Fullerenes, Nanotubes and Carbon Nanostructures

ISSN: 1536-383X (Print) 1536-4046 (Online) Journal homepage: https://www.tandfonline.com/loi/lfnn20

Appropriate conditions for preparing few-layered

graphene oxide and reduced graphene oxide

Shuntao Xu, Jinkun Liu, Yuan Xue, Tianya Wu & Zhengfu Zhang

To cite this article: Shuntao Xu, Jinkun Liu, Yuan Xue, Tianya Wu & Zhengfu Zhang
(2017) Appropriate conditions for preparing few-layered graphene oxide and reduced
graphene oxide, Fullerenes, Nanotubes and Carbon Nanostructures, 25:1, 40-46, DOI:
10.1080/1536383X.2016.1247268

To link to this article: https://doi.org/10.1080/1536383X.2016.1247268

Accepted author version posted online: 27

Oct 2016.
Published online: 27 Oct 2016.

Submit your article to this journal

Article views: 246

View Crossmark data

Citing articles: 3 View citing articles

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=lfnn20
FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES
2017, VOL. 25, NO. 1, 40–46
http://dx.doi.org/10.1080/1536383X.2016.1247268

Appropriate conditions for preparing few-layered graphene oxide and reduced

graphene oxide
Shuntao Xu, Jinkun Liu, Yuan Xue, Tianya Wu, and Zhengfu Zhang
Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, China

ABSTRACT ARTICLE HISTORY

Oxidation time and exfoliated conditions of graphite oxides (GOs) were investigated to prepare few–layer Received 7 October 2016
graphene oxide and reduced graphene oxide via a modified Hummers approach. Different oxidative Accepted 8 October 2016
degree of GOs was prepared by changing oxidation time, and the effects of oxidative degree of GOs in KEYWORDS
different oxidation time were studied by XRD, FT-IR. Afterwards, highly oxidized GOs were used as Graphene oxide; Graphite
precursor to prepare graphene oxide and reduced graphene oxide by ultrasonic dispersion method and oxide; Oxidation time;
thermal expansion method. The exfoliated conditions (ultrasonic power and ultrasonic time, thermal Exfoliation technology
exfoliated temperature) were investigated to prepare few-layered graphene oxide and reduced graphene
oxide.

1. Introduction
Graphene oxide and reduced graphene oxide are the gra-
phene derivatives, which become the significant research
material during the last decade. The graphene oxide was
used in polymer composites and biomedical applications (1).
The reduced graphene oxide is used as energy-related mate-
rials such as super capacitor and lithium-ion batteries (2).
Oxidative-exfoliation of graphite was proposed to produce
large quantities of graphene oxide nanosheets and it is a
promising route to achieve mass production of graphene
oxide and reduced graphene platelets (3). The graphene
oxide is generated from the graphite oxides (GOs) through
the appropriate exfoliated technology separate the tights tack
graphene sheet. The mainly exfoliation technology include
ultrasonic method and thermal expand method, which are
the most common approaches to prepare graphene oxide
and reduced graphene oxide (4). The graphite is oxidized by
strong oxidizing agents such as treatment with KMnO4 and
NaNO3 in concentrated H2SO4 prepare GOs (5). GOs has a
similar layered structure like graphite but the plane of car-
bon atoms in GOs is heavily decorated by oxygen-containing
groups which not only expand the interlayer distance but
also make the atomic-thick layers hydrophilic (6). The oxy-
gen-containing groups and expand of interlayer distance
supply the condition that exfoliating GOs to graphene oxide
and reduced graphene oxide by ultrasonic and thermal
expand method.
GOs are the precursor of preparing graphene oxide and
reduced graphene oxide. Nowadays, the graphene takes very
important role in the field of material science, oxidative-
exfoliation technology as traditional method to produce
functionalized graphene nanosheets and reduced graphene
oxide, which render the research of GOs become focus again.
Currently, the preparation of GOs can be divided into three
major methods: Brodie (7), Staudenmaier (8), Hummers (5),
these methods comprise the primary routes to prepare GOs.
Compared to each other, indispensable gas ClO2 and Oxida-
tions by HNO3 result in the liberation of gaseous NO2
and/or N2O4 in Brodie method is toxic to human beings; the
long process of Staudenmaier method isn’t suitable for
industrial manufacture (9); the Hummer method displays
the characteristic of relative safety, easy to operate and time-
saving in preparation, so it was widely adopted in GOs prep-
aration. Based on Hummers method some modification has
been proposed, these methods are usually named modified
Hummers method, and they are more popular method to
prepare GOs (10). Though many study have been carry out
to character the structure of GOs, and many structural mod-
els of GOs was proposed, such as Rues’s model, Lerf and Kli-
nowski model, the latter is widely accepted GOs model (11).
The precise chemical structure of GOs is still not quite clear,
which contributes to the complexity of GOs due to its partial
amorphous character (6). From all model of GOs, we can
conclude that during oxidation, the carbon plane is deco-
rated with hydroxyl and epoxycarboxyl functional groups
and the integrity of carbon atoms plane was destroyed,
which is the most different between pristine carbon atoms
plane and GOs sheets. There are many publication have set
about to study the GOs, it have been reported that the
amount of oxygenated functional groups in the GOs was var-
ied by changing the amount of KMnO4 from 1 to 6 g in Bro-
die method (12). Another, GOs with different degree of

