NANO: Brief Reports and Reviews

Vol. 4, No. 6 (2009) 359–366

c World Scientific Publishing Company


DOI: 10.1142/S1793292009001939

FLOATING CATALYST CVD SYNTHESIS OF

CARBON NANOTUBES USING IRON (III) CHLORIDE:
INFLUENCES OF THE GROWTH PARAMETERS

MEHRNOUSH KHAVARIAN∗ , SIANG-PIAO CHAI† , SOON HUAT TAN∗

and ABDUL RAHMAN MOHAMED∗,‡
∗School of Chemical Engineering, Engineering Campus

Universiti Sains Malaysia, 14300 Nibong Tebal

Seberang Perai Selatan, Pulau Pinang, Malaysia
†School of Engineering, Monash University

Jalan Lagoon Selatan, 46150 Bandar Sunway

Selangor, Malaysia
‡chrahman@eng.usm.my

Received 5 September 2009

Revised 26 October 2009

Carbon nanotubes (CNTs) were synthesized by a low-cost floating catalyst (FC) chemical vapor
deposition (CVD) method in a horizontal reactor. It was found that iron (III) chloride (FeCl3 )
is a high efficient FC precursor for methane CVD to grow CNTs. In this study, the effects of
reaction temperature and flow ratio of methane to nitrogen (CH4 :N2 ) on the morphology of the
CNTs were investigated. The morphological analysis by scanning electron microscopy (SEM)
and transmission electron microscopy (TEM) revealed that increasing the reaction temperature
and flow ratio of CH4 :N2 grew CNTs of larger diameters. Energy dispersive X-ray (EDX) and
thermogravimetric analysis (TGA) were employed to study the purity of the produced CNTs.
As shown by the TGA, the highest yield of 74.19% was recorded for the CNTs grown at 1000◦ C
and flow ratio CH4 :N2 of 300:200.

Keywords: Floating catalyst; chemical vapor deposition; carbon nanotubes; methane; nitrogen;
iron (III) chloride.

1. Introduction producing CNTs have been reported, including elec-

The synthesis of carbon nanotubes (CNTs) has
attracted much attention due to their unique
characteristics and potential applications in many
fields. Numerous potential applications such as elec-
tronic devices, nanomechanical systems,1 electro-
chemical energy storage,2,3 scanning probes and
sensors,4 field emission sources5 and composite
materials6,7 are proposed. Various methods of
tric arc-discharge,8,9 laser ablation10 and chemical
vapor deposition (CVD).11–15 In order for CNTs to
be commercially utilized, the production of CNTs
has to be achieved at high yield, low cost, high
purity and with much greater control over the key
characteristics such as length and diameter. So far,
the CVD process is the most promising method
for industrial scale production due to the lower

