Ceramics International 45 (2019) 14439–14448

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

XPS and structural studies of high quality graphene oxide and reduced T
graphene oxide prepared by different chemical oxidation methods
R. Al-Gaashania,b,∗, A. Najjarc, Y. Zakariaa, S. Mansoura, M.A. Atieha
a
Qatar Environment and Energy Research Institute (QEERI), Hamad Bin Khalifa University (HBKU), Qatar Foundation, PO Box 5825, Doha, Qatar
b
Physics Department, Faculty of Education, Thamar University, Dhamar, Republic of Yemen
c
College of Life and Health Sciences, Hamad Bin Khalifa University (HBKU), PO Box 34110, Doha, Qatar

A R T I C LE I N FO A B S T R A C T

Keywords: High quality graphene oxide (GO) and reduced graphene oxide (rGO) have been synthesized by chemical oxi-
Graphene oxide dation of graphite flakes via three modified Hummers methods using a mixture of sulfuric acid (H2SO4),
Reduced graphene oxide phosphoric acid (H3PO4) and nitric acid (HNO3) as intercalating agents and potassium permanganate (KMnO4)
Graphite and hydrogen peroxide (H2O2) as oxidizing agents. In this study the production of dangerously explosive gases
Chemical method
was avoided. The temperature was carefully controlled using ice baths, ensuring the temperature was kept at the
XPS
minimum during the reaction. The prepared samples were extensively characterized using various techniques
including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy
(EDS), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy
(FTIR), and X-ray photoelectron spectroscopy (XPS). The results indicated greater presence of oxygen containing
groups and an increase in the (C/O) ratio, both of which served as reliable indicators of high quality graphene
oxide. Atomic ratio of carbon to oxygen (C/O) quantified by XPS was calculated to be 25.67, 1.81, 1.63, and 2.77
of graphite, GO-I, GO-II, and GO-III, respectively. As revealed by FTIR analysis, the GO-I had more hydrophilic
oxygen functional groups compared to GO-II and GO-III.

1. Introduction
Since its discovery in 2004 [1] graphene has attracted much at-
tention in various fields of scientific research and applications ranging
from electronics, where it is used in the manufacture of graphene field
effect transistors [2] to sensors [3] and clean energy devices [4] to-
wards water purification and sterilization of waste water [5]. The im-
mense interest from such wide array of scientific disciplines arose from
the fundamentally unique and spectacular properties of graphene.
Chemically, graphene is two-dimensional nanomaterial and is com-
posed solely of a single layer of arranged carbon atoms. The resulting
honeycomb lattice is held together by σ bonds [2].
There are several ways in which graphene oxide (GO) can be pro-
duced; each have their own advantages and limitations. Mechanical
exfoliation [6], whilst attractive for producing high quality GO is lim-
ited in the way of large scale production feasibility [7]. Both mechan-
ical exfoliation (by means of ultrasonication or stirring) and epitaxial
growth on silicon carbide (SiC) wafer methods have been shown to
produce low yields [8]. Thermal exfoliation and chemical vapor
deposition (CVD) [9] are other methods that have been employed for
producing GO from graphite. However, chemical oxidation, remains the
most commonly favored approach in GO production [10].
Work done by Brodie in the 1859 produced the first ever GO using
potassium chlorate, graphite powder (usually graphite natural flakes)
and concentrated fuming nitric acid [11]. The method was improved by
Staudenmaier in 1898 where he included the use of concentrated sul-
furic acid in addition to the fuming nitric acid [12]. This modification
saw an increase in the amount of oxidized graphene oxide produced
whilst making the method more facile. Hummers and Offeman pub-
lished their paper in 1958 where they described the preparation of what
they called graphitic oxide using potassium permanganate (KMnO4)
and sodium nitrate (NaNO3) in the presence of sulfuric acid [13]. This
became known as the Hummers method and is the most favored method
used today [14]. A common feature of all three methods is the ultimate
oxidation of graphite to different degrees. During the process of oxi-
dizing graphite, functional groups such as hydroxyl groups (OH) con-
taining oxygen were introduced. This sees the expansion of the d-spa-
cing [8] of GO whereby interlayer interactions are restricted. These