CONTACT Zhengfu Zhang zhang-zhengfu@163.com Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming
650093, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lfnn.
© 2017 Taylor & Francis Group, LLC

oxidation was prepared through changing the oxidation
times, which the oxidations times were controlled from 1 to
3 times have been reported and the oxidative degree was esti-
mated through the relative intensity of the infrared absorp-
tion bands and XRD patterns (13,14).
It has been reported that the oxidization treatment in term
of decreasing interlayer Van Waals force can enlarge the inter-
layer space from 0.34 nm to 0.7–1 nm, which creates a possibil-
ity to produce graphene oxide and reduced graphene oxide by
exfoliating the GOs (15). Nowadays ultrasonic and thermal
expand method is the most common method to exfoliated GOs
to graphene oxide and reduced graphene oxide. The oxidation
of graphite render the decrease of interlayer Van der Waals’
force, therefore, the GOs under cavitation and dispersion of
ultrasonic can exfoliate the GOs to graphene oxide. But in gen-
eral, the production rate of sonication-assisted exfoliation is
low since the stratagem was carry out in low-power sonication,
which results the products distribution unevenly. Thus, the
moderate ultrasonic condition needs to systematically study to
prepare individual or few-layer graphene oxide.
Thermal exfoliation is certainly the most common method
of reducing graphene oxide, the thermal exfoliated mechanism
of the stacked structure is extrusion of carbon dioxide gener-
ated by heating GOs to high temperature and at high tempera-
ture gas creates enormous pressure within the stacked layers
result the exfoliation of graphene sheets (GSs) during rapid
heating (16,17). Based on state equation, a pressure of 40 MPa
is generated at 300 C, while 130 MPa is generated at 1000 C
(18). Evaluation of the Hamaker constant predicts that a pres-
sure of only 2.5 MPa is enough to separate two stacked GOs
platelets (18). What is noteworthy is that during thermal exfoli-
ation, functional groups decomposition is generated, which
render the graphene oxide was partly reduced. Thus, thermal
exfoliated graphene oxide is reduced graphene oxide (19). Tem-
perature is a critical cause to synthesis of graphene-like materi-
als through the exfoliation of GOs (19). There are many
publication set about to prepare the graphene oxide at 1050 C,
but, according to Hamaker’ state (18), the 1050 C is not neces-
sary. Thus, in this work we study the influence of exfoliation
temperature on the morphology and structure of graphene
oxide.
From the statement about oxidation–exfoliation method to
prepare GOs, we can conclude that the final products are deter-
mined by oxidative degree of GOs and exfoliation condition.
Thus, we have investigated the oxidative degree of GOs in dif-
ferent oxidation time, the graphene oxide and reduced gra-
phene oxides exfoliated by ultrasonic and thermal method were
investigated by BET, TEM, XRD, FTIR, and Raman spectrum,
and the moderate oxidation time and exfoliated conditions
were studied in this paper.
2. Experimental
2.1. Synthesis of GOs
The GOs was prepared based on improved Hummers method.
18 g potassium permanganate (Jin shan Chemical Reagents Co,
Cheng Du, China) was slowly added to 500 mL flask filled the
mixture of 3 g commercial natural graphite powders (99%,
FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 41
Table 1. The relationship between interlayer distance of GOs and oxidation time.
Samples Oxidation time (h) 2u (deg) Interlayer space (nm)
Graphite 0 26.6 0.334
GOS 2 9.12 0.969
GOS 4 8.18 1.08
GOS 10 6.68 1.32
GOS 15 6.58 1.34
GOS 25 6.06 1.45
37-mm nominal particle size, Ji Xing Sheng An Industry &
Trade Co, Bei Jing, China) and 69 mL 98% sulfuric acid (ana-
lytical grade) before the mixture was cooled down to 0 C by
means of an ice bath. Then, the solution was heated to suitable
oxidation temperature with a water bath, the mixture stirred
with a magnetic stirring bar and oxidization with different oxi-
dation time (shown in Table 1). After reaction, the deionized
water (200 mL) was added into the thick paste with stirring.
After that, temperature was hated to 93 C over 30 min until
the mixed solution became bright yellow. More deionized water
(300 mL) was added into solution, and 3 mL H2O2 (30%) was
gradually added until the bubbling disappeared. Finally, the
mixture was filtrated with filter, the supernatant being decanted
away. Brown remaining solid material was then washed with
HCl-mixed solvent (9/1 volume ratio) and purified water, and
this process being repeated until the pH was neutral. GO was
dried under vacuum at 60 C for 12 h, then totally ground
obtain the GO powders.
2.2. Preparation of graphene oxide and reduced
graphene oxide
GOs prepared as outlined above, the GOs (oxidized 10 h) were
re-dispersed into deionized water, mixture solution was aver-
agely divided into 8 portions and treated by ultrasonic in differ-
ent ultrasonic power and ultrasonic time, then the solution was
centrifugated at 8000 r/min, suspension froze-dried to gra-
phene oxide. Another, the reduced graphene oxide was pre-
pared in different temperature exfoliation. An alumina boat
loaded with GOs was quickly moved into a tube furnace, kept
1 min in tubular furnace at different temperature (400 C,
750 C, 1050 C) to obtain reduce graphene oxide.
3. Characterization
GOs in different oxidation time, graphene oxide and reduced
graphene oxide were analyzed using (Rigaku>D/Max 
2200)
powder X-ray diffractometer with Cu KR (λ D 1.5406 A) radia-
tion at a scan speed of 1 /min and a step size of 0.03 in the
range of 5  2u  80 .
Graphite, GOs in different oxidized time, graphene oxide
and reduced graphene oxide were checked by Raman Spec-
trometer (Renishaw MKI1000) and FTIR spectrometer
(Bruker TENSOR27).
Their microstructure of graphene oxide and reduced gra-
phene oxide was investigated with Transparent Electron
Microscopy (TEM) (FEI-Tecnai G2TF30), the specific surface
area was performed with BET method (Beishid-3H-2000A).
42 S. XU ET AL.