‡
Corresponding author.
359
360 M. Khavarian et al.
temperature requirement, higher yield and excel-
lent self-assembly. However, continuous synthesiz-
ing CNTs over supported catalyst in a CVD process
is hardly achieved and the synthesized CNTs typi-
cally contain impurities such as amorphous carbon,
nanoparticles, C60 and other fullerenes.
Floating catalyst (FC) CVD method is intro-
duced recently in view of its ability to produce
continuously high purity CNTs, and it is involved
with simple equipment set-up.16–18 CVD coupled
with FC method has been recognized as the suitable
process for industrial scale production of CNTs. In
addition, compared with other CVD techniques, FC
avoids special time consumed for catalyst prepara-
tion and catalyst activation. Two main approaches
can be employed to synthesize CNTs via FC-
CVD: The first method is involved with pump-
ing or spraying a catalyst precursor into a furnace
and the precursor is typically metallocene hydro-
carbon solution. The second method is to para-
lyze carbon-containing molecules, such as CH4 ,19–21
C2 H2 ,22,23 C2 H4 ,24 on supported nanosized metal
particles in the gas phase. Extensive work on the
use of simple organometallic complexes such as fer-
rocene (Fe(C5 H5 )2 ) (Refs. 22 and 25) and iron car-
bonyl (Fe(CO)5 ) (Ref. 21) as the FC precursors
are reported. The structure of carbon materials is
dependent on the growth parameters such as reac-
tion temperature, type of catalyst precursor, type
of reactant and reactant flow ratio. The catalyst
particles act as the base for the formation of the
pentagon/heptagon pairs.26 Other morphologies of
CNTs, besides ordinary straight structure, such
as bamboo-shaped,27 conical-shaped28 and coils29
have been produced and these structures attract the
immense interest from the scientists.
In this paper, we report the effects of synthe-
sis parameters, such as growth temperature and
flow rate ratio of N2 /CH4 , on the morphology and
yield of the as-grown CNTs from methane FC-
CVD method using iron (III) chloride (FeCl3 ) as
the catalyst precursor. FeCl3 was used in this study
because it is inexpensive and commercially avail-
able. The study on the synthesis of CNTs using
FeCl3 as a catalyst precursor had been reported
by Hou et al.30 A mixture of toluene with N, N-
dimethylaminoacetate (DMAc) was introduced as
carbon source and hydrogen served as the essen-
tial carrier gas in the synthesis of CNTs. In addi-
tion, Zhang and co-workers24 synthesized carbon
nanofibers (CNFs) from ethylene using FeCl3 as a
floating catalyst. Also, it has been explored that
FeCl3 in its gaseous form has an apparent advantage
for the synthesis of CNTs via the CVD method, e.g.,
preventing the formation of large iron hydroxide
and oxide clusters.31 Due to the potential industrial
application of CNTs, it is desirable to synthesize
CNTs by continuous process.32
Methane, the primary composition of natural
gas, was used as a carbon source in this study con-
sidering methane is highly abundant, less toxic, low
cost and stable at elevated temperatures. Thermo-
dynamically, catalytic decomposition of methane
is a very attractive method for producing CNTs.
Besides, synthesizing CNTs by a FC process from
methane is cleaner compared to the similar process
by using toluene30 and benzene.18 The as-prepared
samples were examined and evaluated by trans-
mission electron microscope (TEM), scanning elec-
tron microscope (SEM), energy dispersive by X-ray
(EDX) and thermogravimetric analysis (TGA).
2. Experimental
2.1. Synthesis of CNTs
CNTs were grown by the FC method in a horizon-
tal tubular quartz reactor with an inner diameter
25 mm and 900 mm length. The schematic diagram
of the CNT synthesis apparatus is shown in Fig. 1.
The FeCl3 on the quartz boat was sublimated and
carried into the reaction zone by methane and nitro-
gen flow. In contrast to two-furnace system,18,33 one
furnace was used in this study for FeCl3 sublima-
tion and CVD reaction. The temperature of which
FeCl3 placed was measured by a set of K-type ther-
mocouple temperature.
The reaction temperatures were varied from
850 C to 1100◦ C. The FeCl3 preheating temper-
◦
atures were within the range of 250◦ C–300◦ C.
Methane gas was introduced into the reactor with
different flow rates, ranging from 100 to 400 ml/min
at a constant nitrogen flow of 200 ml/min. The reac-
tion was lasted for 30 min. The nanotubes were
Fig. 1. Schematic diagram of CNT synthesis apparatus.
 Floating Catalyst CVD Synthesis of Carbon Nanotubes Using Iron (III) Chloride
