RGO-1 was 3–7% (25–135
C),
20–25% (250–350
C) and 38% at 600
C, whereas, for RGO-2, the
trend follows as 2–4% (25–135
C), 15–20% (250–350
C) and 25% at
600
C. These reducing mass losses of RGOs can be attributed to the
absence of most oxygen functional groups in graphene moiety.
Finally, the observed thermal stability of green reduced RGOs are
also well in agreement with the reported literature values [31].
4.7. FESEM analysis
The morphology of graphene was examined by FESEM analysis
in Fig. 10. The aqueous dispersion of GO and RGOs were further
dropped on aluminum foil and FESEM images were taken
 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51 49

Fig. 11. TEM images of RGO-1(a) and RGO-2(b).

Fig. 12. EDX spectrum of RGO-1 and RGO-2.

randomly for each sample. Exfoliation of GO results flakes, which

are smaller in size, more clumped and stacked. But on the other 4.9. Energy dispersive X-ray (EDX) analysis from TEM
hand the FESEM images of RGOs revealed that well separated
platelets are closely associated with each other. Fig. 12 depicts the EDX spectrum of the RGOs. It is apparent
from the spectrum that the synthesized RGOs contain sharp C and
4.8. TEM analysis O peaks with no other impurities confirming the successful in situ
green synthesis of RGOs using different phytoextracts. The peaks of
Transmission electron microscopy (TEM) images of RGO-1 and Si, Ca that appeared in the EDX spectrum of RGO-2 is due to the
RGO-2 are shown in Fig. 11a and b, which are useful to detect the impurities and peak of Cu which appears from the copper grid,
number of layers present in it and also reveals that both RGOs where the samples were prepared. Carbon, oxygen percentages of
possesses micro structural morphology with wrinkled and folded RGOs are shown in Table 1.
structure, indicating its loosely bonded layers and higher interlayer
distance [51,52]. It is exhibited in the exfoliated form which is 4.10. Electrical conductivity
consistent with the FESEM images and also observed that most of
the edges of suspended RGOs tend to fold back and appear Electrical conductivity has also been investigated for GO and
separated in a few layered structures. different RGOs. GO shows the conductivity value of
4.86  104 S/cm, whereas, after reduction, RGOs show slightly
higher conductivities of 1.16  103 S/cm and 3.58  103 S/cm
Table 1 for RGO-1 and RGO-2, respectively. This is due to the partial
Elemental composition of RGO-1 and RGO-2. reduction of functional groups in GO (such as epoxide, hydroxyl,
Sample Carbon Oxygen Copper Calcium Silicon
carboxyl and carbonyl) by phytoextracts and also regeneration
of pi-conjugated sp2 hybridized framework structures in RGOs
RGO-1 67.05% 10.14% 22.81% – –
RGO-2 73.38% 5.3% 8.25% 6.93% 6.15%
(Fig. 13).
50 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
Fig. 13. Conductivity of GO, RGO-1 and RGO-2.
5. Conclusion
In the current work we have presented a study on the green
reduction of GO using two different phytoextracts of Mangifera
indica L. (dry mango leaf) and Solanum tuberosum L. (potato). We
observed that the poly-phenols in plant extract acts both as
reducing and stabilizing agents, thus the resultant graphene
possess good solubility and stability in an aqueous medium. The
different RGOs were characterized by FESEM and TEM analysis
which shows the formation of a few layers of graphene. In addition,
the XRD and UV studies also supported the reduction of graphene.
FTIR analysis provides evidence for the partial elimination of the
oxygen functionalities from the structure of GO. The ID/IG ratio of
RGO-1 and RGO-2 are higher than GO due to the restoration of
sp2carbon networks in graphene moieties which is confirmed by
Raman spectroscopy. Thermal stability data shows significant
stability of the RGOs at higher temperature than GO due to the loss
of some functional group during partial reduction. The EDX
spectrum shows that the C/O atomic ratio increased from GO to
RGO after reduction. It is also found that the electrical conductivi-
ties of RGO-1 and RGO-2 are slightly higher than GO.
