Graphene Synthesis via Deoxidization of Exfoliate-GO under Alkaline Conditions

X. Zhang, Y. Qian, J. Liu, X. Wu, Z. Zhang

We successfully synthesized graphene from exfoliated graphite oxide via deoxidization under al-
kaline conditions. The Hummers method is used to produce exfoliated-GO from graphite powder.
The product is then exfoliated through ultrasonic treatment, and subsequently reduced in an alka-
line environment, also with sonication. Thin films are grown by drying an uniform suspension of
graphene, and characterized by Raman spectroscopy and infrared spectrum. Results suggest the
existence of graphene in produced samples. Relationship between time of ultrasonic treatment and
production rate of graphene is also studied.

I. INTRODUCTION ilar conclusion to that of XRD analysis. It was found

Graphene[1] is a crystalline allotrope of carbon with
2-dimensional properties. In graphene, carbon atoms
are densely packed in a regular sp2 -bonded atomic-scale
chicken wire (hexagonal) pattern, a structure which is
the basal building block of other carbon allotropes[2].
Graphene research has expanded quickly since the sub-
stance was first isolated in 2004. Great research inter-
est has been attracted by graphene due to its unique
electronic[310], mechanical[11, 12], thermal[13] proper-
ties as well as its potential applications[12, 1416].
A variety of method have long been proposed for the
production of graphene, but drawbacks remain. Physi-
cal approaches, such as mechanical exfoliation[17], epi-
taxial growth[18] and chemical vapor deposition[19],
though capable of producing high-quality graphene, have
proved unsuitable for large-scale industrial manufacture.
Chemical synthesis methods include intercalation fol-
lowed by solution-based exfoliation[20], synthesis of small
aromatic compounds through stepwise organic chemi-
cal reactions[21], and chemical reduction of graphene
oxide[22]. Though its mechanisms remain unknown[22],
chemical reduction of graphite oxide proves a promising
and cost-efficient[22, 23] approach of large-scale indus-
trial production of graphene.
However, finding chemical reducing agents for GO
turn out to be tricky. Although a variety of chemicals
including N,Ndimethylformamide(DMF)[24], N-methyl-
2-pyrrolidinone(NMP)[25], sodium borohydride[26], p-
phenylene diamine[27], sodium hydrogen sulfite[26],
poly(amidoamine)[28], hydrohalic acid [29],pyrrole[30]
and hydroquinone[31] are available, most involved reduc-
ing agents are hazardous, limiting their potential appli-
cations. Also, aggregation of graphene caused by the
stacking presents obstacles to the reduction pro-
cess. In this paper we realized an environment-friendly
approach to synthesizing graphene[32] and investigated
the effects of altering ultrasonic treatment time on the
production rate of graphene. The samples were obtained
by chemical reduction of exfoliated-GO with increasing
ultrasonic time. Raman and IR spectroscopy was car-
ried out to qualitatively examine the constitution and
electronic properties of graphene samples. Electrical re-
sistance combined with fracture study was employed to
determine the purity of graphene samples and yield sim-
that, although chemically synthesized samples are rela-
tively low in quality, which is the general case, modest
increase of ultrasonic treatment( 5 min) may increase
the production rate of graphene.
II. EXPERIMENTAL
A. Synthesis of GO
The celebrated Hummers method [33] was employed
for synthesizing graphite oxide from graphite powder.
In a typical procedure, 50mL of concentrated sulfuric
acid(98%) was mixed with 2g of graphite and 1g of
sodium nitrate and stirred at 0-20 C for 20 min in a
500mL beaker in an ice-water bath. The suspension is
then stirred at 30 C for 30 min before it is diluted with
60-100 mL of deionized water. The suspended solution is
left for further reaction for 20 min, and sufficient H2 O2
is added to the solution till it turns dark yellow. The
mixture is then centrifuged and washed repeatedly with
dilute hydrochloric acid till no SO2
4 ions can be detected
in the washes. The resulting suspension is dried at 60-
80 C for 24 h to obtain GO.
B. Synthesis of graphene
Typically, 150mL of GO suspension(1-2mg/mL) is ex-
foliated via ultrasonic treatment (2500W, 0.5min)[23] at
50 C. Different samples are forged by changing the ultra-
sonic time to 6s, 3 min, 6 min and 15 min respectively.
All samples are kept at 50 C for 10 min in total, which
includes the time of ultrasonic treatment, except for the
last one. This measure insures that the only different be-
tween different samples lie in ultrasonic treatment time.
The exfoliated-GO suspension is then mixed with 1mL
of NaOH solution(8M). The mixture is then treated with
ultrasound (2500W, 0.5min) yet again and stirred at
50 C for 9.5 min. The final suspension is left to precipi-
tate. With superfluous solvent discarded, a concentrated
solution is poured into an evaporating dish and dried at
60-80 C for 24 h to obtain graphene film.
 2