collected from the quartz tube at the lower tem-
perature end of the reactor. A water bubbler was
placed just after the reactor to collect the carried
forward CNTs and to absorb the iron vapor.
2.2. Characterization
The morphology of the produced CNTs was inves-
tigated by both TEM (Philips, model CM12) and
SEM system (Supra-35VP). Specimens for the
TEM observation were prepared by sonication of
the carbonaceous materials in acetone. A few drops
of the suspension were placed onto a holey car-
bon copper grid for TEM characterization. In this
paper, filamentous carbons are classified into two
categories on the basis of the structures, represent-
ing CNFs and CNTs. The term nanofiber is referred
to the tubular carbon structures without or with
insignificant hollow core.34 The percentage of exist
elements of CNT samples was analyzed using EDX.
The product purity and the yield of CNTs were
quantitively determined by the thermogravimetric
analysis (TGA) (SDT Q600 TA). TGA/DTA mea-
surements were performed to determine the amount
of the metal (iron) particles in the carbon sample
(a)
(c)
Fig. 2. TEM micrographs of carbon products synthesized at 1100 C at different flow ratios of CH4 :N2 : (a) 100:200,
(b) 200:200, (c) 300:200 and (d) 400:200.
361
and the oxidation temperatures of carbon materi-
als. The ramping rate was set at 10◦ C/min from
room temperature to 900◦ C for 100 ml/min of puri-
fied N2 /air. Statistical analysis was performed using
the TGA data as to estimate the relative amount
of CNTs in the product.
3. Results and Discussion
3.1. Effect of flow rate ratio of
CH4 :N2
At temperatures of above 280◦ C, FeCl3 sublimated
at the preheating zone of the reactor to form active
iron particles. These iron particles were active in
decomposing methane into carbon and hydrogen
and they acted as the nuclei for the growth of
CNTs. Note that in these experiments, hydro-
gen was not introduced together with methane,
formerly thought to be essential in the forma-
tion of CNTs.18,30 It was found that perfectly
straight CNTs was successfully grown by this sim-
ple method.
Figure 2 shows the TEM images of the car-
bon products synthesized at different gas flow
(b)
(d)
◦
362 M. Khavarian et al.
ratios at 1100◦ C. In Fig. 2, three different types
of carbon materials can be observed, representing
CNTs, CNFs and amorphous materials. Figure 2(a)
shows the morphology of the carbonaceous materi-
als formed under the flow ratio of 100:200 (CH4 :N2 ).
It can be observed that amorphous material was in
majority with few observed CNFs.
Figure 2(b) shows the structural morphologies
of the carbon formed at the flow ratio of 200:200.
A mixture of CNFs, CNTs and amorphous carbons
was observed. It is believed that the supply of the
carbon source was not sufficient to form dense CNT
arrays under this gas ratio.35 Well-orientated CNTs
as can be observed in Figs. 2(c) and 2(d) were grown
at the flow ratios of 300:200 and 400:200, respec-
tively. No CNFs were produced and the only impu-
rity that can be seen was a few disordered carbon
particles. The inner core of these straight tubes was
filled with the iron catalyst particles (Fig. 2(c)).
Increasing the flow ratio from 300:200 to 400:200
increased the amount of carbon decomposed from
(a)
(c)
Fig. 3. SEM micrographs of carbon products synthesized at 1100 C at different flow ratios of CH4 :N2 : (a) 100:200,
(b) 200:200, (c) 300:200 and (d) 400:200.
methane. For this reason, the increased amount of
carbon soot was observed.
Figures 3(a)–3(d) show the SEM images of
the agglomerated products obtained at different
CH4 :N2 ratios. Figures 3(a) and 3(b) show the
sphere-like amorphous carbon formed at the flow
ratio 100:200 and short CNTs at 200:200. Increas-
ing the methane flow rate from 100 to 300 ml/min
enhanced the formation of tubular carbon struc-
ture (Fig. 3(c)). It is speculated that an increase
in the methane flow rate increased the carbon con-
centration on the surface of the catalyst particles.
Consequently, it provoked the carbon to precipitate
out of the iron particles at the higher methane flow
rate in the form of CNTs. However, it was observed
that increasing the methane flow rate to 400 ml/min
decreased the formation of CNTs.33
In addition, as shown in Fig. 3(d), amorphous
carbon was clearly seen on the surfaces of CNTs.
The formation of amorphous carbon increased due
to the greater thermal decomposition of methane
(b)
(d)
◦
 Floating Catalyst CVD Synthesis of Carbon Nanotubes Using Iron (III) Chloride 363

