Applied Nanoscience (2018) 8:751–758

https://doi.org/10.1007/s13204-018-0663-6

ORIGINAL ARTICLE

Synthesis of graphene oxide and reduced graphene oxide using

volumetric method by a novel approach without ­NaNO2 or ­NaNO3
Rajitha Gunda1 · Buchi Suresh Madireddy2 · Raj Kishora Dash1

Received: 5 December 2017 / Accepted: 17 January 2018 / Published online: 26 February 2018
© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
In the present work, graphite was processed to graphene oxide (GO) using modified Hummer’s method by volumetric titration
approach, without attaining zero temperature and the addition of toxic chemicals (­ NaNO2/NaNO3). The complete oxidation
of graphite to graphene oxide was obtained by controlled addition (volumetric titration) of ­KMnO4. The addition of higher
­KMnO4 resulted in partial oxidation and 2–3 mono-layers with less defects/disordered structure of reduced graphene oxide
(RGO) sheets were achieved. Samples were analyzed by XRD, FT-IR, Raman analysis, and TEM analysis. X-ray diffraction
displayed the oxidized peak of graphene oxide at 11.9° and reduced graphene oxide at 23.8°. The prolonged stability of the
synthesized GO with lower mole ratios of oxidizing agent was confirmed from UV–visible spectroscopy. Based on the results,
processed graphene oxide is found to be a candidate material for thermally stable capacitor application.

Keywords  Graphene oxide · Reduced graphene oxide · Raman · TEM · Spectroscopy

Introduction “Scotch tape Method”), and epitaxial growth on electri-

Graphene, a two dimensional and the thinnest known mate-
rial, attracted its attention globally because of its unique
optical, mechanical, and electrical properties (Shao et al.
2012; Kazi et al. 2015). Graphene is considered to be a
prominent material for a range of applications starting
from nano-electronics, nano-devices, MEMS, sensors, bio-
medical, energy storage devices, photodetectors, space, etc.
and the unique properties of graphene suggested numerous
applications (Bonaccorso et al. 2010; Sangamesha et al.
2014). Presently, graphene has been explored in the areas
of transistors, transparent conducting electrodes, integrated
circuits, ultra capacitors, bio-devices, and electro-mechan-
ical resonators.
There are several synthesis methods to obtain graphene
or layered graphene, such as CVD, SiC pyrolysis, graphite
oxide reduction, mechanical exfoliation method (also called
* Rajitha Gunda
gundarajitha2006@gmail.com
1
School of Engineering Sciences and Technology, University
of Hyderabad, Hyderabad 500046, Telangana, India
2
International Advanced Research Centre for Powder
Metallurgy and New Materials (ARCI), Balapur,
Hyderabad 500005, Telangana, India
cally insulating surfaces. Synthesis of pure graphene can be
done by CVD and several other methods such as (1) graphite
intercalation by sulphuric acid after mild oxidation by nitric
acid or other strong oxidizer such as potassium chlorate or
potassium permanganate; (2) thermal expansion of sulphu-
ric acid intercalated graphite to obtain expanded graphite
(EG); and (3) sono-acoustic exfoliation of the expanded
graphite filaments (Carotenuto et al. 2012a, b; Carotenut
and Nicolais 2012). Various synthesis techniques such as
Hummer’s and Modified Hummer’s methods were used for
the synthesis of graphene and chemically derived graphene
(Xu et al. 2008; Liu et al. 2010). In 1859, graphene oxide
(GO) was first synthesized by Benjamin C. Brodie by the
treatment of graphite with a mixture of potassium chlorate
and fuming ­HNO3. Hummers’ and Offeman (1958) used
mixture of sulphuric acid, sodium nitrite, and potassium
permanganate to develop GO. Synthesis of graphene using
chemical methods exists from the last decade, but attaining
its structure and morphology is a crucial step and is very dif-
ficult (Brodie 1859; Hummers and Offeman 1958). Besides,
GO has variable optical, mechanical, and electronic proper-
ties that can be tuned by controlling the degree of oxidation
(Villar-Rodil et al. 2009; Paredes et al. 2008). Hummer’s
method as “top–down” approach is widely used graphite as
precursor and this method possesses certain drawbacks, i.e.,