∗
Corresponding author. Qatar Environment and Energy Research Institute (QEERI), Hamad Bin Khalifa University (HBKU), Qatar Foundation, PO Box 5825, Doha,
Qatar.
E-mail address: ralgaashani@hbku.edu.qa (R. Al-Gaashani).

https://doi.org/10.1016/j.ceramint.2019.04.165
Received 17 February 2019; Received in revised form 20 March 2019; Accepted 19 April 2019
Available online 20 April 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
R. Al-Gaashani, et al.
Fig. 1. Processes used in this study for synthesis of graphene oxide (method 1).
Fig. 2. Shows XRD patterns of graphite (a), graphene oxide (GO-I) prepared
using acids mixture of H2SO4, H3PO4, and HNO3 (70: 20:10) (b), graphene
oxide (GO-II) prepared using acids mixture of H2SO4, and H3PO4 (90:10) (c),
and graphene oxide (GO-III) and rGO prepared using ultrasonic bath (d).
polar oxygen-containing groups also result in the GO being hydrophilic,
with the added benefit of being easily dispersed in water and exfoliated
in a wide range of solvents [15].
The downside of all three methods described above involves the
evolution of toxic gases such as nitrogen dioxide (NO2) and dinitrogen
tetroxide (N2O2), both of which are harmful to the environment. In
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Ceramics International 45 (2019) 14439–14448
some cases chlorine dioxide (ClO2) is released as a byproduct. This
product, along with N2O2 are both explosive and hence render the ex-
periments hazardous [14]. The Hummers method has seen many
modifications and improvements [16], where different inorganic acids
have been used in variable ratios and proportions [17]. Different oxi-
dizing agents in different molar ratios have also been tested in order to
further optimize the procedure of producing GO [14].
One of the most important issues relating to the largescale pro-
duction of GO is the safety aspect of the method. Indeed, the traditional
Hummers method has the inherent risk of explosion due to the buildup
of manganese heptoxide (Mn2O7) [18]. Despite attempts to reduce the
temperature of the reactor [16] the control of the temperature
throughout the experiment has proven troublesome and impractical
[10]. Other studies have trailed the production of GO by means where
no toxic gases were produced [14]. Namely, Marcano et al., 2010
doubled the mass of KMnO4 whilst using a combination of sulfuric and
phosphoric acid in a 9:1 ratio. However, the rapid temperature increase
was not addressed in this study and therefore the need for a safer and
temperature controlled method remains of utmost importance when
producing GO. It is also worth noting that lower temperature has been
implicated in producing GO with lower defect [10].
GO with oxygen functional groups can be formed either by oxidized
graphene sheets or graphene oxide sheets that have their basal planes
adhered mostly with hydroxyl, epoxide, carbonyl, and carboxyl groups.
As reported by Lerf–Klinowski, oxygen functional groups localize pre-
sumably at the edges and transform the GO layer surfaces to high hy-
drophilic surfaces while water molecules can readily be inserted into
the interlayer galleries [19].
Recently, a large number of studies have revolved around the pro-
duction of GO for use as a nanofiller for polymeric membranes. The use
of GO was seen to enhance membrane performance attributes such as a
reduction in biofouling processes and increased water flux [20]. In one
such study GO sheets were synthesized for studying the possible anti-
bacterial effects of GO. The authors fabricated GO using a modified
version of the Hummer's method, however the processing temperature
was not maintained below 5 °C [21]. The use of different inorganic
acids were also not employed, rather only 98% sulfuric acid was used
for the production of GO [21].
The demand for high-grade GO over the years has greatly increased.
This is due to the versatility of GO in a wide number of applications.
Recently, GO was reported to find its use in biomedical applications
alongside reduced graphene and zinc oxide nanoparticles [22]. More
recently, a facile synthesis method of GO which possessed significant
enhanced properties for optoelectronic and energy devices was
R. Al-Gaashani, et al. Ceramics International 45 (2019) 14439–14448