Acknowledgements
I. Roy and A. Bhattacharyya like to thank the Technical
Education Quality Improvement Programme [TEQIP], University
of Calcutta for his fellowship. G. Sarkar likes to thank the University
Grant commission, Govt. of India in Rajiv Gandhi National
Fellowship Scheme for his fellowship. We also like to thank
Centre for Research in Nanoscience and Nanotechnology [CRNN],
University of Calcutta for providing FESEM, TEM and others
characterization facilities. Thanks are also due to Dr. Supriya Dutta
for his contribution during the preparation of the manuscript.
References
[1] M.J. Allen, V.C. Tung, R.B. Kaner, Honeycomb carbon: a review of graphene,
Chem. Rev. 110 (2010) 132–145.
[2] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
Science 306 (2004) 666–669.
[3] Y. Hernandez, V. Nicolosi, M. Lotya, F.M. Blighe, Z. Sun, S. De, I.T. McGovern, B.
Holland, M. Byrne, Y.K. Gun’Ko, J.J. Boland, P. Niraj, G. Duesberg, S.
Krishnamurthy, R. Goodhue, J. Hutchison, V. Scardaci, A.C. Ferrari, J.N.
Coleman, High-yield production of graphene by liquid-phase exfoliation of
graphite, Nat. Nanotechnol. 3 (2008) 563–568.
[4] K.S. Kim, Y. Zhao, H. Jang, S.Y. Lee, J.M. Kim, K.S. Kim, J.-H. Ahn, P. Kim, J.-Y. Choi,
B.H. Hong, Large scale pattern growth of graphene films for stretchable
transparent electrodes, Nature 457 (2009) 706–710.
[5] P.W. Sutter, J.I. Flege, E.A. Sutter, Epitaxial graphene on ruthenium, Nat. Mater.
7 (2008) 406–411.
[6] C.-H. Lu, H.-H. Yang, C.-L. Zhu, X. Chen, G.-N. Chen, A graphene platform for
sensing biomolecules, Angew. Chem. Int. Ed. 48 (2009) 4785–4787.
[7] X. Sun, Z. Liu, K. Welsher, J.T. Robinson, A. Goodwin, S. Zaric, H. Dai, Nano-
graphene oxide for cellular imaging and drug delivery, Nano Res. 1 (2008) 203–
212.
[8] Y. Song, K. Qu, C. Zhao, J. Ren, X. Qu, Graphene oxide: intrinsic peroxidase
catalytic activity and its application to glucose detection, Adv. Mater. 22 (2010)
2206–2210.
[9] H. Cheng, X. Sha, L. Chen, A.C. Cooper, M.-L. Foo, G.C. Lau, W.H. Bailey, G.P. Pez,
An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite
compounds, J. Am. Chem. Soc. 131 (2009) 17732–17733.
[10] S. Liu, J.Q. Tian, L. Wang, X.P. Sun, A method for the production of reduced
graphene oxide using benzyl amine as a reducing and stabilizing agent and its
subsequent decoration with Ag nano-particles for enzymeless hydrogen
peroxide detection, Carbon 49 (2011) 3158–3164.
[11] J.H. Jung, D.S. Cheon, F. Liu, K.B. Lee, T.S. Seo, A graphene oxide based
immune-biosensor for pathogen detection, Angew. Chem. Int. Ed. 49 (2010)
5708–5711.
[12] F. Schedin, A.K. Geim, S.V. Morozov, E.W. Hill, P. Blake, M.I. Katsnelson, K.S.
Novoselov, Detection of individual gas molecules adsorbed on graphene, Nat.
Mater. 6 (2007) 652–655.
[13] G. Eda, G. Fanchini, M. Chhowalla, Large-area ultrathin films of reduced
graphene oxide as a transparent and flexible electronic material, Nat.
Nanotechnol. 3 (2008) 270–274.
[14] S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nat.
Nanotechnol. 4 (2009) 217–224.
