8192 J. Phys. Chem.

C 2008, 112, 8192–8195

Facile Synthesis and Characterization of Graphene Nanosheets

Guoxiu Wang,* Juan Yang, Jinsoo Park, Xinglong Gou, Bei Wang, Hao Liu, and Jane Yao
Materials Chemistry Research Group, School of Mechanical, Materials and Mechatronic Engineering,
UniVersity of Wollongong, NSW 2522, Australia
ReceiVed: NoVember 16, 2007; ReVised Manuscript ReceiVed: March 9, 2008

Graphene nanosheets were produced in large quantity via a soft chemistry synthetic route involving graphite
oxidation, ultrasonic exfoliation, and chemical reduction. X-ray diffraction and transmission electron microscopy
(TEM) observations show that graphene nanosheets were produced with sizes in the range of tens to hundreds
of square nanometers and ripple-like corrugations. High resolution TEM (HRTEM) and selected area electron
diffraction (SAED) analysis confirmed the ordered graphite crystal structure of graphene nanosheets. The
optical properties of graphene nanosheets were characterized by Raman spectroscopy.

1. Introduction crystal structure and optical properties of graphene nanosheets

Graphene is a single layer of carbon atoms in a closely packed
honeycomb two-dimensional (2D) lattice. Since its discovery
by K. S. Novoselov and A. K. Geim in 2004,1 it has attracted
numerous investigations into its unique physical, chemical, and
mechanical properties, opening up a new research area for
materials science and condensed-matter physics, and aiming for
a wide-ranging and diversified technological applications.2–6
Owing to the high quality of the sp2 conjugated bond in the
carbon lattice, electrons were found to move ballistically in a
graphene layer without scattering with mobilities exceeding
15 000 m2 V-1 s-1 at ambient temperature. Furthermore, the
charge carriers in graphene crystals mimic relativistic particles
with zero rest mass, being described as massless Dirac
fermins.2,7 These characteristics drive the dreams of developing
graphene based electronics. Although this has not yet been
realized, there are real possibilities for a bright future.
The preparation of high-quality 2D graphene crystals is the
first and most crucial step, not only for fundamental research
but also for device applications. Micromechanical cleavage of
bulk graphite can only produce graphene flakes in limited
quantities. However, the entire process is hard to control. In a
later method, ultrathin epitaxial graphene has been grown on
single-crystal silicon carbide by vacuum graphitization. This
approach allows the fabrication of a patterned graphene
structure, which is desirable for electronic applications.8–10
Recently, polystyrene-graphene based composite materials have
demonstrated extraordinary room temperature electrical con-
ductivity, leading to the development of a new class of
composite materials with enhanced properties and functional-
ities.11 Graphene oxide papers exhibit high mechanical stiffness
and strength, resulting from a unique interlocking-tile arrange-
ment of the nanosize graphene oxide sheets.12 Therefore,
graphene has great potential to be massively used as an
engineering material with the demand exceeding 1 million tons
annually. Micromechanical cleavage and ultrahigh vacuum
graphization certainly cannot meet such a high demand in the
future.
Herein, we report a soft chemical synthesis route toward
massive production of graphene nanoplatelets. We prepared
high-quality graphene nanosheets through this approach. The
* Corresponding author. E-mail: gwang@uow.edu.au.
10.1021/jp710931h CCC: $40.75  2008 American Chemical Society
Published on Web 05/01/2008
were investigated by X-ray diffraction (XRD), transmission
electron microscopy (TEM), high resolution TEM (HRTEM),
and Raman spectroscopy.
2. Experimental Section
Graphene Nanosheet Synthesis. Natural graphite (Aldrich)
was used for the preparation of graphene nanosheets. Graphite
oxide powders were prepared from it by a modification of
Hummers and Offeman’s method.13 Graphite powders were first
oxidized by reacting them with concentrated nitric acid and
sulfuric acid (1:2 in volume). The reaction vessel was immersed
in an ice bath, and potassium chlorate was added slowly. The
reaction was allowed to go on for 120 h to fully oxidize graphite
into graphite oxide (GO). The GO was thoroughly washed and
filtered by deionized water and filtered to remove metal ions
and until pH 7. The GO was suspended in a mixture of ethanol
and water, and exfoliated through ultrasonication for 1 h. We
observed that the suspension gradually evolved into a yellow-
brown solution, during which the bulk GO powders were
transformed into nanoplatelets. The exfoliated GO was reduced
to graphene nanoplatelets by refluxing the GO solution with
hydroquinone for 20 h. The final products were then centrifuged,
washed, and finally vaccuum-dried.
Structural and Raman Spectroscopy Characterization.
The evolution of GO during the oxidation process was monitored
by X-ray diffraction (XRD; Philips 1730 Diffractometer).
Transmission electron microscopy (TEM) and high resolution
TEM (HRTEM) analyses were performed on GO and graphene
powders by using a JEOL2011 TEM facility. TEM samples were
prepared by dispersing GO and graphene dry powders in ethanol
to form a homogeneous suspension. Then, the suspension was
dropped on 200-mesh copper grid for observation. The Raman
spectra of the pristine graphite, GO, and graphene powders were
measured by using a Jobin Yvon HR800 confocal Raman system
with 632.8 nm diode laser excitation on a 300 lines/mm grating
at room temperature.
3. Results and Discussion
Natural flake graphite with an average particle size of 250
µm was used as the starting material. As described previously,
the inter-graphene layers can be intercalated by various molec-
ular species or ions, during which the interlayer spacing along
Characterization of Graphene Nanosheets J. Phys. Chem. C, Vol. 112, No. 22, 2008 8193