III. RESULTS AND DISCUSSION

A. Raman Spectroscopy

Raman spectroscopy was carried out to identify

graphene as well as investigate its structural properties.
Typical Raman spectrum of graphene is characterized
by three peaks, namely the G peak, which is caused by
first-order scattering of E2g phonons of sp2 C atoms, the
1D peak related to a breathing mode -point photons of
A1g symmetry[34], and the 2D peak. As is shown in the
spectra 1, Raman spectrum of graphite displays 1D,2D
peak and G peak, with an ID /IG approximate to 0.13.
That of exfoliated-GO, on the other side, displays mul-
tiple peaks apart from the former two. Different from
both, the spectrum of our samples display distinguished
1D,2D peak and G peak, with an ID /IG around 1. This
provides proof of the existence of graphene in our sam-
ples.
Figure 2 plots ratio I2D /IG against sonication time
t. The ratio increase monotonously with t 5min and
decreases afterwards. As the I2D /IG ratio of typical
graphene falls within the scope of 0.7 to 2.1[35], it can
be seen that our samples are not pure graphene. How-
ever,the maximum ratio I2D /IG (0.65) goes closest to
that of chemically synthesized graphene (0.7)[36], sug-
gesting an optimum amount of sonication in the deoxi-
dization process. The fall of graphene production when
sonication time goes over 5 min may be due to over-
sonication affecting the aggregation of exfoliated-GO and
consequently vitiates the production rate of graphene via
reduction. This explanation is supported by the visible
discrepancy between precipitation rates of different sam-
ples shown in figure 3. In addition, the total ultrasonic
energy (2500W, 5min) roughly agrees with proven meth-
ods (130W, 60min)[23], suggesting energy rather than
time or power as the decisive factor in the exfoliation of
graphite oxide.
Fig 1. Raman spectra of graphite, exfoliated-GO and
Figure 4 plots ratio ID /IG against t. It is known that
graphene
the ID /IG value is a measure of the disorder in the sam-
ple,which can be edges, charge puddles, ripples, or any
other defects. As the ratio remains relatively constant
with increasing t, it may be concluded that ultrasonic
treatment has no significant impact on the defects of
produced graphene, though effects of increasing defects
and dominance of amorphous phase may counter each
other[37].

B. IR Spectroscopy

Figure 5 shows the IR spectrum of our sample

compared to that of graphite used in producing GO.
Graphenes characteristic peaks at 2927, 2830 and 1391
cm1 are visible, suggesting the existence of graphene Fig 2. I2D /IG t relationship
in our samples. Peaks centered at 3440 cm1 can be
attributed to the existence of hydroxyl group. Its in-
tensity in our sample is significantly smaller than that in graphite, which is probably caused by the reduc-

Fig 3. Precipitation of different exfoliated-GO samples
Fig 4. ID /IG t relationship
tion process, but may also have to do with atmospheric
humidity[38]. Visible but weak peaks exist at 819 and
1262 cm1 , which are characteristic peaks of epoxy group
and carboxyl group, respectively. These weak peaks
implies that reduction from exfoliated-GO as graphitic
acid to graphene is not thorough-paced though reason-
ably effective[39]. The peak at 2018 is chiefly related to
unsaturated carbon bonds, and is relatively stronger in
graphite, suggesting formation of C-C bonds in the exfo-
liation or reduction process.
In order to study the contribution of ultrasonic treat-
ment to the production of graphene, we compared IR
spectra of samples sonicated for 0.5 min, 3 min and 6
min and of graphite, as is shown in figure 6. Peaks
at 1403, 2834 and 2927 cm1 , which are characteristic
peaks of graphene, visibly increase with more ultrasonic
time, suggesting an enhancement in graphene produc-
tion caused by modestly increasing sonication time. This
result confirms similar conclusions drawn from Raman
spectroscopy.
C. Composition of rGO samples
XRD analysis was carried out to study the composi-
tion of our samples. However, the resulting spectra shows
an unduly high number of peaks, and such peaks as ex-
3
Fig 5. Comparison of IR spectra of graphite and sample
Fig 6. IR spectra of samples
pected were generally too broad to be distinguished from
background noise. Both of these suggest the existence of
amorphous phase in our samples.
The low concentration of graphene is also backed by
the specific resistance of the sample. One sample is uni-
formly spread out on an evaporating dish with a radius
of around 3cm. The sample film breaks along a diameter
with 1N force exerted symmetrically. Resistance between
two electrodes spaced 3cm apart and placed symmetri-
cally is measured to be around 10M. Combining the
formula of ultimate tensile strength(UTS) and that of
specific resistance, we get
AR R F
= =
L L UTS
where is the specific resistance, A is cross section area,
R denotes resistance, L denotes length of resistance unit

Sample Graphene a-Carbon e-GO
UTS/( 8 5 6 10 both graphene and less conductive materials like amor-
10 10 10 10
m P a)
Fig 7. Order of magnitude of UTS of our sample com-
pared with that of graphene, amorphous carbon and exfoli-
ated graphite oxide. As a semiconductor, GOs resistance is
calculated from its differential conductivity[40]. Electronic
and mechanical properties of other materials are collected
from published works[4144].
and F denotes force at fracture. From this it can be seen
that
RF
UTS =
L
with lhs being the intrinsic properties of the material and
the rhs being measurable quantity. The order of magni-
tudelhs quantity of our samples compared with that of
graphene, amorphous carbon and GO is shown in table
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