[15] S. Stankovich, P.D. Piner, X. Chen, N. Wu, S.T. Nguyen, R.S. Ruoff, Stable aqueous
dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite
oxide in the presence of poly(sodium 4-styrenesulfonate), J. Mater. Chem. 16
(2006) 155–158.
[16] Y. Zhou, Q. Bao, L.A.L. Tang, Y. Zhong, K.P. Loh, Hydro-thermal dehydration for
the green reduction of exfoliated graphene oxide to graphene and
demonstration of tunable optical limiting properties, Chem. Mater. 21 (2009)
2950–2956.
[17] H. Wang, J.T. Robinson, X. Li, H. Dai, Solvothermal reduction of chemically
exfoliated graphene sheets, J. Am. Chem. Soc. 131 (2009) 9910–9911.
[18] J.I. Paredes, S. Villar-Rodil, M.J. Fernández-Merino, L. Guardia, A. Martínez-
Alonso, J.M.D. Tascón, Environmentally friendly approaches toward the mass
production of processable graphene from graphite oxide, J. Mater. Chem. 21
(2011) 298–306.
[19] D.Y. Lee, Z. Khatun, J.-H. Lee, Y. Lee, I. In, Blood compatible graphene/heparin
conjugate through noncovalent chemistry, Biomacromolecules 12 (2012) 336–
341.
[20] C.A. Amarnath, C.E. Hong, N.H. Kim, B.C. Ku, T. Kuila, J.H. Lee, Efficient synthesis
of graphene sheets using pyrrole as a reducing agent, Carbon 49 (2011) 3497–
3502.
[21] D.C. Wei, Y.Q. Liu, Y. Wang, H.L. Zhang, L.P. Huang, G. Yu, Synthesis of n-doped
graphene by chemical vapor deposition and its electrical properties, Nano Lett.
9 (2009) 1752–1758.
[22] J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang, S. Guo, Reduction of graphene
oxide via L-ascorbic acid, Chem. Commun. 46 (2010) 1112–1114.
 S. Sadhukhan et al. / Materials Research Bulletin 79 (2016) 41–51
[23] J. Gao, F. Liu, Y. Liu, N. Ma, Z. Wang, X. Zhang, Environment-friendly method to
produce graphene that employs vitamin C and amino acid, Chem. Mater. 22
(2010) 2213–2218.
[24] C. Shan, H. Yang, D. Han, Q. Zhang, A. Ivaska, N. Liu, Water-soluble graphene
covalently functionalized by biocompatible poly-L-lysine, Langmuir 25 (2009)
12030–12033.
[25] Z. Zhang, H. Chen, C. Xing, M. Guo, F. Xu, X. Wang, H.J. Gruber, B. Zhang, J. Tang,
Sodium citrate: a universal reducing agent for reduction/decoration of
graphene oxide with au nanoparticles, Nano Res. 4 (2011) 599–611.
[26] O. Akhavan, E. Ghaderi, S. Aghayee, Y. Fereydooni, A. Talebi, The use of a
glucose-reduced graphene oxide suspension for photothermal cancer therapy,
J. Mater. Chem. 22 (2012) 13773–13781.
[27] J. Liu, S. Fu, B. Yuan, Y. Li, Z. Deng, Toward a universal adhesive nanosheet for
the assembly of multiple nanoparticles based on a protein-induced reduction/
decoration of graphene oxide, J. Am. Chem. Soc. 132 (2010) 7279–7281.
[28] L.J. Cote, R. Cruz-Silva, J. Huang, Flash reduction and patterning of graphite
oxide and its polymer composite, J. Am. Chem. Soc. 131 (2009) 11027–11032.
[29] K. Ai, Y. Liu, L. Lu, X. Cheng, L. Huo, A novel strategy for making soluble reduced
graphene oxide sheets cheaply by adopting an endogenous reducing agent, J.
Mater. Chem. 21 (2011) 3365–3370.
