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Modified and improved Hummer's synthesis of graphene oxide for capacitors

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 Modern Electronic Materials 3 (2017) 110–116

Contents lists available at ScienceDirect

Modern Electronic Materials

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

Modified and improved Hummer's synthesis of graphene oxide for

capacitors applications☆
⁎
M. Sohaila, , M. Saleemb, Sana Ullaha, Noor Saeedb, Ayesha Afridib, Majid Khanb, M. Arifb
a
Shaheed Benazir Bhutto University, Sheringal Dir (Upper), KP, Pakistan
b
National Center of Excellence in Physical Chemistry, University of Peshawar, KP, Pakistan

A R T I C L E I N F O A BS T RAC T

Keywords: In the present study, we explored whether different characteristics of graphene oxide prepared via two different
Graphene oxide routes have been modified. It was observed that samples obtained via both routes have nearly the same physico-
Hummer's methods chemical characteristics. Spectral (FT-IR and UV-vis) studies showed the synthesis and optical properties of the
FT-IR materials respectively. Optical band gap (Eg) was found to be in the range of 3.1–3.9 eV. Thermal studies
TGA
demonstrated that the prepared materials exhibited stability up to 550 °C. X-ray diffraction evaluated the semi-
XRD
crystalline nature of the materials with crystallite size in the range from 27–28 nm. Dielectric study showed that
Dielectric properties
the materials are active at low frequency range due to interfacial polarization while at higher frequency the
dipoles present in the materials show relaxation behavior. The lowest value of dielectric tan. loss (0.03–0.39)
acquired by both the samples is of immense importance for capacitors. Based on the observations, graphene
oxide prepared is suggested to be used a possible material in thermally stable capacitors and in composite
materials.

1. Introduction the presence of oxygen containing functional groups such as -OH,

Graphene, a single layer of graphite where sp2 bonded carbon
atoms are arranged in a 2D hexagonal frame first reported in 2004 [1].
It acts as the basic building block for graphitic derivatives of all other
dimensionalities, such as fullerenes (0D), carbon nanotubes (1D) and
graphite (3D) [2]. Graphene has attracted a great attention owing to its
unusual structural, physicochemical and mechanical properties [3]. As
reported in literature, graphene possesses a large specific surface area,
high Young's modulus, efficient electron mobility, and good thermal
conductivity [1]. Likewise, its good electrical conductivity and high
optical transmittance (∼ 97.7%) made it admirable candidate to
produce electronic devices such as transparent conductive electrodes,
supercapacitors etc. [4,5]. However, the further study and applications
of graphene has severely limited due to its laborious peeling route of
synthesis and incapability of producing uniform and scalable deposi-
tions [6]. In this sense, for cost effective and facile mass production of
graphene, adaptable chemistry of carbon offers a promising substitute.
It is recommended that chemically modified graphene offer a suitable
alternative in this regard. Recently, the production of graphene oxide
(GO) has attracted immense attention as a promising intermediate for
the preparation of graphene in large quantity [7]. Furthermore, due to
-COOH attached to graphene layers, GO exhibits good hydrophilicity
and hence excellent dispersion in water unlike graphene and graphite
powder [8]. It is evident that the large fraction (50–60%) of GO is
comprised of sp3 hybridized C atoms which are covalently bonded with
oxygen atom in the form of hydroxyl and epoxy groups. The remaining
fraction (40%) is that of sp2 hybridized C and bonded either with
Oxygen in the form of carbonyl and carboxyl groups or with neighbor-
ing C atoms of GO sheet [8]. Such arrangement of atoms in GO makes
it hydrophilic and thus easily dispersible in water. This property also
enables GO to be modified, functionalized, dispersed in other solvents,
deposit and transport as compared to native graphene. The stable
dispersion of GO in numerous solvents enables it to be applied in
devices like transparent conducting films, double layered capacitors,
transistors for large area electronics, flexible displays, fuel and solar
cells, drug carrier and anti-bacterial material [9–13]. GO is also
considered as reinforcing agents in the formation of different compo-
site systems due to its good thermal and mechanical properties [2].
Graphite oxide influences different properties of graphene [14]. GO
composition have been used in CO2 storage and for capturing toxic
metals [15]. GO and rGO based nanocomposites have been synthesized
and used in for their permeation and electrical properties [16,17].