Figure 1. X-ray diffraction patterns of pristine graphite powders and

graphite oxide (GO) at various oxidation stages: 48, 72, and 120 h,
respectively.

the c-axis changes from 3.4 to 6.25–7.5 Å.14,15 We employed a

mixture of sulfuric acid, nitric acid, and potassium chlorate to
oxidize the natural graphite powders in water-based solution.
During this process, hydroxyl, carbonyl, epoxy, and peroxy
groups were bonded to the edges of basal planes of the graphite
structure. Simultaneously, carbon hydrolyzation occurred and
the sp2 bonds changed to sp3 bonds. At the same time, H2O, Figure 2. (a) TEM image of GO nanosheets. (b) HRTEM image of a
NO3-, or SO42- ions could insert themselves into the graphene single GO nanosheet, illustrating their amorphous character. The inset
layer, inducing an increase in the interlayer spacing.16–18 shows the corresponding SAED pattern.
Although there are many models describing the structure of
graphite oxide, the exact structure of GO still remains unclear.
We monitored the graphite oxidation process by X-ray
diffraction. The intermediate oxidized graphite products were
taken from the reaction flask at various oxidation stages. After
washing and vacuum-drying, the powders were examined by
X-ray diffraction. Figure 1 shows the XRD patterns of the
original graphite and the graphite oxide at various oxidation
stages. As oxidation proceeds, the intensity of the (002)
diffraction line (d-space 3.4 Å at 26.23°) gradually weakened
and finally disappeared. Simultaneously, the intensity of the
diffraction peak at 11.8° (corresponding to a d-spacing of 0.749
nm) increased with oxidation. After 120 h of chemical treatment,
the graphite powders were completely oxidized to graphite
oxide. We also noticed that the (002) diffraction line almost
completely disappeared after oxidation for 48 h, indicating that
the full oxidation of graphite powders can be achieved within
a short period.
Figure 3. X-ray diffraction pattern of graphene nanosheets.
The graphite oxide powders were exfoliated via ultrasonic
vibration to produce GO nanoplatelets. The morphology and
structure of the GO were observed by TEM analysis. Figure 2a caused by the evaporation of the oxygen- and hydrogen-
shows a general view of GO nanoplatelets, clearly illustrating containing functionalized groups.
the flake-like shapes of graphite oxide particles. Multilayer GO After chemical reduction through refluxing with hydro-
sheets corrugated together with sizes in the range of tens to quinone, GO nanosheets were reduced to graphene nanosheets
several hundreds of square nanometers. Figure 2b exhibits a and restored to an ordered crystal structure. This is evidenced
high magnification TEM image of a GO nanosheet, showing a by the reappearance of the (002) diffraction line and disappear-
completely amorphous and disordered structure. Selected area ance of the diffraction peak at 11.8° in the XRD pattern (Figure
electron diffraction (SAED, inset in Figure 2b) further confirmed 3). During the reduction process of the graphene oxide nano-
the disordered nature of the GO nanoplatelets. The SAED platelets by hydroquinone, the yellow-brown solution gradually
pattern of GO shows only diffraction rings and the diffraction yielded a black precipitate. Hydroquinone acts as a reducing
dots are unresolved, unambiguously indicating that the GO agent by losing either one H+ from one of its hydroxyls to form
flakes are amorphous. This result is consistent with XRD a monophenolate ion or two H+ from both hydroxyls to form a
analysis. We also found that the GO nanosheets were unstable diphenolate ion (quinone).19
under electron beam bombardment. After a few minutes It is well established that graphite oxides consist of various
exposure to the electron beam during the TEM observation, the different types of oxygen functional groups such as hydroxyl,
GO nanosheets were found to be broken up, which was possibly carbonyl, epoxide, lactone, or ether groups. Although the full
8194 J. Phys. Chem. C, Vol. 112, No. 22, 2008 Wang et al.

