Indian Journal of Chemistry

Vol. 45A, April 2006, pp. 182-187

Template synthesis and characterization of well-aligned carbon nanotubes by

carbonization of polyparaphenylene
T Maiyalagan & B Viswanathan*
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India
Email: bvnathan@iitm.ac.in
Received 18 January 2005; revised 20 February 2006

The synthesis of well-aligned carbon nanotubes by pyrolysis of polyparaphenylene on alumina membrane template is
described here. The prepared nanotubes have been characterized by electron microscopic analyses, Raman spectroscopy and
cyclic voltammetry. Scanning electron micrographs and transmission electron micrographs reveal the hollow structure and
vertically aligned features of the nanotubes. The surface morphology of the nanotubes has been studied by atomic force
microscopy. Raman spectrum shows characteristic bands at 1384 cm-1 (D-band) and 1603 cm-1 (G–band) indicating well-
graphitized nanotubes. The electrochemical behavior of the synthesized carbon nanotube film coated with glassy carbon
electrode shows fast electron transfer and higher current response. The well-aligned carbon nanotube arrays can have
potential applications in lithium-ion battery and other fields.

Since the discovery of carbon nanotubes (CNTs) by
Ijima in 19911, a number of studies on CNTs and
related nanostructures have been carried out. The
extraordinary mechanical and electronic properties of
these structures have led to several applications,
including nanoscale fibres2, nanoelectronic devices3,
probe tips for scanning probe microscopy4 and field
emitter arrays5. CNTs are promising materials for
catalyst supports6 and electrodes for
supercapacitors7,8. Furthermore, it has been proved
that CNTs have better conductivity than graphite. The
synthesis method has the advantage of controlling
composition, morphology and the size of the
nanotubes. The normal sources of carbon to produce
the CNTs are hydrocarbons. The complexity involved
in the synthesis of CNTs using gaseous hydrocarbons
is high. The criteria for selecting the carbon precursor
are that it should be rich in carbon content and should
be easily decomposed to give rise to a pure carbon
deposit. Polymers such as polyacrylonitrile17,
polyvinyl pyrolidone18, polyfurfurylalcohol19,
polypyrrole and polyphenylacetylene16 have been
20

nanostructured morphology, higher surface area and
suitable electronic properties suggest that CNTs have
potential ability to promote electrochemical reactions
in fuel cells9,10. CNTs have been synthesized by arc
discharge11, laser ablation12, pyrolysis13 and various
chemical vapor deposition (CVD) methods14. In CNTs
produced by arc discharge and laser ablation
techniques, difficulties are encountered in the control
of size and alignment of the nanotubes. Further, these
techniques require purification processes to separate
the CNTs from the catalyst particles used in the
synthesis.
The template synthesis method has been widely
used for preparing nanostructured materials15,16,
which involves the synthesis of the desired material
within the pores of a membrane to generate nanotubes
of cylindrical nature with uniform diameter. Among
all the methods of preparation of CNTs, the template
used in template synthesis to produce CNTs.
It is reported that carbon obtained in the pyrolysis
of polymer precursors in the temperature range 500-
1000 ºC is effectively used in lithium ion batteries
Polyparaphenylene derived carbon shows high
storage capacity in lithium ion batteries21. CNTs have
been explored as better electrode material for both
lithium ion batteries and fuel cell applications. The
template synthesized CNTs could be used as high
performance anode material in lithium-ion
batteries22,23. So, the synthesis of polyparaphenylene
derived CNTs by template synthesis has significance
for both lithium ion batteries and fuel cell electrodes.
We report here the synthesis of well-aligned CNTs
using polyparaphenylene as carbon source. This is
formed in situ during the polymerization of benzene
in the alumina membrane template and subsequent
carbonization leading to the formation of carbon
2 INDIAN J CHEM, SEC A, APRIL 2006
nanotubes. The morphology and structural features of
the nanotubes have been investigated using electron
microscopy and Raman spectroscopy and the
electrochemical measurements indicate that this
material is suitable for electrode applications.
Experimental
All the chemicals used were of analytical grade.
Benzene, (Sisco, India), aluminium chloride, copper
chloride and concentrated HF (Merck) were used.
Alumina membranes were obtained from Whatman
Anopore Filters.
Synthesis of carbon nanotubes
Polyparaphenylene (PPP) was prepared on the
alumina membrane template according to the method
of Kovacic and Oziomek24. The alumina membrane
template, immersed in a benzene monomer solution
undergoes cationic polymerization with AlCl3 and
CuCl2. Nitrogen was purged through out the
experiment. During this process, polymer was
produced from the monomers and is deposited within
the pores of the alumina template. The template
synthesis method yielded the tubule of desired
polymer within the pores of the alumina membrane by
controlling the polymerization time and temperature.
After polymerization on the membrane, the membrane
was washed with deionised water and then dried.
Subsequently, this membrane was carbonized in the
electric furnace at 1173 K under argon atmosphere.
The resulting carbon-alumina composite was
immersed in 48% HF at room temperature for 24 h to
remove the alumina template. The nanotubes were
then washed with distilled water to remove the
residual HF and dried at 393 K.
Characterization
The scanning electron micrographs were obtained
using JEOL JSM-840 model working at 15 keV. For
transmission electron microscopic studies, the
nanotubes dispersed in ethanol were drop cast on to a
carbon-coated copper grid followed by solvent
evaporation in air at room temperature. Then, the
images were obtained using a Phillips 420 model,
operating at 120 keV. The nanotubes are sonicated in
acetone for 20 min and then dropped on clean Si
substrates. AFM imaging was performed in air using a
Nanoscope IIIA atomic force microscope (Digital
Instruments, St. Barbara, CA) operating in contact
mode.
The CNTs placed in glass capillary tubes were used
for recording Raman spectrum at room temperature
with 514.5 nm excitation in the backscattered mode
using Bruker FRA106 FT-Raman instrument.
Cyclic voltammetry (CV) measurements were
performed with Bio Analytical System (BAS) 100
B/W electrochemical workstation at room temperature
using a three-electrode configuration cell. The
solutions were deoxygenated by purging with
nitrogen for about 15 min and an atmosphere of
nitrogen was maintained throughout the CV scans. A
GCE (3.00 mm diameter) and a platinum wire were
used as working and auxiliary electrodes respectively.
All potentials were measured versus the AgAgCl
pseudo reference electrode. Prior to CV scans, the
GCE was polished with alumina (<10 µm) on a
Buehler felt pad followed by washing with deionised
water. In order to prepare the composite electrode, the
nanotubes were dispersed ultrasonically in water at a
concentration of 1 mg mL-1 and then 20 µL of this
aliquot was transferred on to a polished glassy carbon
substrate .After evaporation of water, the resulting
thin film was covered with 5wt% Nafion solution
followed by an air-drying step.
Results and discussion
Figs 1a-1c and 1d show SEM and TEM images of
the synthesized carbon nanotubes after the dissolution
of alumina membrane template. SEM images given in
Figs 1a-1c show the morphology of the well aligned
CNTs. The well-aligned nanotubes are grouped into
high-density arrays appearing like bristles which are
reflecting the highly dense straight pores of the
alumina membrane (~109 pores/cm2). Figure 1a shows
the top view of the nanotubes (low magnification).
The side view of the vertically aligned nanotubes
(high magnification) is shown in Fig. 1b. Figure 1c
shows the lateral view of the well-aligned nanotubes
(high magnification) about 50-60 µm in length similar
to the thickness of the alumina membranes. We
performed the TEM analysis to determine the
morphology and the diameter of the nanotube.
TEM images of the synthesized carbon nanotubes
prepared from polyparaphenylene is shown in Fig. 1d.
A more clear view is obtained from the TEM images
and the carbonized specimens are found to have a
hollow structure with open ends. The channels of the
membranes being cylindrical with uniform diameter
and the tube diameter closely matching the pore size