Figure 1. (a) XRD pattern of graphite, dry 2 h at 120 C. 215 £ 166 mm (300 £ 300 DPI). (b) XRD pattern of GOs prepared with various oxidation time, drying 12 h at
120 C.215 £ 166 mm (300 £ 300 DPI).

4. Results and discussion
4.1. Structure evolution of GOs with different
oxidation time
Changing the reaction time for the oxidation of graphite was
employed to tune the oxygen content of GOs. GOs prepared in
different oxidation time and parent graphite were evaluated by
XRD. As shown in Figure1(a), pristine graphite exhibits a high
crystalline degree with a strong and sharp diffraction peak at
2# D 26.5 and 2# D 43 , which is corresponding to the dif-
fraction of the (002) plane and diffraction of the (004), the
interlayer distance of graphite is 0.334 nm through the Bragg
equation (20). XRD pattern of GOs in different oxidation time
is shown in Figure 1(b). It becomes obvious that diffraction
peak at 2# D 6.32 ¡9.12 , which is corresponding to the
characteristic diffraction peak of GOs. The interlayer distance
of GOs is 0.969 nm-1.45 nm according to Bragg equation,
when the oxidation time is from 2 h to 25 h. This happened
because oxygen functional groups were attached on both sides
of the single graphene layer during graphite oxidized. And the
result of the interlayer distance in different oxidation time
increase is shown in Table 1, with the oxidation time increas-
ing, the interlayer distance is enlarged from 0.34 nm to
1.45 nm, but when oxidation time is over 10 h, the increased
amplitude of the interlayer space is unapparent. When oxida-
tion time is 10 h, the interlayer distance is 1.32 nm, and when
the oxidation time increases to 1 5 h, the interlayer distance is
1.34 nm. It is suggested that the graphite had been fully oxi-
dized when oxidation is over 10 h, the more oxidation time
consume results little expand of interlayer distance. Thus, we