Fig. 3. SEM images of graphite (a and b), GO-I graphene oxide (c and d), GO-II graphene oxide (e and f) (the inset in Fig. 3 (f) shows high magnification SEM image
(1 μm)), and GO-III graphene oxide (g and h).

reported. The study used a one-step approach employing electrolysis requirements.

technique. The GO sheets obtained showed superior characteristics in In this study we present findings of fully characterized GO, which
terms of thermal stability [23]. However, it should be noted that elec- have been prepared in a safe manner without the use of oxidizing
trolysis manufacturing processes are known for their energy intensive agents, which cause explosive or toxic gaseous products. Furthermore,

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Fig. 4. EDS spectra of graphite (a), GO-I graphene oxide (b), GO-II graphene oxide (c), and GO-III graphene oxide (d).

Table 1 2. Experimental
EDS elemental analysis of graphite, GO-I graphene oxide, GO-II graphene oxide,
and GO-III graphene oxide. Small Sepeaks appeared in GO-I and GO-II samples 2.1. Materials
due to treatment process with H2SO4.
Sample Elements Weight (Wt. %) Atom. conc. (at. %) Natural graphite flake (−10 mesh, purity 99.9%, manufacturer:
Alfa Aesar, Germany) was used as a raw material to produce graphene
Graphite C 98.72 99.03 oxide. A mixture of nitric acid (HNO3) (67–69%, RomilSpA limited™,
O 01.28 0.97
UK), hydrochloric acid (HCl) (37%, Sigma-Aldrich®, USA), phosphoric
Total 100 100
GO-I C 51.10 58.56 acid (H3PO4) (85 wt %, Honeywell Fluka®, India), and sulfuric acid
O 47.43 40.81 (H2SO4) (95%, VWR Chemicals®, France) were used as intercalating
S 01.47 0.63 agents. Hydrogen peroxide (H2O2) (30%, VWR Chemicals®, France) and
Total 100 100
potassium permanganate (KMnO4) (≥99%, Honeywell Fluka®, India)
GO-II C 54.52 61.93
O 43.81 37.36 were used as strong oxidizing agents. All chemicals were of analytical
S 01.67 0.71 reagent grades and used as received, without further purifications. The
Total 100 100 aqueous solutions were prepared in deionized water.
GO-III C 72.57 77.90 GO and rGO have been produced by oxidizing the graphite flakes by
O 27.43 22.10
three modified Hummers methods using different acids mixtures.
Total 100 100

the approaches utilized in this study demonstrate a cost-effective and
facile procedure for producing high-grade GO, while keeping the pro-
cess time to a minimum. The temperature was maintained below 5 °C
during the addition of different reactants with the use of ice baths and
chilled deionized water. The results indicate an improvement in the
quality of GO produced as well as a significant increase in oxygen
containing functional groups. The C/O ratio was also higher than that
reported in many of the previous studies [24].
2.2. Graphene oxide (GO-I) preparation (method 1)
In a typical experiment, 1 g of the graphite flakes was dispersed in a
ratio of 70: 20: 10 acids mixtures of H2SO4, H3PO4, and HNO3, re-
spectively, in a 500 ml beaker. The mixture was stirred at a medium
rpm for uniform dispersion. 6 g of KMnO4 was slowly added to the
mixture while maintaining the temperature below 5 °C using ice bath.
The solution was then maintained at 45 ± 5 °C for 2 h using an oil
bath. The beaker was then placed back into the ice bath and 100 ml of
deionized water was added slowly to avoid rapid increase in tempera-
ture. The beaker was then placed in the oil bath whilst maintaining the

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Fig. 5. TEM images of graphene oxide prepared using acids mixture of H2SO4, H3PO4, and HNO3 (70:20:10) (a and b), graphene oxide prepared using acids mixture
of H2SO4, and H3PO4 (90:10) (c and d), and graphene oxide (GO-III) prepared using ultrasonic bath (e and f).

