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High-yield synthesis of carbon nanotubes

using a water-soluble catalyst support in
catalytic chemical vapor deposition

Article in Carbon · June 2006

DOI: 10.1016/j.carbon.2005.12.006

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 Letters to the Editor / Carbon 44 (2006) 1298–1352 1343

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High-yield synthesis of carbon nanotubes using a water-soluble

catalyst support in catalytic chemical vapor deposition
Ali Eftekhari *, Parvaneh Jafarkhani, Fathollah Moztarzadeh
Laboratory of Electrochemistry, Materials and Energy Research Center, P.O. Box 14155-4777, Tehran, Iran

Received 25 June 2005; accepted 2 December 2005

Available online 9 January 2006

Keywords: Carbon nanotubes; Catalytically grown carbon; Catalyst support; Carbon yield

Carbon nanotubes have been the subject of a recurrent NaCl was also used [8,9]. However, little attention has been
interest for long. As a result, various types of carbon nano- paid to these pioneering works, since the results were not
tubes are now widely available on the market. A recent sur- satisfactory, and such synthesis routes tend to form other
vey of classical literature by Monthioux [1] reflects history forms of nanostructured carbon materials [9] rather than
of carbon nanotubes, which have been known for about 40 carbon nanotubes. We report here a case of water washable
years. The last peak of interest started in the nineties [2], catalyst support with high-yield. In addition to the ease of
and considerable efforts have been made since then to syn- using washable catalyst support, this synthesis route is even
thesize them via various methods including conventional more efficient than conventional and commercial ones
ones [3–5]. In the present communication, we would like employing metal oxide catalyst supports.
to report a useful approach to enhance conventional syn- In a typical experiment, a catalyst was prepared by dis-
thesis of carbon nanotubes by means of catalytic chemical solving 0.25 g Co(NO3)2, 5 g CaCl2, and 5 g citric acid in
vapor deposition (CCVD), which is a common method for water. Then, it was slowly dried to form a low-density
synthesis of carbon nanotubes [6]. This is of interest for foam. Since the internal part of the foam is not easily acces-
fundamental understanding, and improvement of commer- sible in CCVD process, the foam was ground to form fine
cial synthesis of carbon nanotubes. particles. In this case, the catalyst is uniformly distributed
Catalyst supports are an essential ingredient for the syn- within the matrix of catalyst support. As the result of the
thesis of carbon nanotubes via CCVD. Common examples subsequent thermal decomposition of the foaming agent
are MgO, Al2O3, SiO2, etc., providing high surface area for (citric acid) that takes place before the main CCVD reac-
CCVD reaction. Although it is practical and common in tion, the previous porous structure within the whole pow-
commercial synthesis of carbon nanotubes, subsequent der is maintained yet modified. Such features can be
post-treatments such as washing with acid make problems easily verified from SEM images (not shown). The CCVD
(cost, environment, . . .). Here, we suggest using a catalyst reaction was performed in a horizontal quartz tube furnace
support which can be easily removed with water. The basic by passing a mixture of 1:1:10 C2H2:H2:N2 for 30 min at
idea returns to Steigerwalt and Lukehart [7] who employed 700 °C. Electron microscopy investigations were made
silicate or carbonate as catalyst support. Chloride such as using a Philips XL30 scanning electron microscope and a
Philips transmission electron microscope.
Fig. 1 displays typical scanning and transmission
*
Corresponding author. Tel.: +98 261 621 0009; fax: +98 261 620 1888. electron microscopy (SEM and TEM) images of the car-
E-mail address: eftekhari@merc.ac.ir (A. Eftekhari). bon nanotubes synthesized. The carbon nanotubes have