Figure 2. (a) FTIR spectra patterns of GOs prepared with various oxidation time. 215 £ 166 mm (300 £ 300 DPI). (b) Raman spectra of graphite 215 £ 166 mm
(300 £ 300 DPI). (c) Raman spectra of GOs prepared with various oxidation time. 215 £ 166 mm (300 £ 300 DPI).

conclude that oxidation over 10 h is enough to prepare highly
oxidized GOs.
In order to investigate oxygen-containing groups of GOs,
the obtained samples were subjected to FTIR measurements.
The FITR spectrum results shown in Figure 2(a), one can see
that GOs contain much oxygen-containing groups (21,22).
Absorption bands displayed as follow: a broad and intense
band at 3419 cm¡1 in graphite and GOs, which can be assigned
to O-H stretching vibration; O-H stretching vibration in graph-
ite is attributed to water, the O-H band absorption intensity of
the GOs is stronger than graphite, it is suggested that more O-
H groups are existed in GOs during oxidation. Comparing
absorption peak strength about graphite and GOs, it can be
seen that the strength of GOs is significantly stronger than
graphite. Simultaneously, as the oxidation time prolonging, the
intensity gradually increased, it proves that the content of oxy-
gen-containing groups and oxidative degree of GOs are
increased gradually. A band attribute to deformation vibration
absorption of C-O at 1095 cm¡1, it corresponds to the C-O-C
structure of graphite and GOs. Comparing original graphite, a
new absorption peak at position 1720 cm¡1 appear in the GOs,
it is proved that it belongs to the CDO stretching vibrations.
The bands at 1400 cm¡1 to 1440 cm¡1 and 1290 cm¡1 to
1230 cm¡1 are the C-O absorption of carboxyl, the position of
the C-O absorption peak of carboxyl is partly overlap with C-O
absorption peak in C-O-C. Furthermore, there is an additional
band located at 1620 cm¡1, which can be attributed to unoxi-
dized graphitic domain (23). Through the FTIR analysis, it can
be confirmed that carboxyl, hydroxyl, epoxy, carbonyl existed
in GOs lead to the increase of interlayer distance. When the
oxidative time of GOs was changed from 2 h to 25 h, the posi-
tion of FTIR bands is unchanged, but the strength of absorption
peak is changed obviously and it proves that oxidative degree
increase. However, it is worth noting that the infrared absorp-
tion spectrum almost overlapping after 10 h, 15 h, 25 h oxidiz-
ing, which means the effect of prolonging oxidation time is
indistinctive when oxidation time over 10 h, this will be proved
by following XRD testing results.
Raman spectroscopy is frequently used to study carbona-
ceous materials, the detail testing conditions for Raman spectra
as below. Graphite and GOs: laser energy 50%, scanning 3 s,
integral 3 times, acquisition time 9 s; Graphene oxide: laser
energy 25%, scanning 1 s, integral 1 times, acquisition time 1 s;
Reduced graphene oxide: laser energy 25%, scanning 3 s, inte-
gral 3 times, acquisition time 9 s, and all samples were depos-
ited on silicon wafers in powder form without using any
solvent. Figure 2(b) and (c) are typical Raman spectra of graph-
ite and GOs prepared with various oxidation time. Two charac-
teristic absorption bands have been shown, the G band at
around 1567 cm¡1 and the D band at 1350 cm¡1. In the graph-
ite, the intensity of D is very weak, and it is caused by graphite
edges (24), but in GOs the stronger intensity can be observed
compared original graphite, which is caused by symmetry is
broken or a high density of defects in the samples (25). The G
band is due to the E2g vibration mode, and it is associated with
the vibration of sp2 carbon atoms in a graphitic 2D hexagonal
lattice. Comparing the Raman spectra of graphite and GOs,
one can see that the D band of GOs is stronger than graphite,
which attribute to GOs generate more defects and functional
FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 43
groups during the oxidation process. Graphene layer partly
destroyed results in more edges existed in the graphite oxides,
that is attributed to a large number of functional groups
attached on graphene layer after oxidizing. The intensity ratios
of (ID/IG) in graphite oxide are markedly increased compared
to that of graphite, ID/IG of graphite oxide is 0.83, 0.93, 0.97,
0.98, 0.99, respectively, when oxidation time increased from 3 h
to 25 h, which indicates that formation of the sp3 carbon after
the graphite is oxidized, the defect of graphite oxide is increased
with the oxidation time. From the Figure 2(b), (c), the D band
and G band of GOs are universally broad, which is attributed
to the layer stack with high disorder and defects formation
accompanied with more topological defects and vacancies.
“The defects…XRD pattern” is not clear, the revised sentence
is: The defects mainly associated with the introduction of func-
tional groups and impurity defects during the oxidation, the
increase of ID/IG indicates that the contents of functional
groups and the enlarge of interlayer distance result more
defects in GOs, which is consistent with the analysis of FITR
spectroscopy and XRD patterns. In Figure 2(b), (c), the position
of G band significantly shifts to higher frequencies (blue-shift)
in the graphite oxide and the intensity of D band becomes
stronger during the oxidation time extend, it is attributable to
more disorder defects than graphite.
4.2. Appropriate prepared conditions of graphene oxide
and reduced graphene oxide
Figure 3(a)–(d) is TEM images of graphene oxide under differ-
ent ultrasonic power and different ultrasonic time, (e)-(f) are the
TEM images of reduced graphene oxides in different thermal
exfoliated temperature. The GOs oxidized over 10 h was dis-
persed in 400 mL deionized water solution, and the dispersion
solution was divided into volume equal to 8 sections. In order to
obtain the appropriate prepared technology for graphene oxide,
the ultrasonic exfoliated power and ultrasonic exfoliated time
are investigated. Figure 3(a)–(d) show the TEM images of gra-
phene oxide in different ultrasonic exfoliated power and ultra-
sonic exfoliated time, one can see that morphology of products
are different in different exfoliation condition, especially the
number of layers are very obvious. The ultrasonic power
between 150 and 200 W and treat time between 3 and 5 h are
appropriate condition to using ultrasonic to exfoliate GOs to
graphene oxide, the appropriate condition to prepare products
shown in Figure 3(b) and it is fewer-graphene oxide. The power
is beyond 200 W such as 250 W, supersonic oscillating 2 h
(250 W@2 h), which is shown in Figure 3(b), the products are
small nubbly fragments, which means GOs are broken into frag-
ments under the high Power condition. Another, ultrasonic
time is another important factor to prepare fewer-graphene
oxide. When ultrasonic time is less than 1.5 h, the products
shown in Figure 3(a), which shows GOs exfoliated in200 W,
supersonic oscillating 1.5 h (200 W@2 h), the exfoliation prod-
ucts still keep the intact bulk like GOs. Figure 3(c), (d) shows the
TEM images of fewer-layer graphene oxide under appropriate
ultrasonic exfoliation condition (150 W@3 h and 200 W@5 h).
Figure 3(e), (f), (g) are the TEM images of reduced graphene
oxide through thermal exfoliated at 1050 C, 750 C, and 400 C.
From the TEM images, which can be seen the temperature
44 S. XU ET AL.

