Materials Chemistry and Physics 204 (2018) 1e7

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Materials Chemistry and Physics

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

Synthesis route of reduced graphene oxide via thermal reduction of

chemically exfoliated graphene oxide
Hareema Saleem a, *, Mobeen Haneef a, Hina Y. Abbasi b
a
School of Chemicals and Materials Engineering, National University of Science and Technology (NUST), Sector H-12, Islamabad, Pakistan
b
U.S.-Pakistan Center for Advanced Studies in Energy, National University of Science and Technology (NUST), Sector H-12, Islamabad, Pakistan

h i g h l i g h t s

Chemical exfoliation of graphite flakes.

Thermal reduction of graphene oxide.

UV-Vis spectroscopy showed the hills of GO and rGO at 215 nm and 267 nm.

X-ray diffraction displayed the peaks of GO at 11.8 and rGO at 25.5 .

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

Article history: Graphene, a two-dimensional material, is now considered as a rewarding contestant for nanodevices due
Received 18 May 2017 to its morphology and novel properties. The chemical exfoliation and thermal annealing methods are
Received in revised form appraised as an inventive route towards the production of graphene at prodigious scale. This method is
28 August 2017
utilized for the oxidation of graphite flakes having an oxidizing specialist and thermally reduced the
Accepted 7 October 2017
graphene oxide into reduced graphene oxide. We have examined the samples through different char-
Available online 9 October 2017
acterization techniques. X-ray diffraction displayed the peaks of graphene oxide at 11.8 and reduced
graphene oxide at 25.5 . Scanning electron microscopy images revealed the single and multilayers
Keywords:
Graphene oxide (GO)
morphology. The optical microscopy examined the number of layers of graphene oxide through the
Reduced graphene oxide (rGO) various contrasts of light. UV-Vis spectroscopy showed the hills of graphene oxide and reduced graphene
Oxidizing agent oxide at 215 nm and 267 nm. Fourier transform infrared spectroscopy has been utilized to examine the
Chemical exfoliation method resonating modes.
Thermal annealing © 2017 Elsevier B.V. All rights reserved.

1. Introduction environment friendly nature. Still, we have challenges to make

Today, the “Nanotechnology” plays a vital role in many fields
including biosciences, electronics, aerospace, automobiles, defense,
computers, agriculture, foods technology, consumer products and
also has shown major advancements in energy by minimizing the
losses and increasing the efficiency of energy generation. Due to the
increased surface to the volume ratio, interfaces and reduced size
effects, dramatic positive changes in the properties of various ma-
terials for a broad range can be observed and utilized for devel-
opment. Many efficient devices are made on basis of
nanotechnology with the benefits of reliability, compatibility and
* Corresponding author.
E-mail addresses: hareemasaleem@gmail.com (H. Saleem), mobeen_me03@
scme.nust.edu.pk (M. Haneef), 16phdhina@uspcase.nust.edu.pk (H.Y. Abbasi).
more efficient devices with required efficiencies by optimization of
an availability and cost of raw materials, manufacturing costs and
selection of size dependents properties of raw materials. In recent
developments in carbon allotropes, graphene has proven itself
better in energy technologies as compare to carbon nanotubes,
fullerene (C60), diamond, and graphite. It possesses unique size
dependent properties such as morphological, electrical, optical to
enhance the energy conversion, piezosensitive, and storage
performances.
In 2004, Graphene was discovered by Andre Geim and Kon-
stantin Novoselov when they isolated graphene by peeling graphite
with adhesive tape. This provides good quality micron sized gra-
phene [1]. Graphene is two-dimensional sheet of sp2-hybridized
carbon atoms. This network of extended honeycomb is the
elementary construction block of other carbon allotropes as it can