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752
use of strong oxidizers, uncontrollable thickness, smaller
flake size, and multi-step (Tang et al. 2012; Becerril et al.
2008). Recently, GO has attracted research interest due to its
increased solubility in polar and non-polar solvents (Dreyer
et al. 2010; Matloob and Guirguis 2016). Synthesis by Hum-
mer’s method in wet solution of strong acids and oxidizing
agents is highly inhomogeneous, which is difficult to clearly
determine the process of GO formation and content of differ-
ent oxygen-containing groups (Yi et al. 2013). Therefore, the
complete removal of oxygen groups is strenuous by chemical
or thermal reduction. This in turn limits graphene (pure)
synthesis and utilizes in fabrication of device-based applica-
tions, where chemical functionalization was achieved based
on Hummer’s method.
Keeping in view, to overcome all the above problems
and out of all existing and established methods, Hummer’s
process was used for the synthesis of GO by (i.e., redox
titration) volumetric titration method in which the synthesis
method reduces the defects and has high yields of graphene
which can be scalable to industrial level and easy in han-
dling the precursors during practical works. Review studies
on chemical methods of graphene synthesis were found to
be a step by step redox reaction (i.e., oxidation and reduc-
tion); exfoliation of graphite oxide to graphene oxide and
converted back to graphene by chemical reduction has better
yields and the properties vary with different reducing agents
such as hydroquinone, dimethylhydrazine, sodium citrate,
hexamethylene tetramine, ethylenediamine (EDA), thermal
treatments, sonochemical, and laser plasma (Liu et al. 2010).
GO consists of hexagonal carbon network having both sp2
and sp3 hybridized carbons bearing hydroxyl & epoxide on
either side of the sheet, where as the sheet edges are mostly
decorated by carboxyl & carbonyl groups (Won et al. 2010).
The strong bonding in between the layers of graphite is very
difficult to extract directly the graphene sheets, and hence,
oxygenated groups are introduced by oxidation of graph-
ite, so that it can reduce the mutual bonding, deducing the
exfoliation of graphite oxide by ultrasonication in different
solvents (Titelman et al. 2005).
Graphene is a new and multifunctional material that can
be easily obtained from graphite by various chemical routes.
Graphene oxide produced by exfoliation of graphite oxide
has been traditionally considered to be a precursor for gra-
phene synthesis, since it is the intermediate product besides
the formation of graphene (Chen et al. 2012; Stankovich
et al. 2007). The oxygen bonding and presence of sp3 hybrid-
ized carbon network in reduced graphene oxide (rGO) were
obtained, because partial reduction can be used as doped
semiconductor, since the negative charge on oxygen atom
provides charge flow in between anion and the positively
charged carbonium ion (Shao et al. 2012; Li et al. 2008; He
et al. 2011). Rapidly growing interest on graphene is well
known for its properties, where the values are incomparable
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Applied Nanoscience (2018) 8:751–758
to the highest theoretical values which were found from the
literature and is evident from the high yields of graphene via
chemical technique by the oxidation and subsequent reduc-
tion of graphite to GO followed by the reduced graphene
oxide sheets. Hence, GO with controlled structure and mor-
phology can be referred as precursor to deduce graphene
applications in various fields such as sensors, energy storage
devices, photodetectors, and drug delivery (Kazi et al. 2015).
In the present study, graphene oxide is processed from
graphite using Hummer’s method by volumetric titration
approach, without attaining zero temperature and the addi-
tion of toxic chemicals ­(NaNO2/NaNO3). The complete
oxidation of graphite to graphene oxide was obtained by
controlled addition (volumetric titration) of K ­ MnO4. The
final samples were characterized by XRD, Raman, FT-IR,
TEM, and UV-spectroscopic techniques and the results are
discussed.
Experimental details