Fig. 4. EDX spectrum taken from the nanotube synthesized at 1100◦ C at a flow ratio of 300:200.

at the higher methane flow rate. The amorphous (300:200). Table 1 shows the yield of the carbon for-
carbon deposited on the surface of iron particles, mation as estimated by TGA and the outer diame-
thus deactivating the iron for growing CNTs. It is ters of CNTs as measured from TEM images. It was
expected that the extra carbon atoms from methane found that temperature affected the yield of CNTs
decomposition could enhance the radial growth significantly. No carbon was formed at a tempera-
of CNTs, resulting in increasing the diameter of ture of 850◦ C and increasing the reaction temper-
CNTs.35 By examining the TEM images presented ature increased the yield of CNTs. The maximum
in Figs. 2(c) and 2(d), the average inner and outer yield of CNTs (ca. 74.19%) was obtained at 1000◦ C.
diameters of the CNTs synthesized at the flow ratios The TEM images of the products formed
of 300:200 and 400:200 were 15.45 and 16.67 nm, at different reaction temperatures are shown in
and 39.10 and 46.87 nm, respectively. Figs. 5(a)–5(c). No tubular carbon structure was
Figure 4 shows the EDX results of the nanotube grown at 900◦ C (Fig. 5(a)). Thermodynamically,
synthesized at 1100◦ C at the flow ratio of 300:200. the solubility of carbon in iron increased with
The result divulges that the weight percent of cat- temperature.40 At a low temperature, there was no
alyst particles, identified as iron/iron oxide in the well-interaction between carbon and iron atoms. If
product, was very low. The elemental compositions the temperature was too low, the methane would
for carbon, oxygen, iron and chlorine were 85.47, not be decomposed completely, hence the limited
12.62, 1.23 and 0.69%, respectively. The chloride carbon source was not enough to form long and
decomposed from FeCl3 precursor can bond with straight CNTs. Low activity of the iron catalyst
hydrogen radicals resulted from methane decompo- and low carbon source were the main factors to
sition. Combination of chlorine and hydrogen radi- cause the formation of disordered CNTs at a lower
cal provides a C-rich and H-deficient condition that
favors the formation of sp2 -like graphitic structures
and CNTs growth.36 Probably, the degree of “hol- Table 1. Operating conditions, production yield and outer
lowness” of the CNTs increased with increasing the diameter of the synthesized CNTs (reaction time: 30 min,
the mass of FeCl3 : 0.2 g).
chloride content in carbon precursors.37 Many reac-
tions have also been performed with the chlorinated Reaction Flow rate ratio Outer
carbon reactants and the products obtained include temp. (◦ C) CH4 :N2 Yield (%) diameter (nm)
the hollow carbon nanospheres.38,39
1100 300:200 59.00 39.10
1000 300:200 74.19 37.00
3.2. Effect of reaction temperature 950 300:200 53.27 35.20
900 300:200 16.80 —
The growth of CNTs was further explored as a 850 300:200 — —
function of temperature at the preferred flow ratio
364 M. Khavarian et al.
(a)
(c)
Fig. 5. TEM micrographs of carbon products synthesized at flow ratios of 300:200 (CH4 :N2 ) at different reaction tempera-
tures: (a) 900◦ C, (b) 950◦ C, (c) 1000◦ C and (d) showing the bamboo-like CNTs at 1000◦ C.
temperature. Figure 5(b) shows the straight CNTs
with significant hollow cores synthesized at 950◦ C.
In Fig. 5(c), amorphous carbon as marked by arrows
was observed on the CNTs synthesized at 1000◦ C.
The decrease in the density of the iron particles
due to the aggregation of the iron particles at
high temperatures is believed to cause the forma-
tion of amorphous carbon at 1000◦ C.35 In addition,
bamboo-like CNTs were synthesized at 1000◦ C as
shown in Fig. 5(d).
Based on the TGA result shown in Table 1,
one can note that increasing the reaction tempera-
ture to 1000◦ C gave the highest yield of CNTs, but
the yield was decreased to 59.00% with increasing
the temperature to 1100◦ C. From the TEM anal-
ysis, the average outer diameters of CNTs grown
at 950◦ C, 1000◦ C and 1100◦ C were 35.20, 37.00
and 39.10 nm, respectively. Increasing the reaction
temperature resulted in increasing the diameter of
the CNTs formed.30 Probably, this was due to the