https://doi.org/10.1016/j.matchemphys.2017.10.020
0254-0584/© 2017 Elsevier B.V. All rights reserved.
2 H. Saleem et al. / Materials Chemistry and Physics 204 (2018) 1e7
be loaded to form graphite (3D), it can be rolled to form nanotubes
(1D), and enfolded to form fullerenes (0D). p-conjugation of long
range in graphene produces amazing electrical, mechanical, and
thermal properties [2].
The different method to synthesis the graphene are: micro-
mechanical cleavage of natural graphite flakes using a Scotch Tape
[1], epitaxial growth of graphene on SiC [3], thermal or plasma
enhanced chemical vapor deposition (CVD) of graphene [4e6],
chemical exfoliation of graphitic materials [7e10], bottom-up
synthesis from organic compounds, and electrochemical exfolia-
tion of graphite [11]. Only the chemical exfoliation method is
considered as a typical way toward the generation of graphene with
ease and in huge amount [12]. The ideal graphene sheets that can
be achieved by this mechanical exfoliation technique have proven
to be highly ordered, exhibit outstanding surface areas
(2630 m2 g1), high Young's modulus (1 TPa), highest hardness,
flexible elastic, ultra thickness, high thermal conductivity
(5000 W mK1), and strong chemical durability [13]. Having zero
rest mass of charge carriers, electrons travel with the speed of light
through the crystal. Such electron transport has never been prac-
tically seen in any semiconductor, and as a result graphene has
proved to be the most conductive non-superconducting material
with a room temperature resistivity of just 106/cm.
The following potential applications of graphene are: (a) The
electronic devices contain graphene have ultrafast terahertz elec-
tron flexibility that gives smaller, quicker, less expensive digital
products such as field transistors [14], spintronics [15], and opto-
electronics [16], (b) Graphene loaded polymer composites have
high electrical and heat conductivity, good mechanical strength,
and low percolation threshold [17], (c) It is used in display pro-
grams such as touch displays [18], (d) Graphene centered electro-
chemical storage space energy devices, (e) Graphene is used as
transport, performing electrodes [19], and (f) Many other applica-
tions in bio-, electrochemical, and chemical sensors [20], dye-
sensitized and organic solar panels, hydrogen storage, catalysts
[21] and photo catalysts [22].
Here, we report the chemical and thermal synthesis routes to-
wards the massive production of reduced graphene oxide. We
prepared high quality graphene nanosheets through this approach.
The crystal structure, morphology and optical properties were
investigated by X-ray dffraction (XRD), scanning electron micro-
scopy (SEM), optical microscopy, UV-Vis spectroscopy, and Fourier
transform infrared spectroscopy (FTIR).
2. Experimental
2.1. Chemical exfoliation method
Oxidized the graphite flakes by chemical exfoliation method.
Mixed 3 g of graphite flakes with 9:1 mixture of concentrated
H2SO4/H3PO4 (360:40 ml) and 18 g of KMnO4. Stirred the mixture
mechanically at 35-40 C for 4e5 h to produce the slightly
exothermic reaction. Heated and stirred it at 50 C for 12 h. Then
cooled it to room temperature and poured 400 ml ice of distilled
water and 5 ml hydrogen peroxide H2O2 in a mixture to complete
the reaction. The dark pink color was converted into mustard color.
Washed the mixture with 1 M HCl and distilled water till the pH of