Peer review under responsibility of the National University of Science and Technology MISiS.
⁎
Corresponding author.
E-mail address: msohail2000@gmail.com (M. Sohail).

http://dx.doi.org/10.1016/j.moem.2017.07.002
Received 31 March 2017; Received in revised form 4 July 2017; Accepted 18 July 2017
2452-1779/ © 2017 The National University of Science and Technology MISiS. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
M. Sohail et al.
GO is prepared by common Hummers’ method designed many
years ago, [18] and other modified Hummers’ techniques [16].
During preparation, oxidation of graphite powders is carried out
by severe chemical regent (e.g. KNO3 KMnO4 NaNO3 and H2SO4),
and the resulting material is then exfoliated in water via mechanical
energy. Huang and colleagues [19] established an appropriate and
high yield method for the synthesis of uniform GO nano-sheets
based on a modified Hummer's method, where oxidation based on
KMnO4-H2SO4 was used continually to cut large GO sheets into
smaller GO nano-sheets having different lateral size. GO can then be
significantly restored or reduced to graphene sheets by chemical
reducing agents or thermal annealing which is generally known as
reduced graphene oxide (rGO) [20]. The unique properties of
possessing several designable functional groups and high surface-
to-volume ratio opens new gates for graphene oxide in the applica-
tion of biomedicine, such as bio-imaging and bio-sensing. GO has
rich surface bearing various functional groups and its easy surface
modification is an important feature that makes GO valuable over
other carbon materials. The band gap of GO can be controlled by
varying the ratio of sp2 to sp3 hybridized states. When fully oxidized
GO behaves as an insulator however, at partial oxidation level, it
behaves as a semiconductor. Regarding polarization-dielectric prop-
erties relationships, it is supposed that the existence of –OH,
–COOH and C=O groups on GO surface facilitates the presence of
interfacial polarization, which is perhaps favorable for the improve-
ment of dielectric constant of GO. Up to the best of our knowledge,
the existing literature is deficient regarding the dielectric analysis of
GO prepared via different routes and their applications in capacitors.
In the present study, we prepared GO thin films and powders via
using modified and improved protocols of Hummer's method respec-
tively. Structural, optical, thermal, dielectric and electric properties of
the prepared samples were investigated. The prepared materials were
used in capacitors to check their durability.
2. Experimental
2.1. Materials
The chemicals used in the experiments during this work were
graphite flakes, sulfuric acid (99%), hydrogen peroxide and orthopho-
sphoric acid purchased from Sharlu (Spain) while potassium perman-
ganate and potassium nitrate were supplied by BDH Chemicals
(England). Aqueous solutions of the reagents were prepared in MilliQ
doubly distilled water with conductivity 0.51 μS cm-1 and pH = 7. All
the chemicals were of analytical reagent grade and were used without
further purification.
2.2. Methodology
2.2.1. Preparation of GO via modified Hummer's protocol
During this experiment, GO was synthesized by chemical oxidation
and physical exfoliation procedures. Natural graphite flakes (0,5 g) +
25 ml H2SO4 (98% w/w) + 0.5 g KNO3 were taken in a 500 ml glass
beaker placed in an ice bath (0–5 °C) under vigorous magnetic stirring.
After about 10 min. KMnO4 (3 g) was slowly added to this solution. The