Synthesis of GO and RGO
In a typical experiment, graphene oxide (GO) was syn-
thesized by chemical route via volumetric titration tech-
nique using chemical precursors such as graphite powder
(< 45 µm, 99.999% pure), sulphuric acid (99.99%), potas-
sium permanganate (99%), and hydrogen peroxide and
hydrazine hydrate (99%). A mixture of 1 gm graphite pow-
der in 10 ml of sulphuric acid ­(H2SO4) was continuously
stirred for an hour, followed by slow dropwise addition of
­KMnO4 with 0.2 (S1) mole (%) ratio over the period of
20 min and the reaction was carried out at room tempera-
ture with the color change to dark green and slowly rise in
temperature to 60 °C during the addition of K ­ MnO4, and
after few seconds (30 s), there was a gradual decrease in
temperature to 40 °C. Then after, the solution was stirred for
120 min and by adding ­H2O2 and ­H2O. The GO was settled
out and it was continuously stirred for 1 h and the filtered
product was washed with DI water and 5% HCl was added
to dissolve metals and final wash with methanol. The final
product was dried under vacuum at 50 °C for 24 h and the
experiment was repeated with 0.24 (S2), 0.3 (S3), and 0.5
(S4) mol% of ­KMnO4, respectively.
GO was dispersed in DI water using an ultrasonication
bath (Branson 40 kHz) subjected to reduction using Hydra-
zine hydrate (99.99%) at 75 °C under a cooling condenser for
4 h with constant stirring. After complete reaction, the prod-
uct is settled as reduced graphene oxide and it was filtered
and washed with DI water for several times until it neutral-
izes. Finally, the product was dried in an oven at 50 °C for
24 h under vacuum. All the GO samples were analyzed by
XRD (Bruker D8 Advance), FT-IR (Perkin Elmer Frontier),
Applied Nanoscience (2018) 8:751–758 753
TEM (FEI TECHNAI G2, G-Square, F-TWIN), Particle Size
Analyzer (nano sizer, Malvern), Raman (Witech) for struc-
ture and bonding and UV–visible spectroscopy measurement
(V670 spectrophotometer, Jasco). Figure 1a–d shows the
particle size distribution of synthesized graphene oxide and
a narrow distribution is observed at lower concentrations of
­KMnO4 indicating the more homogeneous powder through
the synthesis by volumetric titration approach. At higher
concentrations, multi-peaks were observed and might be due
to agglomeration of the particles. Average particle size is
found to be in the range of 200–250 nm for the samples S1,
S2, and S3 due to lower concentration of ­KMnO4.
Mechanism of GO synthesis
Sulfuric acid was used as a solvent in the oxidative mix-
ture, since it easily penetrates (intercalates) in the graphene
structure and thus facilitates the oxidation process. The oxi-
dizing mixture contains a very low amount of water (less
than 1 wt%) and, therefore, is extremely active and able
to produce graphite oxide species with a carbon/oxygen
Fig. 1  a–d Particle size distribution (histogram plots) of graphene oxide powder samples S1, S2, S3, and S4
ratio of 2:4, depending on the applied reaction conditions
(treatment time and temperature). The oxidation reaction
can be enhanced using ­KMnO4 as a strong oxidizing agent
in the presence of acid and ­NaNO2/NaNO3 as a catalyst.
Synthesis of GO without N ­ aNO2/NaNO3 excludes the N ­ a+
−
and ­NO3 ions, but the oxidation in the presence of sodium
nitrate or sodium nitrite liberates toxic gases such as ­NO2
and ­N2O4, which are hazardous to human life and in the
absence of these ions it undergoes zero order on proton con-
centration with one-electron and one-proton PCET mecha-
nism because of disproportionate reaction (Huynh et al.
2014).
When graphite was treated by strong oxidizing chemical
species, oxidation results in hydroxyls groups (–OH), ether
bridges (–O–), carbonyls (–CHO), and carboxylic groups
(–COOH) in the carbonaceous structure. These functional
groups were involved during the formation of GO by com-
plete oxidation of graphite-to-graphite/graphene oxide.
Typically, –OH, –CHO, epoxy (ether bridges), and –COOH
groups are bonded to partially unsaturated graphite network
both at edges and the inner regions of the plane. Graphite
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754 Applied Nanoscience (2018) 8:751–758