mechanisms of GO reduction are not clear yet, the reduction

process must involve the removal of the above oxygen functional
groups. Since the GO can be directly converted to the crystalline
graphene (d002 ) 3.4 Å), the conjugated graphene network (sp2
carbon) must be reestablished during the reduction process,
which is associated with the ring-opening of the epoxides.20,21
Graphene oxide nanosheets are hydrophilic. The GO nanosheet
solution in water is stable indefinitely, while graphene nano-
platelets are hydrophobic. We noted that the graphene nano-
platelets can be dispersed into a homogeneous suspension in
water via ultrasonic vibration, but the dispersion can only be
stable for a few hours due to their hydrophobic nature.
The obtained graphene nanosheets were fully analyzed by
TEM and HRTEM observations. Figure 4a shows a low
magnification TEM image of graphene nanosheets. Large
graphene nanosheets (a few hundred square nanometers) were
observed to be situated on the top of the copper grid, where Figure 4. (a) Low magnification TEM image of graphene nanosheets,
they resemble crumpled silk veil waves. Graphene nanosheets resembling crumpled silk. The featureless regions indicated by the
were rippled and entangled with each other. They are transparent arrows are monolayer graphene nanosheets. (b) TEM image of a scrolled
and exhibit a very stable nature under the electron beam. The gaphene nanosheet.
most transparent and featureless regions indicated by arrows in
Figure 4a are likely to be monolayer graphene nanosheets. We
also observed scrolled graphene nanosheets (as shown in Figure
2b). As reported previously,22 corrugation and scrolling are
intrinsic to graphene nanosheets. This is because the thermo-
dynamic stability of the 2D membrane results from microscopic
crumpling via bending or buckling. Figure 5 shows a high
magnification TEM image of a graphene nanosheet. The ordered
graphite lattices are clearly visible. However, the disordered
regions are also found, indicating that the graphene nanosheets
were partially restored to ordered crystal structure. The graphitic
laminar structure can be resolved in the ordered region. We
performed selected area electron diffraction (SAED) on this
region along the [001] zone axis. The SAED pattern is shown
as the inset in Figure 5. The well-defined diffraction spots Figure 5. HRTEM image of a single graphene nanosheet. The inset
confirm the crystalline structure of the graphene nanoplatelets is the selected area electron diffraction pattern (SAED), which confirms
the crystalline nature of the graphene nanosheet.
obtained via chemical reduction of graphite oxides. Therefore,
the XRD, HRTEM, and SAED analyses clearly demonstrated
that hydroquinone reduction can produce crystalline 2D graphene at 2700 cm-1, while the G′ line (the overtone of the G line) is
nanosheets. around 3248 cm-1. Figure 7 shows Raman spectra of pristine
The thermal behaviors of the GO, graphene nanosheets, and graphite and graphene nanosheets. The Raman spectrum of the
pristine graphite powders were investigated by thermogravmetric pristine natural graphite displays a strong G line at 1582 cm-1,
analysis (TGA) in dry air. The TGA curves of the pristine a weak D line at 1350 cm-1, a broad D′ line at 2690 cm-1, and
graphite, GO, and graphene nanoplatelets are shown in Figure a very weak G′ line at 3245 cm-1. In the Raman spectrum of
6. The pristine graphite starts to lose weight at 650 °C due to graphene nanosheets, the G band is broadened and shifted
combustion to carbon dioxide. The GO powders exhibit two upward to 1595 cm-1. At the same time, the intensity of the D
steps of mass loss at 200 and 550 °C, which are attributed to band at 1350 cm-1 increases substantially. These phenomena
the removal of oxygen-containing groups and carbon oxidation, could be attributed to the significant decrease of the size of the
respectively. Graphene nanosheets show a mass loss, starting in-plane sp2 domains due to oxidation and ultrasonic exfoliation,
at an onset temperature of 250 °C, illustrating a much lower and partially ordered graphite crystal structure of graphene
thermal stability compared to the bulk graphite powders. nanosheets.21
Raman spectroscopy is a powerful nondestructive tool to
characterize carbonaceous materials, particularly for distinguish-
4. Conclusions
ing ordered and disordered crystal structures of carbon. The
typical features for carbon in Raman spectra are the G line Graphene nanosheets can be massively prepared by a soft
around 1582 cm-1 and the D line around 1350 cm-1. The G chemistry route. TEM and HRTEM observations confirmed the
line is usually assigned to the E2g phonon of C sp2 atoms, while crystalline nature of graphene nanosheets and also demonstrated
the D line is a breathing mode of κ-point phonons of A1g that graphene nanosheets naturally corrugated into ripples, like
symmetry.23,24 The overtone of the D line, the D′ line, is located wavy silk. TGA analysis found that graphene nanosheets have
Characterization of Graphene Nanosheets
Figure 6. TGA curves of pristine natural graphite, graphene nanosheets,
and exfoliated graphite oxide.
Figure 7. Raman spectra of pristine natural graphite and graphene
nanosheets.
much lower thermal stability than pristine natural graphite
powders. This is possibly caused by the size effect. Raman
spectroscopy measurement indicates the small size of the in-
plane sp2 domains of graphene nanosheets.
Acknowledgment. Financial support by a grant (DP0772999)
from the Australian Research Council (ARC) is gratefully
J. Phys. Chem. C, Vol. 112, No. 22, 2008 8195
acknowledged. We thank Prof. X.Y. Kong for performing the
TEM analysis.
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