Figure 3. (a) TEM pattern of graphene oxide (200 W@1.5 h). (b) TEM pattern of graphene oxide (250 W@2 h). (c) TEM pattern of graphene oxide (150 W@3 h). Figure 3.
(d) TEM pattern of graphene oxide (200 W@5 h). (e) TEM pattern of reduced graphene oxide (exfoliated at 1050 C). Figure 3. (f) TEM pattern of reduced graphene oxide
(exfoliate at 750 C). (g) TEM pattern of reduced graphene oxide (exfoliated at 400 C).

between 750 C and 1050 C, the graphite oxide was completely
exfoliated to fewer-layer reduced graphene oxide and the size of
sheet is between 500 nm and 2 mm. Large crumple exists in
reduced graphene plane, which is attributed large specific sur-
face area, and its value reach to 352.949 m2g¡1. But, it’s worth
noting that exfoliation temperature at 400 C the products are
multilayer. Thus, using fast thermal exfoliation method to pre-
pare large fewer-layer reduced graphene oxide, exfoliation tem-
perature should be over 750 C.
The graphene oxide and reduced graphene oxide are charac-
terized by XRD, IR, Raman, results show in Figure 4(a), (b), (c).
The GOs and reduced graphene oxide are characterized with
BET method, the results are shown in Figure 4(d). From the
XRD pattern of Figure 4(a), one can see that diffraction peak at
2# D 10 is indistinct, which suggests that the GOs are exfoliated
to graphene oxide and reduced graphene oxide, the sectional
oxygen-containing groups was removed in solution and thermal
treatment (26,27). However, in the XRD pattern of graphene
oxide and reduced graphene oxide show a weak peak in at 2# D
9.5 and 2# D 10 , which indicated oxygen-containing groups
still existed in graphene oxide and reduced graphene though the
oxygen-containing groups were partly removed during exfolia-
tion. Raman patterns of graphene oxide and reduced graphene
oxide shown in Figure 4.(b). At ca.1347 cm¡1 and ca.1578 cm¡1
are referred to as the D and G bands of graphene oxide,
ca.1349 cm¡1 and ca.1590 cm¡1 are referred to as the D and G
bands of reduced graphene oxide. The D mode originates from a
breathing mode of k-point phonons of Alg symmetry, it is related
to structural defects in the graphene sheets, and G is usually
assigned to the E2g phonon of C sp2 atoms. The intensity ratio of
D to G (ID/IG) reflects the disorder degree of the measured car-
bonaceous materials. The ID/IG results of graphene oxide and
reduced graphene oxide are 0.98 and 0.861, respectively, com-
parison on that to graphite (0.094) indicates that there are
defects existing in graphene oxide and reduced graphene oxide,
in detail, the defects of graphene oxide derive from the func-
tional groups and fragments and the defects of reduced graphene
oxide are caused by the size of the in-plane sp2 domains and par-
tially disorder of graphene layer, because the thermal treatment
the functional groups were partly removed, which is graphitic