temperature at 85 °C for 1 h. The mixture was stirred at a moderate rate
throughout the experiment. The experiment was brought to an end by
the simultaneous addition of 120 ml of deionized water and 15 ml H2O2
(30%). The reduction of the permanganate and manganese dioxide
could be easily observed by the color change from caramel brown to a
greenish yellow solution. The solution was left to reach room tem-
perature before being washed with an additional 25 ml of 9:1 deionized
water to HCl acid to remove metal ions and acids. The mixture was
centrifuged at 5000 rpm for 30 min at room temperature. The washing
was repeated many times using deionized water to wash out the acid.
The pH was checked continually and the washing was stopped once the
solution reached a neutral pH. The solution was placed in glass beakers
and incubated overnight in an oven at 85 °C. The preparation steps are
outlined in Fig. 1.
2.3. Graphene oxide (GO-II) preparation (method 2)
Graphene oxide (GO-II) was prepared using the same experimental

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steps detailed in the previous section of GO-I preparation with a change

of acid mixture to be H2SO4 (90%) and H3PO4 (10%) (90: 10).

2.4. Reduced graphene oxide (rGO) and graphene oxide (GO-III)

preparation (method 3)

The effect of ultrasonication on preparation of GO-III was studied

using an ultrasonic bath to produce rGO. The acid mixture with gra-
phite and KMnO4 were placed in an ultrasonic water bath at room
temperature and subjected to 1 h of ultrasound treatment in the ultra-
sonic bath before adding 120 ml of deionized water and 15 ml H2O2
(30%) to end the reaction. Then, the same experimental steps used to
prepare graphene oxide (GO-II) were applied for the remainder of the
experiment.

2.5. Characterization of samples

A Bruker D8 Advance X-Ray diffractometer (XRD) using Cu-Kα ra-

Fig. 6. Shows FT-IR spectra of graphite (a), graphene oxide (GO-I) prepared
using acids mixture of H2SO4, H3PO4, and HNO3 (70:20:10) (b), graphene oxide
(GO-II) prepared using acid mixture of H2SO4, and H3PO4 (90:10) (c), and
graphene oxide (GO-III) prepared using ultrasonic bath (d).
diation source (λ = 0.15418 nm), operated at 40 KV and 15 mA was
used to study the prepared GO samples. The morphology of samples
was observed using high-resolution transmission electron microscopy
(HRTEM) (FEI Talos200X) and Quanta 650 scanning electron micro-
scope (SEM) equipped with Bruker energy dispersive X-ray spectro-
meter (EDS). Thermo Scientific NICOLET iS50 FT-IR spectrometer was

Table 2
XPS compositional analysis, fitted parameters, and C/O atomic ratio of the C 1s, and O 1s spectra of the graphite and the as-prepared samples GO- (I, II, and III).
Samples Peaks Binding energy (eV) Peak area FWHM (eV) Atomic conc. (%) (C/O)a Phase/Groups
(C/O)b