supernatant liquid reached 7 [23,24].
2.2. Exfoliation of graphene oxide (GO)
To exfoliate the GO, sonicated the GO dispersion under normal
condition for 30 min. The homogeneous brown dispersion was
produced which was utilized for reduction. Dried the solution in
the vacuum oven at 40  C for 24 h [25].
2.3. Thermal reduction of graphene oxide
The GO was annealed in a Nabertherm Gmbh N17/HR-400V
Muffle heating furnace at 500  C at a heating rate of 2  C min1
for 2 h and allowed to cool in furnace till the temperature decreased
till 50 ± 5  C. The GO was completely converted into reduced gra-
phene oxide (rGO) [26,27].
2.4. Characterization
The X-Ray Diffraction STOE q-q was used with CuKa radiation
with wavelength 1.5406 Å and scintillation detector as sensor
equipment, scanning electron microscope (SEM) analysis in this
research was performed by JEOL scanning electron microscope
(JSM 6490LA), optical microscopy, UV-Vis spectroscopy (wave-
length 200 nm-1100 nm), Fourier transform infrared spectroscopy
(FTIR) were used to investigate the structural, optical, and func-
tional properties of graphene oxide (GO) and reduced graphene
oxide (rGO).
3. Results and discussions
3.1. X-ray diffraction (XRD)
XRD is used for the determination of crystal structure and lattice
parameters. During the oxidation process, we observed that the
intense peaks of the (002) plane (d-space 3.4 Å at 26.23 ) of
graphite flakes gradually debilitated and vanished which increased
the inter-planar distance from 3.4 Å to 7.5 Å and shifted the
diffraction peak of the plane (002) from 26.47 to 11.8 shown in
Fig. 1 [28]. This enlargement of inter-planar distance is due to the
entrapping of oxygen functional groups between the graphene
oxide sheets [27,29]. This is confirmed by the Bragg's equation 2d
sin q ¼ n l, shows the inverse relation of inter planar ‘d’ to the
diffraction angle ‘2W’.
After thermal reduction of graphene oxide, GO was reduced to
rGO and the ordered crystal structure of reduced graphene oxide
(rGO) was restored. This is verified by the reappearance of the (002)
diffraction peak at 25.5 and disappearance of the diffraction peak
(001) at 11.8 in XRD pattern in Fig. 2 [12,30]. During the reduction
of GO, the yellow brown solution gradually transferred into black
precipitate.
3.2. Scanning electron microscope (SEM)
In scanning electron microscopy, the surface of the specimen is
analyzed by an electron beam. SEM samples of graphene oxide (GO)
and reduced graphene oxide (rGO) were prepared by sonication of
GO in ethanol for 30 min. Dried the sample on a glass slide by
heating under an incandescent lamp. SEM image of graphite flakes
shows the flat surface with ordered layer structure [31]. Invariance,
graphene oxide reveals randomly aggregated, thin, crumpled layers
structure. It exhibits that the oriented layer structure of graphite
has been unbalanced due to its oxidation. In Fig. 3, the graphite
sheets have exfoliated into mono or multi-layer graphene oxide
(GO) sheets [27,32].
Fig. 4 shows the SEM images of reduced graphene oxide ori-
ented as randomly crumpled silk veil waves. The nanosheets are
rippled and entangled with each other. The lamella structure of
wrinkled rGO nanosheets is due to the van der Waal's interactions.
They are transparent and the lateral dimensions of the sheets
ranged from hundreds of nanometers to several micrometers
[30,33].
 H. Saleem et al. / Materials Chemistry and Physics 204 (2018) 1e7 3