beaker was then transferred to a water bath (35 °C) and the solution
was again stirred for 1 h thus a thick dark paste was produced. In the
meanwhile, 100 ml de-ionized water was added to this solution under
stirring at 90 °C for 30 min accompanying dropwise addition of 30%
H2O2. Finally, dark brown solution was obtained which was then
filtered and washed with 100 ml distilled water until neutral pH. The
cakes obtained after filtration, were dispersed in water by mild
sonication for 1 h to become a suspension which was centrifuged at
4000 RPM (10 min twice). The supernatant (small GO pieces/water
soluble byproducts) was discarded while GO films (G1) were obtained
from the sediment under air-dry.
111
Modern Electronic Materials 3 (2017) 110–116
Graphite powder
Modified Hummer’s Improved Hummer’s
Method Method
G1 G2
Fig. 1. Flow sheet for the synthesis of GO via two different routes.
2.2.2. Preparation of GO via improved Hummer's protocol
During this experiment, 230 ml conc. H2SO4 was taken in a 2 L
Erlenmeyer flask and was cooled to 0 °C in an ice bath. Graphite
powder (10 g) and KNO3 (5 g) were gradually added to the flask under
magnetic stirring. The temperature of the system was increasing and at
about 20 °C, 30 g KMnO4 was slowly put into the suspension. The
system was then converted into a water bath at 35 °C and stirred for 2 h
while forming a thick paste. Subsequently, de-ionized water (230 ml)
was slowly added to this system and the suspension was maintained
at 98 °C for about 30 min and then diluted further with warm de-
ionized water to 1.4 L. To reduce residual permanganate and manga-
nese dioxide, the solution was treated with H2O2 (30%). The resulting
deep brown slurry was taken in dialysis membrane and was dialyzed
against distilled water for 7 days. Then further exfoliation was done
through ultra-sonication for 1 h. Unexfoliated GO layers were removed
by centrifugation at 4000 RPM (10 min twice). The solid GO powders
(G2) were obtained after drying the sample in a vacuum oven for 24 h
at 60 °C. The two routes are summarized in Fig. 1 while the mechanism
of formation for GO via both routes is shown in Scheme 1.
2.2.3. Characterization
Structural properties of the prepared materials were studied with
XRD (JDX-3532 JEOL Japan), FT-IR analysis via IR Prestige-21
(USA), optical properties were analyzed UV–Vis spectroscopy
(Perken Elmer, USA) and TG/DTA (Diamond TG/DTA Perken Elmer,
USA) was used to examine thermal properties. Detailed dielectric and
electrical properties of the samples were examined with RF
Impedance/Material Analyzer (Agilent E4 997 A, USA).
3. Results and discussion
3.1. FT-IR analysis
Functional group determination in G1 and G2 was done by FT-IR
spectroscopy in order to confirm their synthesis as shown in Fig. 2.
Some of the absorption bands around 3400, 3150, 1730, 1633, 1415,
1250, and 1077 cm−1 are ascribed to the residual oxygen functionalities
on GO which were still present on the surface with a lower transmit-
tance value. The hydroxyl (OH) stretching vibration of the C-OH
groups at GO surface is represented by a broad shoulder at
3450 cm−1. A weak band between 1620-30 cm−1 is assigned to the
C=O stretching vibrations of the –COOH groups [21]. Peak at
1285 cm−1 represents the O-H deformation of the C-OH group while
a weak band at 1028 cm−1 is accredited to C-O stretching vibrations.
The peak at 1730 cm-1 was assigned to the C=O stretching vibration
M. Sohail et al. Modern Electronic Materials 3 (2017) 110–116