oxide is a colored (from yellow to dark green, depending
on the oxidation level) water-soluble material. This type of
graphite oxide can be conveniently used to prepare graphene
with good thermal and electrical conductivity. The combina-
tion of oxidation and thermal reduction treatments allows
in-depth disordered graphitic structure and decreases the
physical interactions among the carbon sheets (Carotenuto
et al. 2012c).
Results and discussion
Figure 2a, b shows the XRD patterns of GO and rGO sam-
ples. XRD analysis represents an increase in the broadness
with ­KMnO4 content, where the oxidation reaction initiated
with a change in color from black to dark greenish followed
by brown color. The peak broadened with the lower concen-
tration of oxidizing agent and a sharp peak shifts towards left
to lower 2θ values with an increase in oxidation keeps the
time period constant. Variation in the degree of oxidation
can cause a substantial change in structural and material
properties. XRD broad peak shows with nano-crystalline
and slow step (rate determining) oxidation reaction (Becerril
et al. 2008; Dreyer et al. 2010). Table 1 shows the effect of
­KMnO4 on GO synthesis with a change in mol% of K ­ MnO4
and dspacing. With an increase in the addition of ­KMnO4,
there was no much change in dspacing, but the sample S2 had
shown an increase in inter-planar distance, and hence, sam-
ples S1 and S2 are considered for the further analysis.
From the XRD patterns, parent graphite shows a very
sharp peak at 2θ = 26.5º which corresponds to (002) plane
with an inter-layer distance of 0.342 nm in addition to small
peaks at 2θ = 44.56° and 77.51° are associated with original
graphite powder (Matloob and Guirguis 2016). Figure 2a
shows graphene oxide formation (GO) from volumetric
titration by the oxidation with different concentrations of
oxidizing agent and the characteristic graphitic peak com-
pletely disappeared and a new diffraction peak was appeared
at about 11.89° for the sample S2 with an inter-planar spac-
ing of 0.74 nm. Whereas, the GO samples S1, S3, and S4
showed partial oxidation with the diffraction peaks found
at 13.59°, 13.13°, and 13.6° and the corresponding values
of dspacing are in the range of 0.65–0.67 nm, respectively.
The results indicated that there is no much increase in inter-
planar distance of the samples with the extent of oxidation
which could be seen from samples S1 and S2. The oxygen
functional groups attached on both sides of the graphene
sheets and the raised atomic scale roughness to the origi-
nally flat graphene sheets were responsible for the enlarged
layer spacing (Shao et al. 2012). An increase in oxidation
is observed in the samples S1, S2 over S3 and S4 from the
XRD analysis of their peak positions. Samples S1 and S2
were observed to be abnormal in their behavior from others,
and hence, GO samples S1 and S2 with the corresponding
rGO samples were studied for further analysis. Figure 2b
shows the XRD patterns of graphene oxide and reduced
graphene oxide for the sample S2. The broad peak at 23.5°
Table 1  2θ and d spacing of GO samples
S. no. sample code KMnO4 (mol%) 2θ d spacing (nm)
1 Sample 1-GO (S1) 0.2 13.27 0.667
2 Sample 2-GO (S2) 0.24 11.93 0.741
3 Sample 3-GO (S3) 0.3 13.06 0.677
4 Sample 4-GO (S4) 0.5 13.55 0.653