Graphite (1) C 1s 284.76 70009.30 0.59 92.61 (25.67)a CeC

(2) C 1s 287.00 1000.31 1.15 1.33 CeO
(3) C 1s 288.28 875.27 1.35 1.16 C=O
(4) C 1s 289.50 875.27 1.35 1.16 OeC=O
(5) C 1s 291.28 3500.56 2.25 – π- π* Satellite
(1) O 1s 531.22 2325.42 1.20 1.32 OeC=O
(2) O 1s 532.45 2959.49 1.20 1.68 C=O
(3) O 1s 533.29 421.95 0.77 0.24 CeOH
(4) O 1s 533.95 879.40 1.25 0.50 CeOeC
Total 100
GO-I (1) C 1s 284.82 17653.27 1.42 13.06 (1.81)a CeC
(2) C 1s 286.62 39809.74 1.42 29.46 (1.43)b CeO
(3) C 1s 287.78 22473.69 1.42 16.63 C=O
(4) C 1s 289.12 7042.23 1.41 5.21 OeC=O
(5) C 1s 290.90 681.97 1.42 – π- π* Satellite
(1) O 1s 531.50 14782.08 1.35 4.01 OeC=O
(2) O 1s 532.34 51706.23 1.23 14.01 C=O
(3) O 1s 533.10 45584.04 1.23 12.36 CeOH
(4) O 1s 534.07 19384.42 1.35 5.26 CeOeC
Total 100
GO-II (1) C 1s 284.80 22161.80 1.11 20.24 (1.63)a CeC
(2) C 1s 286.82 39354.78 1.12 35.95 (1.66)b CeO
(3) C 1s 288.30 5254.50 1.44 4.80 C=O
(4) C 1s 289.70 1067.14 1.44 0.97 OeC=O
(5) C 1s 292.51 1192.73 1.55 – π- π* Satellite
(1) O 1s 530.97 4688.07 0.96 1.61 OeC=O
(2) O 1s 531.77 17690.59 0.96 6.06 C=O
(3) O 1s 532.60 65830.99 1.19 22.55 CeOH
(4) O 1s 533.33 22833.94 1.44 7.82 CeOeC
Total 100
GO-III (1) C 1s 284.83 37636.94 1.24 41.76 (2.77)a CeC
(2) C 1s 286.99 20739.10 1.15 23.03 (3.52)b CeO
(3) C 1s 288.43 5382.79 1.35 5.98 C=O
(4) C 1s 289.50 2413.86 1.35 2.68 OeC=O
(5) C 1s 291.20 1363.45 1.88 – π- π* Satellite
(1) O 1s 531.19 4911.12 1.35 2.13 OeC=O
(2) O 1s 532.26 18976.21 1.35 8.24 C=O
(3) O 1s 533.01 28848.95 1.25 12.53 CeOH
(4) O 1s 533.80 8390.21 1.44 3.65 CeOeC
Total 100

a
Atomic ratio of carbon to oxygen quantified by XPS.
b
Atomic ratio of carbon to oxygen quantified by EDS.