[30] X.-Y. Tang, Z. Cao, H.-B. Zhang, J. Liu, Z.-Z. Yu, Growth of silver nanocrystals on
graphene by simultaneous reduction of graphene oxide and silver ions with a
rapid and efficient one-step approach, Chem. Commun. 47 (2011) 3084–3086.
[31] T. Kuila, S. Bose, P. Khanra, A.K. Mishra, N.H. Kim, J.H. Lee, A green approach for
the reduction of graphene oxide by wild carrot root, Carbon 50 (2012) 914–921.
[32] Y. Wang, Z. Shi, J. Yin, Facile synthesis of soluble graphene via a green reduction
of graphene oxide in tea solution and its biocomposites, ACS Appl. Mater.
Interfaces 3 (2011) 1127–1133.
[33] S. Gurunathan, J.W. Han, V. Eppakayala, J.H. Kim, Microbial reduction of
graphene oxide by Escherichia coli: a green chemistry approach, Colloids Surf.
B: Biointerfaces 102 (2013) 772–777.
[34] M.J. Fernández-Merino, L. Guardia, J.I. Paredes, S. Villar-Rodil, P. Solis-
Fernández, A. Martinez-Alonso, J.M.D. Tascón, Vitamin C is an ideal substitute
for hydrazine in the reduction of graphene oxide suspensions, J. Phys. Chem. C
114 (2010) 6426–6432.
[35] C.R. Brown, Antioxidants in potato, Am. J. Potato Res. 82 (2005) 163–172.
[36] J.A. Severi, Z.P. Lima, H. Kushima, A.R.M.S. Brito, L.C. Dos Santos, W. Vilegas, C.A.
Hiruma-Lima, Polyphenols with anti ulcerogenic action from aqueous extract
of mango leaves (Mangiferaindica L.), Molecules 14 (2009) 1098–1110.
[37] W.S. Hummers Jr, R.E. Offerman, Preparation of graphite oxide, J. Am. Chem.
Soc. 80 (1958) 1339.
[38] W. Fan, Q. Lai, Q. Zhang, Y. Wang, Nanocomposites of TiO2 and reduced
graphene oxide as efficient photocatalysts for hydrogen evolution, J. Phys.
Chem. C 115 (2011) 10694–10701.
[39] P. Khanra, T. Kuila, N.H. Kim, S.H. Bae, D.S. Yu, J.H. Lee, In situ synthesis of
reduced graphene oxide/polyethyleneimine composite and its gas barrier
properties, Chem. Eng. J. 183 (2012) 526–533.
[40] S. Thakur, N. Karak, Green reduction of graphene oxide by aqueous
phytoextracts, Carbon 50 (2012) 5331–5339.
[41] A.J.F. Carvalho, A.A.S. Curvelo, J.A.M. Agnelli, A first insight on composites of
thermoplastic starch and kaolin, Carbohydr. Polym. 45 (2001) 189–194.
[42] C. Nethravathi, M. Rajamathi, Chemically modified graphene sheets produced
by the solvothermal reduction of colloidal dispersions of graphite oxide,
Carbon 46 (2008) 1994–1998.
51
[43] G. Goncalves, P.A.A.P. Marques, C.M. Granadeiro, H.I.S. Nogueira, M.K. Singh, J.
Grásio, Surface modification of graphene nanosheets with gold nanoparticles:
the role of oxygen moieties at graphene surface on gold nucleation and
growth, Chem. Mater. 21 (2009) 4796–4802.
[44] Z. Lin, Y. Yao, Z. Li, Y. Liu, Z. Li, C.P. Wong, Solvent-assisted thermal reduction of
graphite oxide, J. Phys. Chem. C 114 (2010) 14819–14825.
[45] ASTM Standard D4187-92, Zeta potential of colloids in water and waste water,
Am. Soc. Test. Mater. (1985).
[46] Y. Wang, S.J. Zhen, Y. Zhang, Y.F. Li, C.Z. Huang, Facile fabrication of metal
nanoparticle/graphene oxide hybrids: a new strategy to directly illuminate
graphene for optical imaging, J. Phys. Chem. C 115 (2011) 12815–12821.