600 (002) GO-S2

rGO-S2
500
Intensity (arb. units)

400 (001)
(101)

300

200

100

0
0 20 40 60 80

2θ (degree)

(a) (b)

Fig. 2  a XRD plots of GO samples (1) 0.2 mol% (2) 0.24 mol% (3) 0.5 mol% (4) 0.3 mol%, respectively, and b comparison of GO and rGO for
sample S2

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Applied Nanoscience (2018) 8:751–758 755

indicates a random picking of graphene sheets in the rGO.
This peak is corresponding to (002) plane of graphite, which
is due to the removal of oxygen atoms. This confirms the
reduction process of graphene oxide to reduced graphene
oxide.
synthesis of fully oxidized GO was recovered by volumet-
ric drop by the addition of ­KMnO4 without ice bath and/or
­NaNO2.
Raman spectra of GO and rGO

FT‑IR spectroscopy Figure 4 shows the Raman spectra of GO and rGO sam-
ples (S1 and S2). Two peaks around 1500 cm −1 (D and
Figure 3a shows the FT-IR spectrum of GO samples. We G bands) are essentially identical to the characteristic
can infer that the effect of K
­ MnO4 on GO samples S1 and peaks of graphene oxide. A comparison of the spectra
S2 showed strong –OH bond stretch because of the interca- of graphene oxide with that of reduced graphene oxide
lated water molecules (OH) in between the graphitic layers shows that the D and G bands of graphene which are
at 3430 cm−1; C=O vibrations stretching was observed from observed at 1355 and 1605 cm −1   shifted to 1340 and
the sample S2 due to the carbonyl and carboxylic groups at 1586 cm −1 , respectively. This further confirms the
1730 cm−1, whereas with C=C aromatic stretch corresponds
to medium and multiple peaks at 1380 and 1600  cm−1,
respectively. FT-IR results show that with an increase in
the amount of K ­ MnO4, the oxidation decreases, since the
concentration of ­[H+] was suppressed due to the addition
of ­H2O2 (Shao et al. 2012; Paredes et al. 2008). Figure 3b
shows the FT-IR spectrum of GO and rGO samples. The
spectrum shows a peak of reduced graphene oxide repre-
senting O–H stretching vibrations observed at 3400 cm−1
which was significantly reduced due to de-oxygenation.
C–O-stretching vibrations observed at 1060 cm−1 are due
to the remaining carbonyl groups after the reduction process.
This further confirms the reduction of graphene oxide.
The experimental results from Figs. 2 and 3 revealed
that keeping the other parameters constant, increasing the
­KMnO4 (volumetric method) is not favorable for fully
oxidized graphite oxide. However, it is concluded that d
spacing of samples (S1, S2, S3, and S4) is almost same by
increasing the ­KMnO4. The subsequent synthesis of RGO Fig. 4  Comparison of D and G-band intensities with varied K
­ MnO4
was performed with samples S1 and S2. In our experiment, concentrations of samples S1 and S2

Fig. 3  a Comparison of GO and RGO of samples S1 and S2 and graphite, b GO with varying K
­ MnO4 concentrations