Scheme 1. : Formation mechanism of Graphene oxide.

and the other typical absorption bands at 1633, 1040, and 1220 cm−1 3.2. Structural analysis
are attributed to the stretching vibration of sp2 hybridized carbon and
C-OH stretching respectively in G1 and G2 [22]. XRD analysis was used to observe the crystalline structure of the G1
and G2 films. The patterns were noted in the 2-theta (2θ) range from 5°
to 80°. Both the samples exhibit a 001 reflection at about 10°
90 corresponding to a basal spacing of d001 = 7.33 Å. Peaks at different
positions represent semi-crystalline and amorphous behavior of the
80 samples (Fig. 3). The sharp peak observed at 2θ = 10.400° (Fig. 3 (G1))
Absorbance (a.u)

with an interlayer spacing of 8.499 Å indicating the presence of oxygen-

Sp2 C in GO

containing functional groups (–OH, –COOH) formed during the

70
C=O C-H (-OH )
oxidation of graphite. A small broad peak at 2θ = 25.90° with an
(COOH) interlayer spacing 3.437 Å is ascribed to the lower degree of crystal-
60 lization and existence of any imperfections which shows the presence of
CO2 molecules [22]. Relative to G1, G2 crystallinity has been decreased
50 further while appearing certain broad peaks at 2θ = 25.2°, 26.7° and
42.7° with 4.001, 3.470 and 2.128 Å interlayer spacing respectively in
40 its XRD pattern. This may be attributed to the presence of un-oxidized
400 900 1400 1900 2400 2900 3400 3900 graphite flakes which results in the occurrence of phase change in the
material thus shifting the sample to more amorphous form. The
Wave number (cm-1)
average crystallite size of G1 and G2 samples was calculated by using
Fig. 2. Functional group analysis of G1 and G2.

112
M. Sohail et al. Modern Electronic Materials 3 (2017) 110–116

6.62

3.47
4000 Table 1

4.00
Optical band gap calculated for G1 and G2 samples.
3500
Sample ID Medium Optical band Gap (eV)
3000
G1 Water 3.9 ± 23
Intensity (a.u)

2500 G2 -do- 3.5 ± 01

G1

2.12
Ethanol
2000
G2 G1 -do- 3.4 ± 40
1500
8.49

G2 -do- 3.1 ± 11
3.49
3.43

1000
2.92

6
500 1st
5
0 2nd
10 20 30 40 50 60 70 80
4
3rd

Weight Loss
2θ˚
Fig. 3. XRD patterns for G1 and G2. 3 G1
G2
Scherer's formula as follows: 2

D = kλ / βcos θ (1)
1

where λ is X-ray wavelength (1.541 Å), D represents the average

0
crystallite size, β is line broadening in radians and θ is Bragg's angle
100 200 300 400 500 600 700
and k is Scherer's constant (0.9). The average crystallite size calculated
for both G1 and G2 was in the range from 27–28 nm with a lattice Temperature (˚C)
strain = 0.0112–0.0058 respectively, which is small enough (< 50 nm) Fig. 5. TGA curves for G1 and G2 samples.
for getting appropriate signal to noise ratio in high density recording
media in magnetic recording systems. 3.4. Thermal properties

Fig. 5 illustrates TGA curves for G1 and G2 where major weight

3.3. Optical properties
The formation of GO samples and their optical characteristics were
verified by UV-vis spectroscopy in the range from 200–800 nm (Fig. 4).
G1 and G2 solutions prepared in water and ethanol were examined
under UV light. The spectra of samples in both solvents show that there
is a peak centered at about 230–240 nm and nearly constant absor-
bance occurs above 600 nm. The spectra for G1 (aqueous) and G2
(ethanol) showed that the more ordered structure of GO may be due to
the retention of the carbon rings in the basal planes of GO. Nearly at
~200–230 nm transition of electrons from π–π* occurred. Both the
samples exhibited an additional shoulder in their spectra which is
ascribed to n–π* electronic transition [22]. The absorption edge of G1
is near to 300 nm. Using famous Tauc's relation, optical band gap
energy (Eg) for G1 and G2 was calculated and is summarized in Table 1.
The Eg values decrease from G1 to G2 (3.9–3.1 eV) in both solutions
which infers that the samples are insulators in nature.
losses occur at 120 °C. This is ascribed to the release of CO2, CO and
steam (water vapors) from most of the predisposed functional groups
in GO [23]. The second degradation step starts at about 170 °C and
completes at 220 °C. This is attributed to the stable graphene oxide
layers at this temperature. Beyond 200 °C, GO is converting to rGO
while losing most of its functionalities with increasing temperature.
The slow weight loss in the heating range from 300–600 °C corre-
sponds to the elimination of more stable oxygen functionalities that are
present in G1 and G2. The intense curvature appeared in TGA plots at
300–500 °C shows the occurrence of two antagonistic activities, i.e.,
loss of doubly bonded C=O component (release of by-products follow-
ing trapping) and concurrent feeding of C–O singly-bonded oxygen
groups. Both G1 and G2 accomplished complete degradation at about
550 °C. Fig. 6 reveals the DTA profiles of the G1 and G2. The DTA
curves of G1 and G2 demonstrate endothermic peaks between 100°
and 130 °C followed by two large exothermic peaks at 200 °C and
530 °C. The endothermic peak represents the glass transition tempera-