[47] Z.J. Fan, W. Kai, J. Yan, T. Wei, L.J. Zhi, J. Feng, Y.M. Ren, L.P. Song, F. Wei, Facile
synthesis of graphene nanosheets via Fe reduction of exfoliated graphite oxide,
ACS Nano 5 (2011) 191–198.
[48] H.K. Jeong, Y.P. Lee, M.H. Jin, E.S. Kim, J.J. Bae, Y.H. Lee, Thermal stability of
graphite oxide, Chem. Phys. Lett. 470 (2009) 255–258.
[49] W. Chen, L. Yan, P.R. Bangal, Preparation of graphene by the rapid and mild
thermal reduction of graphene oxide induced by microwaves, Carbon 48
(2010) 1146–1152.
[50] T.K. Ghosh, S. Gope, D. Mondal, B. Bhowmik, Md. M.R. Mollick, D. Maity, I. Roy,
G. Sarkar, S. Sadhukhan, D. Rana, M. Chakraborty, D. Chattopadhyay,
Assessment of morphology and property of graphene oxide-
hydroxypropylmethylcellulose nanocomposite films, Int. J. Biol. Macromol. 66
(2014) 338–345.
[51] I. Roy, A. Bhattacharyya, G. Sarkar, N.R. Saha, D. Rana, P.P. Ghosh, M. Palit, A.R.
Das, D. Chattopadhyay, In situ synthesis of reduced graphene oxide/cuprous
oxide nanocomposite: a reusable catalyst, RSC Adv. 4 (2014) 52044–52052.
[52] I. Roy, D. Rana, G. Sarkar, A. Bhattacharyya, N.R. Saha, S. Mondal, S. Pattanayak,
S. Chattopadhyay, D. Chattopadhyay, Physical and electrochemical
characterization of reduced graphene oxide/silver nanocomposites
synthesized by adopting green approach, RSC Adv. 5 (2015) 25357–25364.
[53] X. Qi, K.-Y. Pu, X. Zhou, H. Li, B. Liu, F. Boey, W. Huang, H. Zhang, Conjugated-
polyelectrolyte-functionalized reduced graphene oxide with excellent
solubility and stability in polar solvents, Small 6 (2010) 663–669.
[54] B. Kartick, S.K. Srivastava, I. Srivastava, Green synthesis of graphene, J. Nanosci.
Nanotechnol. 13 (2013) 4320–4324.
[55] Taleb H. Ibrahim, Youssef Chehade, Mohamed Abou Zour, Corrosion inhibition
of mild steel using potato peel extract in 2M HCl solution, Int. J. Electrochem.
Sci. 6 (2011) 6542–6556.
[56] Andreas Schieber, Marleny D. Aranda Saldana, Potato peels: a source of
nutritionally and pharmacologically interesting compounds, Food 3 (2009)
23–29 (special issue 2) Global Science Books.
[57] Abdelnaser Abdelghany Elzaawely, Shinkichi Tawata, Preliminary
phytochemical investigation on mango (Mangifera indica L.) leaves, World J.
Agric. Sci. 6 (6) (2010) 735–739.
[58] Karen C. Karen, Karen M. Schaichg, Polyphenol antioxidants from potato peels:
extraction optimization and application to stabilizing lipid oxidation in foods,
Proceedings of the National Conference on Undergraduate Research (NCUR)
2011, Ithaca College, New York, March 31–April 2, 2011.
[59] S.M.R. Ribeiro, L.C.A. Barbosa, J.H. Queiroz, M. Knodler, A. Schieber, Phenolic
compounds and antioxidant capacity of Brazilian mango (Mangifera indica L.)
varieties, Food Chem. 110 (2008) 620–626.
[60] Suman Thakur, Niranjan Karak, Alternative methods and nature-based
reagents for the reduction of graphene oxide, Carbon 94 (2015) 224–242.