increase in the solubility of carbon in iron at high
temperatures that contributed to the growth of
CNTs of larger diameters.40
(b)
(d)
3.3. TGA analysis of the
as-synthesized CNTs
The CNTs synthesized at 1000◦ C were investigated
by TGA/DTA and the results are shown in Fig. 6.
Figures 6(a) and 6(b) present the TGA graph and
the derivative thermogravimetric (DTA) curves for
the as-synthesized CNTs, respectively. As shown in
Fig. 6(a), an initial weight loss (ca. 1.261 wt%) from
ambient temperature to 300◦ C was attributed to
the removal of absorbed water and oxidation of the
disordered carbon.
A second weight loss (ca. 2.165 wt%) observed
in between 300◦ C and 400◦ C can be attributed to
the oxidation of the amorphous. The third weight
loss (ca. 74.19 wt%) centered between 400◦ C and
720◦ C is corresponded to the oxidation of the CNTs.
The total weight loss up to a temperature of 400◦ C
was less than 3.5 wt%, suggesting that the amount
of disordered carbon was very low. The residue
after complete oxidation of the carbon samples
was ca. 22.07 wt%. The residue was dissolved in
the hydrochloric acid and the color of the solution
 Floating Catalyst CVD Synthesis of Carbon Nanotubes Using Iron (III) Chloride
(a)
(b)
Fig. 6. (a) TGA and (b) DTA curves for CNTs synthesized
at 1000◦ C at flow ratio 300:200 (CH4 :N2 ).
turned to red, indicating that iron species was
the main constituent of the residue.41 Interestingly,
the DTA curve shown in Fig. 6(b) displays two
peaks with the maximum weight loss per degree
tend at 565.01◦ C, suggesting that two types of
CNTs appeared in the sample. It is consistent with
the TEM results which showed that CNTs synthe-
sized in this condition were ordinary CNTs and
bamboo-like CNTs as shown in Figs. 5(b) and 5(d),
respectively.
3.4. Growth mechanism of CNTs
It is commonly agreed that the formation mech-
anism of the CNTs involves three main stages:
nucleation, growth and termination. The nucle-
ation marks the onset of the carbon nanostructure
formation and divides the reaction sequence into
two well-defined periods: induction and growth.42
Firstly, metal catalyst particles acted as the nuclei
for the growth of CNTs in the gas phase. FeCl3
365
sublimated to form active iron catalyst particles for
decomposition of methane. Induction elapses until
the achievement of carbon precipitation. The ini-
tial precipitation of carbon is nucleation. The nucle-
ation is the first step and crucial for CNT formation
and structural control. The growth as the period in
which the carbon nanostructure increased its length
until the reaction was stopped. The understanding
of growth mechanism of CNTs is very important to
control their structures, which in turn will be the
basis for their further theoretical studies and appli-
cations. When the catalysts were entirely encapsu-
lated by the graphitic layers, the growth of CNTs
was terminated.
4. Conclusion
We have demonstrated in this paper that FC-CVD
of methane using FeCl3 as a catalyst precursor is
effective for the growth of CNTs. The synthesis pro-
cess has been investigated with regard to the two
different reaction parameters: the reaction tempera-
tures and the gas flow ratio of CH4 :N2 . It was found
that an increase in the reaction temperature or the
flow ratio of CH4 :N2 increased the diameter of the
CNTs formed. As revealed by the TGA and electron
microscopy, the highest yield of CNTs, i.e., 74.19%,
was obtained at 1000◦ C and the synthesized nano-
tubes possessed the average diameter of ca. 40 nm.
Besides the ordinary straight structural orientation,
bamboo-like morphology could be observed. In most
cases, catalytic particles were found seated in the
narrow cavities of the nanotubes.
Acknowledgments
The authors gratefully acknowledge the finan-
cial support provided by the Universiti Sains
Malaysia (USM) under the Research University
Grant Scheme (Project A/C No. 814003), the
Malaysian Technology Development Corporation
(MTDC) under the Commercialization of Research
and Development Fund (CRDF) (Project A/C No.
MBF065-USM/05) and the Cradle Fund Sdn. Bhd.
under the University-Cradle Investment Program
(U-CIP) (Project No: U-CIP-B47).
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