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Fig. 7. XPS survey spectra of graphite (a), graphene oxide (GO-I) prepared
using acids mixture of H2SO4, H3PO4, and HNO3 (70:20:10) (b), graphene oxide
(GO-II) prepared using acid mixture of H2SO4, and H3PO4 (90:10) (c), and
graphene oxide (GO-III) prepared using ultrasonic bath (d).
used to measure IR spectra. The chemical states of composing elements
of GO's were investigated by X-ray photoelectron spectroscopy (XPS)
using ThermoFisher ESCALAB 250i system. The binding energy values
of XPS lines were calibrated using the C 1s peak of adventitious carbon
at 284.8 eV as a reference.
3. Results and discussion
3.1. Structural characteristics of the samples
The graphite powder and synthesized GOs samples were analyzed
by XRD to study structural changes before and after acid treatments, in
particular, the interlayer distances. Fig. 2(a) shows XRD pattern of
graphite powder. The very sharp diffraction peaks observed at 26.50
and 54.64 2θ- Bragg angle, corresponds to (002) and (004) reflections
of graphite hexagonal structure, respectively. Fig. 2(b–d) shows the
XRD patterns of the prepared graphene oxides. The diffraction peak
detected at 2θ of about 10.9° can be attributed to the (001) plane of the
hexagonal crystalline structure of graphene oxide. For GO-I (Fig. 2 (b)),
the corresponding d (001)-spacing at 2θ = 10.9° was calculated using
Bragg's law to be 8.15 Å. However, the d (001) - spacing at 2θ = 11.2 and
2θ = 12.6° was calculated to be 7.94 and 7.07 Å of GO-II and GO-III
(Fig. 2 (c) and (d), respectively). The hydrophilic oxygen-containing
functional groups formed in the basal plane of GO sheets absorbed
water molecules, thereby increasing the d-spacing. It has been reported
that the interlayer distance of GO changes with the quantity of absorbed
water molecules in the basal plane galleries and structural defects to be
in the range of 6.1 Å for dry GO to 12 Å for hydrated GO [19]. Fig. 2 (d)
also displays a wide diffraction peak (200) located at 2θ = 25.4° cor-
responding to rGO with d-spacing of 3.46 Å which is almost close to the
typical thickness of pure single-layer graphene flake (3.4 Å) [25].
The XRD results indicated that, the GO-I had a higher quantity of
hydrophilic oxygen-containing functional groups compared to GO-II
and GO-III, due to higher inter-planar spacing. The absorbed water
molecules and the oxygen functional groups in the basal plane hold the
GO sheets together with an increased d-spacing. The XRD results (Fig. 2
(d)) also confirmed the reduction portion of GO to rGO when exposed to
ultrasound treatment for 1 h.
Morphological properties of the raw graphite and prepared GO
samples were studied by SEM. Fig. 3 (a and b) display the SEM images
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of the graphite particles before acid treatment, where rough surfaces
resembling leaf-like structures were observed. However, post acid
treated graphite samples; Fig. 3 (c to h) displayed the expected smooth
surfaces with wrinkles and folded regions. These observations could be
accounted for by the Sp3 carbons and formation of oxygen-containing
functional groups in the basal planes and various GO structural defects
[26,27]. From the SEM images (Fig. 3(g) and h), the degree of ag-
gregation of rGO is clearly higher than those of the GO samples shown
in Fig.3 (c to f). The reduction of oxygen containing functional groups
located in the basal plane of the Sp2 carbon permitted the lamellas of
the reduced GO sheets to be held together via weak van der Waal forces.
Consequently, rGO sheets were found to be highly aggregated with
crumpled features, as shown in their SEM images (Fig. 3 (g) and (h))
[26].
The elemental analysis of graphite as well the prepared GO samples
was investigated using EDS (Fig. 4 and Table 1). The O/C atomic per-
centage (at. %) of the oxygen contents increased from 0.98% for the
raw graphite (Fig. 4 (a)) to ∼ 41% for GO-I and 38% for GO-II (Fig. 4
(b)). However GO-III samples showed a lower oxygen content with
22.10% (at. %) compared to GO-I. This can be attributed to the fact that
a portion of GO-III was reduced to rGO when exposed to ultrasonic
treatment for 1 h, as confirmed by XRD (Fig. 2 (d)).
Fig. 5 depicts the TEM images of the three types of the graphene
oxide nanosheets (GO I, II and III). The presence of reduced graphene