Figure 4. (a) XRD pattern of graphene oxide and reduced graphene oxide 215 £ 166 mm (300 £ 300 DPI). (b) Raman pattern of graphene oxide and reduced graphene
oxide. 215 £ 166 mm (300 £ 300 DPI). (c) FTIR spectra of graphene oxide (200 W@3 h) and reduced graphene oxide (exfoliated at 1050 C) 215 £ 166 mm (300 £ 300 DPI).
(d) Specific surface area of GOs and reduced graphene oxide oxidized with 2 h,10 h, 25 h. 215 £ 166 mm (300 £ 300 DPI).
“self-healing.” Comparing graphene oxide and reduced gra-
phene oxide to graphite (Figure 2. (b)), the position of D peak
and G peak shifts to higher frequencies, this shift could partially
responsible for the G band with higher frequency in graphene
oxide and reduced graphene oxide (28). The 2D-band peak is
centered at 2680 cm¡1-300 cm¡1 that it is called 2D band and
can be used as an exact fingerprint for the number of graphene
layers. The 2D band can be explained by a double resonance
Raman process and has a close correlation with the electronic
band structure of the graphitic materials, with increase of num-
ber of graphene layer, the electronic band structure vary and
approaches that of graphite (29). For single layer graphene, the
2D band can be fitted with a sharp and symmetric peak while
the 2D band shifts to higher wave number values and becomes
broader when the graphene thickness increases from single to
fewer layer graphene (30). Thus, we can conclude that the gra-
phene oxide and reduced graphene oxide are fewer-layer.
FTIR measurement results of graphene oxide and reduced
graphene oxide are shown in Figure 4(c) for the purpose of
characterizing the difference between graphene oxide and
reduced graphene oxide. It can be seen that graphene oxide
contains much more functional groups than reduced graphene
oxide. Infrared spectroscopy of reduced graphene oxide is very
similar to graphite and it further proved graphitic “self-healing”
in heat treatment. Figure 4(d) shows BET results of graphite
oxide and reduced graphene oxide, which was oxidized 2 h,
10 h, and 25 h. The specific surface area increased with the oxi-
dation time, BET results show the specific surface areas of
graphite oxide linearly increase oxidation time, it mainly due to
the interlayer distance enlarging. The BET values of GOs and
reduced graphene oxide increase with different oxidation time,
and its maximum value is 389.01 m2g¡1 (oxidized 25 h).
FULLERENES, NANOTUBES AND CARBON NANOSTRUCTURES 45
Comparing the BET results of reduced graphene oxide in
oxidized10 h and 25 h, the incremental amplitude of specific
surface area is faint. It proved that graphite oxide under oxidiz-
ing 10 h and 25 had little difference in exfoliation effect, and
this is consistent with XRD interlayer distance analysis and IR
infrared functional groups analysis. Combining with analysis
about the oxidative degree and exfoliation effect, the oxidation
time with10 h is suitable for preparation of GOs; the prepara-
tion of graphene oxide is ultrasonic exfoliation at ultrasonic
power 150–200 W and ultrasonic time between 3 to 5 h; prepa-
ration of reduced graphene oxide is thermal exfoliated tempera-
ture range in 750–1050 C and exfoliation time is 30 s to 1 min.
5. Conclusion
Different oxidative degree GOs were synthesized via change the
oxidation time and the content of oxygen-containing groups
and interlayer distance were increased during the oxidation
time increases. Eventually, through the FTIR spectra and XRD
pattern analysis, the appropriate oxidation time to prepare
highly oxidized is oxidized GOs is 10 h at 40 C. Another,
fewer-layers graphene oxide and reduced graphene oxide were
prepared by ultrasonic and thermal exfoliation. Appropriate
conditions to prepare fewer-layer graphene oxide is ultrasonic
power in 150–200 W supersonic oscillating 3 h to 5 h. prepara-
