CARBON 4 8 ( 2 0 1 0 ) 2 5 5 –2 5 9

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Large scale synthesis of N-doped multi-layered graphene

sheets by simple arc-discharge method
a,b
Nan Li , Zhiyong Wang a, Keke Zhao a, Zujin Shi a,*
, Zhennan Gu a, Shukun Xu b

a
Beijing National Laboratory for Molecular Sciences, State Key Lab of Rare Earth Materials Chemistry and Applications, College of Chemistry
and Molecular Engineering, Peking University, Beijing 100871, People’s Republic of China
b
Department of Chemistry, Northeastern University, Shenyang 110004, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Article history: N-doped multi-layered graphene sheets were synthesized in large scale by the method of
Received 1 July 2009 direct current arc-discharge between pure graphite rods. For the use of NH3 as one of the
Accepted 5 September 2009 buffer gas, the multi-layered graphene sheets were doped with N without the addition of
Available online 11 September 2009 other nitrogen source. The product so obtained has been characterized by transmission
electron microscopy, Raman spectroscopy, thermogravimetric analysis, X-ray photoelec-
tron spectroscopy and element analysis. The graphene sheets are mainly of 2–6 layers
and their sizes are about 100–200 nm. The multi-layered graphene sheets can be purified
by a simple heat treatment process. The content of N atoms on the multi-layered graphene
sheets can be tuned by simply changing the proportion of NH3 in the atmosphere.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Although its fascinating properties endow graphene great

Since the stirring found in 2004, the free standing graphene
[1], one of the hottest topics in pure and applied physics,
chemistry and materials science, has received more and
more attention. Graphene is one-atom-thick layer of sp2-
hybridized carbon tightly packed into a two-dimensional
honeycomb lattice, and is a basic building unit for graphitic
materials of all other dimensionalities [2]. Even though sev-
eral other forms of sp2 carbon nanostructured materials, for
example, fullerene [3] and carbon nanotube [4] have been
prepared, isolated, and studied during the past two decades,
single-layer graphene has only recently been examined [5].
Over the past several years, a great deal of intensive research
has been generated by graphene due to its unique electrical,
thermal, mechanical, optical and other characteristics [6,7].
With the understanding of their physical properties, the
promises for application are growing in areas of nanoelec-
tronics, sensors, composites, batteries, supercapacitors and
hydrogen storage [8].
potential as the new generation of carbon nanomaterial, the
large scale production of graphene has become a stumbling
block on the road of further application. So during the past
several years, many scientists have dedicated to the synthesis
of graphene. Up to now, several methods have been developed
exclusively to prepare graphene, which include microme-
chanical cleavage [9], polycrystalline Ni employing chemical
vapor deposition technique [10], solvent thermal reaction
[11], thermal desorption of Si from SiC substrates [12], chem-
ical routes via graphite intercalation compounds [13] or
graphite oxide [14]. However, fewer methods can be used to
prepare graphene in large scale and high purity. Only recently,
Choucair et al. [15] reported the synthesis of graphene in
gram-scale.
In the last two decades, arc-discharge method was widely
used to prepare carbon-based nanomaterials, such as fuller-
ene and nanotube. Graphene sheets, another member of the
carbonous family, can also be synthesized by arc-discharge
method [16]. As a convenient experimental technique, the

* Corresponding author: Fax: +86 10 62751708.

E-mail address: zjshi@pku.edu.cn (Z. Shi).
0008-6223/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2009.09.013
256 CARBON 4 8 ( 2 0 1 0 ) 2 5 5 –2 5 9

buffer gas used during arc-discharge process can be changed

freely, so we used NH3 and He as the buffer gas and prepared
N-doped multi-layered graphene sheets (NH3 as the nitrogen
source) in large scale, which could be applied to successive
production. Owing to its metal free production, the effect of
metal impurities can be excluded during further investiga-
tion. Furthermore, the production of N-doped multi-layered
graphene sheets by arc-discharge method does not need strict
vacuum thus is a timesaving method compared with the
preparation of fullerene and carbon nanotube. In this paper,
we present this simple and reproducible method in detail.