oxide is seen in Fig. 5 (e and f) confirms the results seen in the XRD and
XPS analyses. All TEM images show clear folding, indicating the for-
mation of oxygen functional groups, as confirmed by the FTIR (Fig. 6)
and XPS (Table 2) data.
FTIR was used to determine the formed functional groups on the
graphene oxide samples. Fig. 6 represents the FTIR spectra of the (a)
graphite powder used as a raw material and the prepared graphene
oxide (GO-I) (b-d). The FTIR spectrum of GO shows a peak at
3425 cm−1, which represents the OeH stretching of the COOH group
while the bond centered at 2972 cm−1 is attributed to CeH stretching.
The peaks at approximately 1735 and 1635 cm−1 represent carboxyl/
carbonyl (C=O) and aromatic (C=C) stretching groups, respectively.
The broad peak occurring at 1450 cm−1 is due to OeH deformations of
CeOH groups, and the sharp peaks at 1083 and 1050 cm−1 represent
CeO stretching [28] while the peak at about 800 cm−1 is attributed
to = CeH bond. The absorption band centered approximately at
2340 cm−1 (Fig. 6 (c)) can be assigned to atmospheric CO2 (O=C=O).
During the ultrasonic treatment, some amount of carbon-oxygen func-
tional groups in the GO-III sample were reduced, resulting in reduced
graphene oxide yields as shown in Fig. 6 (c) and XRD pattern (Fig. 2
GO-III). The results of the FTIR spectra indicated that the GO-I pos-
sessed the highest content of oxygen functional groups compared to
GO-II and GO-III samples. Fig. 6 (d) clearly shows the reduction of the
carbon-oxygen functional groups in the GO-III sample, indicating that
part of GO was reduced to rGO as confirmed by XRD.
3.2. Compositional studies of the synthesized samples
The synthesized samples were further analyzed by X-ray photo-
electron spectroscopy (XPS) to further evaluate the chemical states of
various elements and the presence of functional groups. The survey
scan spectra of all samples showed mainly the presence of carbon and
oxygen with trace amount of sulfur (Fig. 7 (b) and (c)), which was a
result of process contamination.
Fig. 8 shows high-resolution XPS spectra of C 1s region. The de-
convoluted high resolution XPS C 1s region spectra of graphite used as
raw material is shown in Fig. 8 (a). The deconvoluted C 1s peaks 1, 2, 3,
4, and 5, as shown in Fig. 8 (a), showed peak binding energies of
284.76, 287.00, 288.28, 289.50, and 291.28 eV which correspond to
CeC (92.61 at.%), CeO (1.33 at.%), C=O (1.16 at.%), OeC=O
(1.16 at.%), and π- π* satellite bonds, respectively. However, after acid
treatments, the deconvoluted C 1s peaks 1, 2, 3, 4, and 5 with binding
R. Al-Gaashani, et al.
Fig. 8. Typical high-resolution XPS spectra of C 1s region of graphite (a), graphene oxide (GO-I) prepared using acids mixture of H2SO4, H3PO4, and HNO3 (70:20:10)
(b), graphene oxide (GO-II) prepared using acid mixture of H2SO4, and H3PO4 (90:10) (c), and graphene oxide (GO-III) prepared using ultrasonic bath (d).
energies of 284.82, 286.62, 287.78, 289.12, and 290.90 eV, assigned to
the CeC (13.06 at.%), CeO (29.46 at.%), C=O (16.63 at.%), OeC=O
(5.21 at.%), and π- π* satellite groups, respectively, of the graphene
oxide phase (Fig. 8 (b)). Similarity, the deconvoluted C 1s peaks 1, 2, 3,
and 4 with binding energies of 284.80, 286.82, 288.30, 289.70, and
292.51 eV represent the CeC (20.24 at.%), CeO (35.95 at.%), C=O
(4.80 at.%), OeC=O (0.97 at.%), and π- π* satellite bonds, respec-
tively, for the graphene oxide phase prepared using method 2 (Fig. 8
(c)). On the other hand, the deconvoluted C 1s peaks 1, 2, 3, 4 and 5
with binding energies of 284.83, 286.99, 288.43, 289.5, and 291.2 eV
are related to the CeC (41.76 at.%), CeO (23.03 at.%), C=O (5.98 at.
%), OeC=O (2.68 at.%), and π- π* satellite bonds, respectively, for the
graphene oxide and reduce graphene oxide phases prepared using
method 3 (Fig. 8 (d)) [19,29–32].
Fig. 9 shows high-resolution XPS spectra of O 1s region. The de-
convoluted O 1s peaks 1, 2, 3, and 4 with binding energies of 531.22,
532.45, 533.29, and 533.95 eV represent the OeC=O (1.32 at.%),
C=O (1.68 at.%), CeOH (0.24 at.%), and CeOeC (0.50 at.%), respec-
tively, of graphite phase (Fig. 9 (a)). The deconvoluted O 1s peaks 1, 2,
3, and 4 with binding energies of 531.50, 532.34, 533.10, and
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534.07 eV represent the OeC=O (4.01 at.%), C=O (14.01 at.%),
CeOH (12.36 at.%), and CeOeC (5.26 at.%), groups, respectively, for