tion of fewer–layer reduced graphene oxide is thermal tempera-
ture between 750 C and 1050 C.
Acknowledgments
This work was supported by the Joint Funds of the National Natural Sci-
ence Foundation of China (Grant No. U1202272). We acknowledge
46 S. XU ET AL.
operator Danzhi Xu for their help in the measurement of Raman spectral.
The BET detection work with the help of Yuanfeng Huan professor in
Kunming Sino-Platinum Metals Co., Ltd.
References
1. Bitounis, D., Ali-Boucetta, H., Hong, B. H., Min, D. H., and Kostare-
los, K. (2013) Prospects and challenges of graphene in biomedical
applications. Adv Mater, 25(16): 2258–2268.
2. Ramadoss, A., Saravanakumar, B., and Kim, S. J. (2015) Thermally
reduced graphene oxide-coated fabrics for flexible supercapacitors
and self-powered systems. Nano Energy, 15: 587–597.
3. Dikin, D. A., Stankovich, S., Zimney, E. J., Piner, R. D., Dommett,
G. H. B., Evmenenko, G., Nguyen, S. T., and Ruoff, R. S. (2007) Prepa-
ration and characterization of graphene oxide paper. Nature, 448
(7152): 457–460.
4. Zanon, E., Mancini, A., Pavanello, I. G., Bertolino, M., and Grosso, M.
(2013) A review on thermal exfoliation of graphene oxide. J. Mater
Sci., 95(5): 5343–5350.
5. Hummers, W. S., and Offeman, R. E. (1958) Preparation of graphitic
oxide. J. Am. Chem. Soc., 80(6): 1339.
6. Pei, S., and Cheng, H. M. (2012) The reduction of graphene oxide.
Carbon., 50(50): 3210–3228.
7. Cote, L. J., Kim, J., Tung, V. C., Luo, J., Kim, F., and Huang, J. (2011)
Graphene oxide as surfactant sheets. Pure. Appl. Chem., 83(1): 95–110.
8. Ong, B. K., Poh, H. L., Chua, C. K., and Pumera, M. (2012) Graphenes
prepared by Hummers, Staudenmaier and Hofmann methods for
analysis of TNT-based nitroaromatic explosives in seawater. Electro-
analysis, 24(11): 2085–2093.
9. Sheshmani, S., and Fashapoyeh, M.A. (2013) Suitable chemical meth-
ods for preparation of graphene oxide, graphene and surface function-
alized graphene nanosheets. Acta. Chim. Slov., 60(4): 813–825.
10. Zhao, J., Pei, S., Ren, W., Gao, L., and Cheng, H. M. (2010) Efficient
preparation of large-area graphene oxide sheets for transparent con-
ductive films. ACS Nano, 4(9): 5245–5252.
11. Dreyer, D. R., Park, S., Bielawski, C. W., and Ruoff, R. S. (2009) The
chemistry of graphene oxide. Chem. Soc. Rev., 39(1): 228–240.
12. Krishnamoorthy, K., Veerapandian, M., and Yun, K. (2013) The
chemical and structural analysis of graphene oxide with different
degrees of oxidation. Carbon, 53(1): 38–49.
13. Lee, W., Suzuki, S., and Miyayama, M. (2013) Lithium storage proper-
ties of graphene sheets derived from graphite oxides with different
oxidation degree. Ceram. Int., 39: S753–S756.
14. Tateishi, H., Koinuma, M., Miyamoto, S., Kamei, Y., Hatakeyama,
K., Ogata, C., Taniguchi, T., Funatsu, A., and Matsumoto, Y.
(2014) Effect of the electrochemical oxidation/reduction cycle on
the electrochemical capacitance of graphite oxide. Carbon, 76(9):
40–45.
15. Blanton, T. N., and Majumdar, D. (2012) X-ray diffraction characteri-
zation of polymer intercalated graphite oxide. Powder Diffr, 27(27):
104–107.
16. Eda, G., Fanchini, G., and Chhowalla, M. (2008) Large-area ultrathin
films of reduced graphene oxide as a transparent and flexible elec-
tronic material. Nat Nanotechnol, 3(5): 270–274.
17. Fan, X., Peng, W., Li, Y., Li, X., Wang, S., and Zhang, G. (2008) Deox-
ygenation of exfoliated graphite oxide under alkaline conditions: A
green route to graphene preparation. Adv Mater, 20(23): 4490–4493.
18. McAllister, M. J., Li, J. L., Adamson, D. H., Schniepp, H. C., Abdala, A.
A., Liu, J., Alonso, M. H., Milius, D. L., Car, R., Prud’homme, R. K., and
Aksay, I. A. (2007) Single sheet functionalized graphene by oxidation
and thermal expansion of graphite. Chem Mater, 19(18): 4396–4404.