1.6

1.4 100

1.2 80
Tc
Absorption (a.u)

G1(H2O) 60 Tg
Microvolts (µV)

1
40
0.8 G2 (H2O) G1
20 G2
0.6 G1 (Ethanol)
0
G2 (Ethanol)
0.4
-20
0.2 -40

0 -60
200 300 400 500 600 700 800 50 150 250 350 450 550
Wavelenght (nm) T (°C)
Fig. 4. UV-vis. Spectra for G1 and G2 in water and ethanol. Fig. 6. DTA curves for G1 and G2 samples.

113
M. Sohail et al. Modern Electronic Materials 3 (2017) 110–116

1.00E+03

1.00E+02

Resistance (Ohm)
1.00E+01

G1
1.00E+00
G2

1.00E-01

1.00E-02
1.00E+06 1.00E+07 1.00E+08 1.00E+09 1.00E+10
Frequency (Hz)
Fig. 9. Variation of resistance with increasing frequency for G1 and G2 at ambient
temperature.

Fig. 7. Frequency dependence dielectric parameters (ɛʹ, ɛk, tanδ) (a) G1 and (b) G2.
Fig. 10. Nyquist plot of complex impedance (Zʹ vs. Zk) for G1 and G2 as a function of
frequency.

1.00E+02
1.17E+1
Ac Conductivity (S cm-1)

1.00E+01 Table 2
The fitted impedance measurements of both samples from G1 to G2.
1.00E+00
Sample ID Complex Modulus Resistance Capacitance Conductivity (σ)
1.00E-01 G1 (M*) (×107 Ω) (×10-11 F) (×10-6 S cm-1)
1.33E-2 G2
1.00E-02 G1 1.80 ± 10 2.20 ± 00 6.90 ± 02 1.17 ± 00
G2 1.51 ± 23 2.08 ± 11 4.65 ± 03 1.33 ± 10
1.00E-03

1.00E-04 materials. The dielectric performance depends upon electronic/ionic

1.00E-05
1.00E+06 1.00E+07 1.00E+08 1.00E+09
Frequency (Hz)
Fig. 8. Frequency dependence ac conductivity of G1 and G2 at room temperature.
ture (Tg) while the crystallization temperature (Tc) is denoted by the
exothermic peak. For G1 and G2, Tg is 120 °C where the materials
adopt viscous nature from their glassy and semi-crystalline form. For
both samples, Tc is in the range from 200 °C and 220 °C where their
molecules obtain enough freedom to spontaneously assemble them-
selves into a crystalline form.
3.5. Dielectric properties
Dielectric properties for G1 and G2 were investigated in the
frequency range from 1 MHz to 3 GHz at ambient temperature.
Dielectric constant (ε'), dielectric loss (ε'') and dielectric tangent loss
(tan δ) as a function of frequency are shown in Fig. 7a and b. As evident,
the dielectric parameters have large values in the low frequency (MHz)
region. It can be described on the basis of dielectric performance of the
orientation and space charge polarization. The real part ε' is related to
the bulk of polarization that occur in the material while ε'' (imaginary
part) is a measure of the energy dissipation that originates in GO frame
work. The space charge effect and unusual dielectric dispersion in the
materials enhance the values of dielectric parameters in low frequency
region. With increasing current frequency, the dipoles present in the
system are unable to modify themselves and respond. Consequently,
dielectric relaxation occurs which decreases the effects of ε′, ε′′ and tan δ
at high current frequency. It has been observed that induced electric
moment in G1 and G2 due to the presence of certain sp2 hybridized
carbon atoms has also an impact on its dielectric properties. The induced
electric moment polarization cannot adjust with the applied electric field
frequency at high range. However, the role of ionic conduction towards
total loss became outstanding at low frequency range in GO [24]. It is
apparent that ε', ε'' and tan δ are almost constant up to a specific
frequency range 1.5–1.9 GHz, after which resonance occurs with the
increase in frequency. In other words, a non-Debye behavior is examined
at high frequency in both the samples. This is also attributed to the fact
that electron hopping frequency becomes equal to the applied field
frequency at higher level. Frequency dependent tanδ is an important
parameter and it must be as low as possible in an ideal capacitor. Here in