2. Experimental

To prepare N-doped multi-layered graphene sheets, direct

current (DC) arc-discharge was carried out in a water-cooled
stainless steel chamber as described previously [17]. Two elec-
trodes were both /8 mm pure graphite rod. The current was Fig. 1 – TEM image of multi-layered graphene sheets
held at 120 A. As the rods were brought close together, dis- produced by DC arc-discharge method.
charge occurred resulting in the formation of plasma. The an-
ode was vaporized in He and NH3 mixing atmosphere of
760 Torr. As the anode was consumed, the rods were kept at
a constant distant from each other of about 1 mm by rotating
the cathode. When the discharge ended, the soot generated
was collected under ambient conditions. In our experiments,
we only collected the soot deposited on the inner wall of the
reaction chamber, avoiding the substance at the bottom of the
chamber, for the latter tends to contain other graphitic parti-
cles. The condition that is favorable for obtaining N-doped
multi-layer graphene sheets in our experiment is the high
proportion of NH3 (above 50%, V/V).
Morphology and structure analysis of the samples was car-
ried out on high-resolution transmission electron microscope
(HRTEM, Hitachi H-9000NAR) with an accelerating voltage of
100 kV. Raman spectra were recorded from 500 to 3000 cm 1
with a Jobin Yvon HR-800 spectrometer with an excitation Fig. 2 – HRTEM images showing the edge of multi-layered
wavelength of 488 nm. Thermogravimetric analysis (TGA) graphene sheets consisting of two (a), three (b) and four (c)
was performed on a Q50TGA thermogravimetric analyzer layers.
(Thermal Analysis Inc., USA) from room temperature to
1273 K at a rate of 10 °C/min under air flow of 30 mL/min. X- of flat graphene by HRTEM. However, when the edge of graph-
ray photoelectron spectroscopy (XPS) measurements were ta- ene is folded, the graphene’s layers can be distinguished
ken on an AXIS-Ultra instrument (Kratos Inc., England) using through the folded edge. Fig. 2a–c is the HRTEM images of
monochromatic Al Ka radiation (ht = 1486.71 eV). Element multi-layered graphene sheets with layer numbers of 2–4.
analysis for N was carried out on vario EL instrument (Ele- According to the HRTEM observation, our multi-layered
mentar Analysensysteme GmbH, Germany). graphene sheets are mainly of 2–6 layers.
The most efficient way to provide a quick and easy struc-
3. Results and discussion tural and quality characterization of the samples is Raman
spectroscopy. Fig. 3 shows the Raman spectra of the products.
We used H2 as the reactive gas during the arc-discharge pro- There are three dominant peaks. The two most intense fea-
cess at first. But we could not obtain satisfied experimental tures are the G band at 1560 cm 1 and the 2D band at
result each time in our reaction chamber. Owing to the simi- 2600 cm 1. The peak at 1350 cm 1 is the D band. The G
larity between H2 and NH3 (both of them decompose to reac- band corresponds to the zone center E2g mode [18] related
tive hydrogen under high temperature), we turned our steps to phonon vibrations in sp2 carbon materials [19]. The 2D
to another reactive gas, which is NH3. For the use of NH3, band has nothing to do with the G band, but is an overtone
we successfully synthesized N-doped multi-layered graphene of the disorder-induced D band, which is frequently observed
sheets without the addition of other nitrogen source. In Fig. 1, in carbon materials [20]. The D band arising from disorder is
we can see large area of high purity multi-layer graphene weak in a single-layer graphene and increases in intensity
sheets with the size of 100–200 nm. Fig. 2 is the HRTEM with the numbers of layers [21]. The 2D band is also sensitive
images of the product. In principle, we cannot see the layers to the number of layers. The shape of the D and 2D band,
 CARBON 4 8 (2 0 1 0) 2 5 5–25 9
Fig. 3 – Raman spectra of the two samples prepared in
mixing atmosphere of NH3 and He with the different ratio of
NH3/He (V/V): (a) NH3:He = 1:0 and (b) NH3:He = 1:1.
more specially the absence of a typical graphite shoulder, is a
characteristic feature of single-layer graphene. The intensity
ratio of the D band to the G band is measured and denoted
as the R value to analysis the structure of graphitic materials
[19,22]. The IG/I2D is also changed with the layers of graphene
[10]. The R value is by definition inversely proportional to
quality. The R value is 0.26 (Fig. 3a) and 0.23 (Fig. 3b) for
our multi-layered graphene sheets and the IG/I2D is 1.90
and 1.57. This indicates that the N-doped multi-layered
graphene sheets produced by our method bear well crystal-
line structure and the number of graphene’s layers is not
influenced significantly by the content of NH3.
Fig. 4 shows the TGA curve of the N-doped multi-layered