3000 (001)

2000
Intensity (a.u.)

1000

GO
0

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85

Fig. 1. XRD of graphene oxide (GO).

300

(002)

200
Intensity (a.u.)

100

rGO

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85
2
Fig. 2. XRD of reduced graphene oxide (rGO).
4 H. Saleem et al. / Materials Chemistry and Physics 204 (2018) 1e7
Fig. 3. SEM images of Graphene Oxide (GO) layers.
Fig. 4. SEM images of Reduced Graphene Oxide (rGO).
3.3. Optical microscopy
The sample of GO for optical microscopy was made by sonicat-
ion of GO in water for 10 min. Spin coated the sample over an
oxidized silicone substrate. By using the Fresnel law, examined the
contrast on substrate used as reference thickness and light wave
length. We have examined the reliance of the contrast on the SiO2
thickness and light wavelength using Fresnel law. In Fig. 5, the
silicon substrate is purple in color. The brighter contrast shows the
high reflection of light from multi layers of GO and dull contrast
shows the lower reflection from the few and monolayers of GO [34].
3.4. UV-Vis spectroscopy
UV-Vis spectroscopy is mainly used to evaluate transmission or
absorptions in fluids and opaque solids. Add the solution of 10 mg
graphene oxide in 10 ml distilled water and 10 mg reduced gra-
phene oxide in 10 ml distilled water for the UV-Vis spectroscopy of
GO and rGO specimens.
In the oxidation process of graphite, the oxygen attached to the
graphene layers enhances the attraction of the layers which
intensify their solvency in water. This changed the yellow color of
the solution into brown. There can be different shades of brown
color depending upon the concentration of GO. In Fig. 6, the GO
Fig. 5. Optical image of Graphene Oxide (GO) at 500x, and at 1000x.
shows the absorption peak at 215 nm. The absorption peak varies
on the oxidation of graphite [35].
When GO is being reduced, the absorption peak of oxidized
graphene shifts to a greater wavelength from 215 nm to 267 nm.
This is due to the desorption of the oxygen attached to the graphene
layers after the thermal annealing shown in Fig. 7. As an impact of
this, the color has changed from brownish to dark [35]. Graphene
oxide nanosheets are hydrophilic and reduced graphene oxide
(rGO) nanosheets are hydrophobic. We noticed that GO solution is
stable in the water while rGO can homogenously disperse in water
via ultrasonic vibrations but the dispersion can only be stable for
few hours due to their hydrophobic nature.
3.5. FT-IR (Fourier Transform Infrared spectroscopy)
Fourier Transform Infrared spectroscopy (FTIR) spectra provide
information about the functional groups in a sample. At a 5 tons
pressure in a die, the 5 mm pallet of graphene oxide was prepared
by the mixture of dried graphene oxide and heated potassium
bromide. In Fig. 8, the existence of C¼O, C¼C, O-H, C-H bonds is
giving the surety of formation of graphene oxide [27]. In the graph,
the peaks of O-H (stretching vibrations), sp3 C-H, C¼O (stretching
vibrations) and C¼C (skeletal vibrations from unoxidized graphitic
domain) bonds show at 3394 nm, 2920 nm, 1723 nm, and 1619 nm
wavelengths. It is well established that GO contains various types of
oxygen functional groups such as hydroxyl, carbonyl, alkene and
cyanide functional groups.
The reduction process of GO must involve the removal of oxygen
functional groups. FT-IR spectra of reduced graphene oxide (rGO)
displays that after the thermal reduction of graphene oxide, most of
the oxides groups are removed in Fig. 9. However, hydroxyl group
(O-H) and cyanide (C-N) are still attached with the layers of rGO
due to the imperfect reaction with these groups [36].
4. Conclusion
Graphene oxide (GO) and reduced graphene oxide (rGO) were
synthesized by chemical exfoliation and thermal methods.
Graphite flakes were oxidized by KMnO4, H2SO4, and H3PO4 into
graphene oxide (GO) and annealed the GO to convert into reduced
graphene oxide (rGO). This is the novelty of work. In Modified
Hummer's Method, the graphene oxide is reduced by hydrazine
hydrate. In this work, graphene oxide was reduced by annealing at
500  C. Compared the results of graphene oxide and reduced gra-
phene oxide through different characterization techniques. In XRD,
the Bragg equation and inter planner distances showed the for-
mation of GO and rGO. SEM images displayed the random wrinkled
and crumpled silk waves morphologies of graphene oxide and
reduced graphene oxide. Different shades of contrast in optical
 H. Saleem et al. / Materials Chemistry and Physics 204 (2018) 1e7 5

Absorption 4

GO

1
200 250 300 350 400
Wavelegth(nm)
Fig. 6. UV-Vis spectrum of Graphene Oxide (GO).

2.6

2.5
Absorption

rGO

2.4

2.3
270 280 290 300
Wavelength(nm)
Fig. 7. UV-Vis spectrum of Reduced Graphene Oxide (rGO).
6 H. Saleem et al. / Materials Chemistry and Physics 204 (2018) 1e7

65

GO

% Transmittance

60

C=O

55

-C=C C=C -OH

C-N sp3 C-H
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavelength (nm)

Fig. 8. FT-IR graph of Graphene oxide (GO).

75

rGO
70
% Transmittance

65

60

C-N C=C
C-H
55 O-H

50
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavelength (nm)

Fig. 9. FT-IR of reduced graphene oxide (rGO).

microscopy showed the multi and monolayers of GO. UV-Vis References

spectrum exhibited the peaks of GO and rGO at 215 nm and
267 nm with the color changes from brown to darkish brown.
In FTIR, the presence of carbonyl, hydroxyl bonds proved the for-
mation of GO and removal of oxides groups gave the synthesis of
rGO.
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