114
M. Sohail et al.
our case, both G1 and G2 exhibit lowest values of tanδ (0.03–0.39). In
this regard, our prepared GO will be suitable candidates for applications
in capacitors.
The above data was used to investigate the ac conductivity of G1
and G2 in the frequency range 1.0 MHz to 3.0 GHz at room tempera-
ture in order to explore the mechanism of conduction. Using the
following Eqs. (2) and (3) [25], ac conductivity of the samples was
calculated.
̥ [3] H. Zhang, Z. Honglu, A. Aldalbahi, X. Zuo, C. Fan, X. Mi, Fluorescent biosensors
σac = ε′εωtanδ (2)
ω = 2πf (3)
where ε' is dielectric constant, ε̥ is the permittivity of free space (8.85 ×
10–12 F m−1), ω is the angular frequency of the applied field and tanδ is
dielectric loss. About linear variation of ac conductivity with increasing
frequency up to 1.58–1.6 Hz was observed for both samples (Fig. 8).
The results confirmed the presence of dominant conductivity disper-
sion in G1 and G2. Above 1.8 Hz, a resonance type (non-Debye)
behavior was observed. At low frequency, the ac performance of the
materials is attributed to the jumping of charge carriers, but as the
frequency increased, hopping of charge carriers occurred between the
localized states and hence the conductivity increased. Probably the
conduction may also be due the presence of small polarons present in
GO sheets. Furthermore, resistance (Rs) was noted to decrease for G1
and G2 with increasing current frequency which reflects the increase in
conductance of the materials (Fig. 9). It was found that at the point
where conductance was the highest, resistance was the lowest. The
variation in conductance in the range of 2 Hz and 3 Hz may be due to
the semi-crystalline and amorphous nature of G1 and G2.
Frequency-dependent impedance properties of G1 and G2 were
analyzed. Fig. 10 shows a Nyquist plot (Zʹ vs. Zk) for samples over a
wide range of frequency (1 MHz–3 GHz) at ambient temperature.
Using relation 4, impedance |Z| and phase angle θ values were utilized
to measure Zʹ and Zk. Supplementary parameters such as complex
impedance (Z*), complex permittivity (ε*) and complex electrical
modulus (M*) were extracted from the given data using Eqs. (5)–(7).
The detailed mathematical features of impedance formalism are
generally found in the literature [22–27].
Z′ = Z cosθ , Z ʺ = | Z | sinθ (4)
Z*(ω) = (Z′−!Z ʺ) (5)
ε*(ω) = (ε′ − ! ε ʺ) (6)
1 [17] S. Sadhukhan, T.K. Ghosh, D. Rana, I. Roy, A. Bhattacharyya, G. Sarkar,
M *(ω) = (ω) = (Mʹ + !M ʺ)
ε* (7)
where single bar (ʹ) represents the real part and double bar (k)
represents the imaginary part of all the parameters.
The shape of the plot is about a semicircle type which is character-
istically observed in super ionic materials showing lattice disorder. The
intercept of the semicircle on the Zʹ-axis represents the bulk resistance
(Rb) of the samples [28,29]. The center of the semicircle was found
somewhere below the real axis, which signifies that the nature of ions is
non-Debye during relaxation time. The appearance of semicircle at
high frequency region is due to the interfacial effects. However, at the
origin, the curve represents the bulk relaxation of dipoles in the
samples. Different parameters extracted from dielectric studies are
summarized in Table 2.
4. Conclusions
Graphene oxide was prepared by both modified and improved
Hummer's protocols. It was found that the materials obtained in both
cases exhibit nearly similar physico-chemical characteristics except a
little bit difference in crystalline nature. The former method produced
somewhat ordered structure of GO while the latter produced amorphous
materials. Optical, thermal, and dielectric properties studied suggest the
115
Modern Electronic Materials 3 (2017) 110–116
prepared materials to be used as suitable materials for thermally stable
capacitors and also as fillers/matrices in various composites.
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