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reduction of graphene oxide to graphene. In addition, the
rise in D-band intensity and an increase in the ID/IG ratio
observed in the GO samples (S1 and S2) also confirms the
complete formation of GO due to the presence of func-
tional groups as observed from FTIR analysis (Fig. 3b).
There is an increase in G-band and 2D-band intensities of
rGO samples (S1 and S2). These observations showed an
increase in the aromatic size and decrease in the D-band
intensity because of the reduction of GO samples, i.e.,
S1 and S2, that was confirmed from Fig. 2b. XRD analy-
sis shows a complete reduction of GO with 2θ at 23.8°
indicating the retained graphitic structure and is also
supported by the presence of C=C aromatic stretch at
1622 and 1635.3 cm−1, respectively, from Fig. 3a. FT-IR
analysis observed the reduction process using hydrazine
monohydrate as reducing agent of GO samples (S1 and
S2) (Villar-Rodil et al. 2009). With the lower concentra-
tions of oxidizing agent, an increase in the oxidation tem-
peratures increased the ratio of sp3 domain formation and
the ID/IG ratio, which generates the defects. The ordering
of the sp2 and sp3 structures of the graphitic material var-
ied with an increased d spacing of the GO samples (S1
and S2). The effect of oxidizing agent on GO that alters
the reduction reaction temperatures where the sp2 domain
size varies with the addition of higher concentrations of
­KMnO4 is reported (Bansal et al. 2014; Gong 2011).
Fig. 5  TEM image analysis of sample S1 represents (a–c) and sample S2 represents (d–f)
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Applied Nanoscience (2018) 8:751–758
TEM analysis
TEM was employed to observe the morphology of the sam-
ples. Figure 5a–f of the samples S1 and S2 synthesized
GO by volumetric method shows the exfoliated graphene
oxide nanosheets by ultrasonication obtained with the thin-
layered structure nanosheets. The flat large dimension GO
nanosheets and few-layered morphology are observed and
HR-TEM images (Fig.  5b, e) confirmed the few-layered
structure. There are some evidences of partially exfoliated
graphene oxide sheets. The results indicated that resultant
graphene sheets were obtained by dispersion with single-
and few-layered sheets from the TEM analysis. The SED
images of rGO samples S1 and S2 (Fig. 5c, f) show the
crystalline nature of as-synthesized rGO without significant
structural defects. Hence, the synthesis of GO and rGO by
volumetric approach could be scaled up successfully (Szabo
et al. 2006; Noroozi et al. 2016).
UV spectroscopy
Figure 6 represents the UV spectroscopy of GO samples (S1,
S2, S3, and S4). GO is observed to be more stable due to the
formation of epoxide and ether functional groups confirmed
from FT-IR analysis, the band at 1630 cm−1 assigned to the
deformation vibration of adsorbed water molecules and also
the C–C skeletal vibrations due to the un-oxidized graphitic
domains within GO molecules shifts towards 1560 cm−1.
Applied Nanoscience (2018) 8:751–758 757
Fig. 6  UV spectroscopy of a GO varying K
­ MnO4 (mol%) samples S1, S2, S3, and S4 in aqueous solution, b rGO sample S1
The strong band at 1050 cm−1 is due to the vibrations from
C–O groups. The effect of ­KMnO4 with lower concentrations
shows partial re-conjugation of π network from UV–visible
spectroscopic analysis of graphene oxide sample, i.e., (S1)
that showed two characteristic peaks at 231 nm and shoulder
peak ~ 300 nm which corresponds to the π–π* transitions of
aromatic C–C stretch and π–π* transitions from C=O bond.
Hence, with an increase in ­KMnO4 (mol%), the absorbance
(%) is decreased. The GO synthesized with higher mole %
of ­KMnO4 (i.e., samples S3 and S4) confirmed the decrease
in extent of oxidation with the minimal functional groups
such as –OH, C=O, –COOH, C–O–C, and –COOR. In this
case, the GO samples were found to be highly unstable as
observed from the UV-spectroscopic analysis (Chen et al.
2013). The UV spectra of reduced graphene oxide on the
other hand show the red shift at 280 nm. The spectrum of
graphene oxide has an absorption peak at 230 nm, which
is shifted in graphene. This is a red shift which is due to
the electronic configuration of graphene in the reduction of
graphene oxide. The absorption peak at 230 nm is attributed
to the transition of aromatic C–C ring. The UV spectra of
reduced graphene oxide on the other hand show the red shift
at 280 nm and this absorption peak is attributed to transition
of C–O bonds.
Conclusion
Graphite was successfully processed to graphene oxide (GO)
using modified Hummer’s method by volumetric titration
approach, without attaining the zero temperature and extent
of oxidation in the absence of toxic chemicals such as N
­ aNO2
or ­NaNO3. Complete oxidation of graphite to graphene oxide
was obtained by controlled addition (volumetric titration)
of ­KMnO4. Experimental results revealed that the addition
of higher K­ MnO4 in which partial oxidation was obtained
and 2–3 mono-layers with less defects/disordered reduced
graphene oxide (RGO) nanosheets was achieved from this
process. X-ray diffraction displayed the peaks of graphene
oxide at 11.9° and reduced graphene oxide at 23.8°. TEM
analysis indicated that the resultant graphene sheets are dis-
persion of single and few layer nanosheets which were well
exfoliated without significant structural defects. UV–vis-
ible spectroscopic analysis of graphene oxide (S1) sample
shows two characteristic peaks at 231 nm and shoulder peak
at ~ 300 nm corresponds to π–π* transitions of aromatic
C–C stretch and π–π* transition from C=O bond.
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