graphene sheets. There are two significant drops in mass
around 387 and 688 °C. The former is assigned to the oxida-
tion of amorphous carbon, and the latter is attributed to the
combustion of the carbon skeleton of graphene sheets. From
the TGA curve, we can conclude that the N-doped multi-lay-
ered graphene sheets is thermally stable and starts to lose
Fig. 4 – TGA curve of N-doped multi-layered graphene
sheets.
257
mass upon heating at 500 °C and the content of graphene
sheets in raw soot is 79 wt.%. After the heat treatment at
450 °C for 1 h in the atmosphere of air, there was not any
amorphous carbon in the soot (Fig. 5). From the experimental
results we can see that the N-doped multi-layered graphene
sheets produced by our method can be purified by a simple
heat treatment process.
The XPS results shown in Fig. 6 confirm the existence of N.
The peaks appeared at 284.50, 399.59 and 532.70 eV can be as-
signed to C1s, N1s and O1s. No extra peaks except C, N and O
were observed, indicating the high purity of the product. Oxy-
gen can be included due to exposure to the air. In graphene
sheets, the C atoms are mostly constrained to a sp2-hybrid-
ization. There are two types of N bonding for N-doped graph-
ene sheets [23]. One is substitutional doping, which N is
bonded to three C atoms in a sp2 configuration. The other is
the pyridine-type doping, which N is bonded with two coordi-
nated bondings. From the position of the N1s level, we can dis-
tinguish the N-doping type. Fig. 7 is the high-resolution XPS
spectra of N1s. From it we can see that the N1s core level lied
at 399.59 eV is in good agreement with the spectral feature of
pyridine-type N-doping [24]. Furthermore, element analysis
was used to reveal the precise N content of the N-doped mul-
ti-layered graphene sheets. The result shows that the content
of N is 1% for the sample produced in the atmosphere of
pure NH3.
The successful synthesis of N-doped multi-layered graph-
ene sheets by arc-discharge method permits us to get an in-
sight into the growth mechanism of graphene sheets. First,
in our experimental procedure, we use pure graphite rod as
electrode to avoid the formation of metallofullerenes, sin-
gle-wall carbon nanotubes and double-wall carbon nano-
tubes. According to [25–27], we use NH3 and He as the
buffer gas during arc-discharge process. NH3 not only acts
as the nitrogen source, but also suppresses the formation of
fullerenes. NH3 also plays another important role for the for-
mation of N-doped multi-layered graphene sheets besides the
as-described function. It decomposes to nitrogen and hydro-
gen under the high temperature during discharge process.
The high reactive hydrogen terminates the dangling carbon
Fig. 5 – TGA curve of multi-layered graphene sheets after
heat treatment at 450 °C for 1 h.
258 CARBON
Fig. 6 – XPS spectra of the two samples prepared in mixing
atmosphere of NH3 and He with the different ratio of NH3/He
(V/V): (a) NH3:He = 1:1 and (b) NH3:He = 1:0.
Fig. 7 – High-resolution XPS spectrum of N1s.
bonds at the edge of graphene sheets thereby preventing the
graphene sheets from closing [28]. If the content of NH3 is low,
for example 25% (V/V), graphene sheets with graphitic balls
are produced. This confirms the crucial role of NH3 for the
production of N-doped multi-layered graphene sheets. At
the same time, the high pressure of buffer gas and high cur-
rent provide more energy to prompt the ionization of anode,
which engenders bigger carbon clusters. This further guaran-
tees the shape of graphene sheets [29].
4 8 ( 2 0 1 0 ) 2 5 5 –2 5 9
In our experimental instrument, it takes 25 min to con-
sume a 30-cm-long anode graphite rod to get 4 g N-doped
multi-layered graphene sheets. In term of this rate, we can
get 9.6 g graphene sheets per hour. This provides the possi-
bility for industrialized production. The successful large scale
production of N-doped multi-layered graphene sheets using
DC arc-discharge method makes the further application of
graphene sheets become possible and many intensive studies
are undergoing.
4. Conclusions
In conclusion, we described a possible route for the mass pro-
duction of multi-layered graphene sheets. Through the use of
NH3, we have successfully synthesized N-doped multi-lay-
ered graphene sheets by DC arc-discharge method. This tech-
nique seems very promising because it carves a way in large
scale production of graphene sheets without use of any
metallic catalyst, which is crucial for the further study and
application. An extensive characterization of the multi-lay-
ered graphene sheets by TEM, Raman spectra, TGA and XPS
is presented.
Acknowledgments
We are grateful for the financial support of this work by the
NSFC (Nos. 20771010, 504371004 and 90206048) and MOST
(Grants 2006CB932701 and 2007AA03Z3110).
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