19. Botas, C., Alvarez, P., Blanco, C., Santamarıa, R., Granda, M., Gutier-
rez, M. D., Reinoso, F. R., and Menendez, R. (2013) Critical tempera-
tures in the synthesis of graphene-like materials by thermal
exfoliation–reduction of graphite oxide. Carbon, 52(2): 476–485.
20. Venugopal, G., Krishnamoorthy, K., Mohan, R., and Kim, S. J. (2012)
An investigation of the electrical transport properties of graphene-
oxide thin films. Mater Chem Phys., 132(1): 29–33.
21. Szabo, T., Berkesi, O., Forg o, P., Josepovits, K., Sanakis, Y., Petridis,
D., and Dekany, I. (2006) Evolution of surface functional groups in a
series of progressively oxidized graphite oxides. Chem Mater., 18(11):
2740–2749.
22. Han, Y., and Lu, Y. (2007) Preparation and characterization of graph-
ite oxide/polypyrrole composites. Carbon, 45(12): 2394–2399.
23. Si, Y., and Samulski, E. T. (2008) Synthesis of water soluble graphene.
Nano Lett., 8(6): 1679–1682.
24. Kudin, K. N., Ozbas, B., Schniepp, H. C., Prud’homme, R. K., Aksay,
I. A., and Car, R. (2008) Raman spectra of graphite oxide and func-
tionalized graphene sheets. Nano Lett., 8(1): 36–41.
25. Kaniyoor, A., and Ramaprabhu, S. (2012) A Raman spectroscopic
investigation of graphite oxide derived graphene. AIP Adv., 2(3):
1136–1144.
26. Krishnamoorthy, K., Veerapandian, M., Mohan, R., and Kim, S. J.
(2012) Investigation of Raman and photoluminescence studies of
reduced graphene oxide sheets. J. Appl. Phys. A., 106(106): 501–506.
27. Graf, D., Molitor, F., Ensslin, K., Stampfer, C., Jungen, A., Hierold, C.,
and Wirtz, L. (2007) Raman imaging of graphene. Solid State Com-
mun., 143(1–2): 44–46.
28. Eigler, S., Dotzer, C., and Hirsch, A. (2012) Visualization of defect
densities in reduced graphene oxide. Carbon, 50(10): 3666–3673.
29. Yoon, D., Moon, H., and Cheong, H. (2009) Variations in the Raman
spectrum as a function of the number of graphene layers. J. Korean.
Phys Soc., 5530: 1299–1309.
30. Seresht, R. J., Jahanshahi, M., Rashidi, A., and Ghoreyshi, A. A.
(2013) Synthesize and characterization of graphene nanosheets
with high surface area and nano-porous structure. Appl. Surf. Sci.,
276(3): 672–681.