0008-6223/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2005.12.006
1344 Letters to the Editor / Carbon 44 (2006) 1298–1352

metal oxides. The main problem associated with the ab-

sence of high surface area catalyst supports (such as
MgO, SiO2, etc.) is a low-yield of products due to lower
accessibility of the catalyst involved in the CCVD reaction.
However, in spite of the low-porosity obstacle was even
worse in the system under investigation (in comparison
with common metal oxides), the water washable catalyst
supports appeared to provide an appropriate accessibility
for the CCVD reaction, as the resulting carbon was
weighted (after washing the catalyst support with water)
to be 4.7 g. This means that the synthesis yield was more
than 1500% in with respect to the initial weight of catalyst.
This is truly high, as the yield of optimized synthesis of car-
bon nanotubes via CCVD is lower than 700% [10,11]. To
ascertain that the resulting product is actually carbon, ther-
mogravimetric (TG) investigations were made (Fig. 2). It is
obvious that 94% of the product is burned at 500 °C, pre-
sumably as a single species. This species was demonstrated
to be carbon nanotubes by TEM (Fig. 1). Correspondingly,
an extensive investigation of large amount of the sample by
means of TEM did not show the existence of any non-fila-
mentous carbon species. Thus, the high yield efficiency of
this approach for the synthesis of MWNTs can be con-
cluded, with a yield in the range of 94%. The remaining
material is the catalyst, which was not dissolved in water.
Very interestingly, this high-yield synthesis makes
unnecessary subsequent treatment for removing the
remaining catalyst. In other words, the metallic impurity
is about 5%, which is quite common even in commercial
samples (at least low-cost samples). Anyway, for our exper-
iment material, it is possible to remove a part of the metal-
lic impurity by washing in HNO3 to obtain carbon product
with only 2% metallic impurity.
In addition, Raman spectra were recorded using an Al-
mega Raman spectrometer with an Ar+ laser at an excita-
tion wavelength of 514.5 nm. The Raman spectrum of the
resulting product indicates two peaks at 1586 and
1340 cm 1 (Fig. 3), corresponding to the vibration of sp2-
bonded carbon atoms in a 2D hexagonal lattice and the
vibrations of carbon atoms with dangling bonds in the
plane terminations of turbostratic and poorly ordered car-

100
Fig. 1. (a) SEM, (b) and (c) TEM images of the carbon nanotubes
synthesized by means of calcium chloride as catalyst support and citric 80
Weight (% wt.)

acid as foaming agent. Despite the low resolution of the micrographs, the
tubular texture can be ascertained along with the bamboo texture from (c),
60
thereby indicating that MWNTs are herringbone-type.

40

diameters ranging from 30 to 150 nm. In general, it is obvi- 20

ous that ideal multi-wall carbon nanotubes (MWNTs) are 5.2 %
formed as well as those prepared with conventional meth- 0
ods. In other words, water washable catalyst support did 0 200 400 600
Temperature (degree)
not affect the structure of MWNTs, and it is applicable
as well as known porous catalysts supports made from Fig. 2. Thermogravimetric (TG) analysis of the carbon nanotubes.
 Letters to the Editor / Carbon 44 (2006) 1298–1352 1345

4000 can swallow the catalyst particles, leading to the formation

of carbon-encapsulated cobalt nanoparticles [8]. This is the
reason why the yield of carbon nanotubes synthesis is
higher for catalyst support of alkali-earth metal chlorides.
Intensity (a.u.)

High melting point of BaCl2 (963 °C) overcomes this prob-

lem. In the case of CaCl2 having a low melting point
(782 °C), the thermal decomposition of the foaming agent
avoids the aforementioned swallowing effect. However,
these are just speculations based on the experimental re-
sults obtained. It is vivid that there are different factors
500 affecting the carbon nanotubes synthesis. For instance, it
500 1000 1500 2000
is not clear why the foaming agent is not applicable for
Raman Shift (cm-1)
the case of BaCl2. We repeated the experiments several
Fig. 3. Raman spectrum of the carbon nanotubes. times, but the results were completely reproducible.
It is obvious that the peculiar phenomena observed for
alkali-earth metal chloride catalyst supports need extensive
investigations to reveal the exact mechanisms involved.
bon, respectively. The ratio of these peaks, in the range of
However, we aim to communicate such astonishing results
G/D = 60/40, indicates that the carbon nanotubes exhibit a
without claiming an exact mechanism because a 2000%
rather defective structure, however in an extent which is
yield is no common in the available processes for carbon
quite common for CCVD-prepared nanotubes. This is
nanotubes synthesis, as it may introduce new strategy for
quite consistent with what can be guessed from the TEM
designing catalysts for carbon nanotubes synthesis via
images, despite their low resolution.
CCVD in commercial processes.
The high-yield synthesis is related to the catalyst support
employed. Similar water washable catalyst supports such
as alkali metal chlorides result in yield lower than 200%, References
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