the graphene oxide phase prepared using method (1) (Fig. 9 (b)).
However, the deconvoluted O 1s peaks 1, 2, 3, and 4 for the graphene
oxide phase prepared using method 2 have binding energies at 530.97,
531.77, 532.60, and 533.33 eV which are attributed to the OeC=O
(1.61 at.%), C=O (6.06 at.%), CeOH (22.55 at.%), and CeOeC
(7.82 at.%), respectively, (Fig. 9 (c)). The high-resolution XPS spectrum
of O 1s region of GO and rGO prepared by method 3 was fitted to peaks
1, 2, 3, and 4 with binding energies of 531.19, 532.26, 533.01, and
533.80 eV which represent the OeC=O (2.13 at.%), C=O (8.24 at.%),
CeOH (12.53 at.%), and CeOeC (3.65 at.%), respectively, (Fig. 9 (d))
[31,33–35]. The quantified atomic concentration of all phases and
functional groups was calculated using XPS analysis and shown in
Table 2. The atomic ratio of carbon to oxygen (C/O) quantified by XPS
was calculated to be 25.67, 1.81, 1.63, and 2.77 for graphite, GO-I, GO-
II, and GO-III samples, respectively, (Table 2). These ratios are in close
agreement with values calculated using EDS analysis as shown in Tables
1 & 2 and Fig. 4. From the XPS analysis, the atomic concentration (at.%)
of the oxygen-containing moieties, such as carbonyl, and carboxyl
R. Al-Gaashani, et al.
Fig. 9. Typical high-resolution XPS spectra in O 1s region of graphite (a), graphene oxide (GO-I) prepared using acids mixture of H2SO4, H3PO4, and HNO3 (70:20:10)
(b), graphene oxide (GO-II) prepared using acid mixture of H2SO4, and H3PO4 (90:10) (c), and graphene oxide (GO-III) prepared using ultrasonic bath (d).
groups of the GO-I and GO-II, considerably increased, showing that the
surfaces of GO-I and GO-II are more hydrophilic than that of graphite
and GO-III, while the sp2 hybridized zone on GO-I and GO-II are much
less than that of graphite and GO-III [36]. After exposing GO-III to ul-
trasound for 1 h, the C: O ratio of GO significantly increased from 1.63
to 2.77, indicating that part of GO was reduced to rGO as confirmed by
XRD and FTIR data.
4. Conclusions
We have reported facile and safe methods to synthesize high quality
graphene oxide (GO) and reduced graphene oxide (rGO) without the
production of toxic and explosive gases, whilst maintaining a low
production temperature. The morphological, structural and composi-
tional analyses showed that the synthesized materials were strongly
dependent on the mixture of acids. The structural analyses of all sam-
ples revealed the presence of a crystalline GO phase and confirmed the
reduction portion of GO to rGO when exposed to ultrasound treatment
for 1 h. The XPS and EDS analyses confirmed the atomic concentration
(at. %) of oxygen-containing moieties, such as carbonyl, and carboxyl
groups of the GO-I and GO-II, considerably increased, showing that
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Ceramics International 45 (2019) 14439–14448
surfaces of GO-I and GO-II were more hydrophilic than that of graphite
and GO-III, while the sp2 hybridized zone on GO-I and GO-II were much
less than that of graphite and GO-III samples. FTIR results further
confirmed that, the GO-I samples contained more oxygen functional
groups, compared to the other GO prepared samples. This further in-
creased the (O/C) ratio in the samples, rendering them higher-grade
graphene oxide. According to the quantified XPS data, GO-I sample
were found to possess the highest atomic ratio of carbon to oxygen (C/
O). The high quality graphene oxide produced has many applications
and uses in a number of scientific fields, such as in the design of
membranes incorporating GO as nanofillers for water treatment appli-
cations. GO with such high oxygen content would render the membrane
strongly hydrophilic. This would improve membrane characteristics,
including reduction in biofouling and increased flux. The demand for
high quality GO makes the samples produced and analyzed in this study
a promising way forward in GO production.
Acknowledgments
The authors would like to thank the support of Qatar Environmental
and Energy Research Institute and Hamad Bin Khalifa University. The
R. Al-Gaashani, et al. Ceramics International 45 (2019) 14439–14448

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members; Dr. Dhanasekaran Thirunavukkarasu (FTIR), Dr. Akshath [20] A. Najjar, S. Sabri, R. Al-Gaashani, V. Kochkodan, M.A. Atieh, Enhanced fouling
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