of the template used, monodispersed nanotubes of the
desired material were obtained.
AFM images of the synthesized carbon nanotubes
deposited on a silicon substrate are shown in Fig. 2.
The AFM tip was carefully scanned across the tube
surface in a direction perpendicular to the tube axis.
From the AFM images, a part of the long nanotube is
appearing to be cylindrical in shape and is found to be
terminated by a symmetric hemispherical cap.
Because of the finite size of the AFM tip, convolution
between the blunt AFM tip and the tube body will be
giving rise to an apparently greater lateral dimension
than the actual diameter of the tube25.
The graphitic nature of nanotubes obtained from
the carbonization of polyparaphenylene was
investigated by Raman spectroscopy. Figure 3 shows
Raman spectrum for the sample. It shows two peaks at
1384 and 1590 cm-1. The peak at 1590 cm-1 (G-band)
corresponds to the high frequency E2g first-order
mode, which can be attributed to the opposing
movement of two neighboring carbon atoms in a
graphitic sheet26,27. The peak at 1384 cm-1 (D-band)
could be as a result of defects in the curved graphitic
sheets, tube ends and finite size crystalline domains of
the tubes28. From the Raman scattering spectra, it is
seen that the degree of crystallinity increases with the
rise in temperature. We notice that the relative
intensity of 1590 cm-1 peak is higher than the 1384
cm-1 peak indicating the crystallinity of the
synthesized carbon nanotubes. As temperature
increases to 1000 ºC, the peak at 1590 cm-1 (G-band)
increases and attains higher crystallinity.
Figure 4 shows the cyclic voltammograms of CNT-
Nafion coated glassy carbon electrodes in 1 M H2SO4
scanned between -0.2 V and + 0.8 V versus Ag/AgCl
at a scan rate of 50 mV/s. It is clear from the
voltammograms that the GC/CNT-Nafion electrode
shows higher current response than all other
electrodes with the same geometric area. The peak
potentials of + 0.4 V and + 0.45 V in the forward and
reverse scan of the GC/CNT-Nafion electrode also
suggest the reversible nature of the redox process. The
higher electroactive surface area, which is effectively
utilized is reflected from the higher electrochemical
current response. To understand the electron transfer
kinetics of the nanotube electrode, Fe(CN)64-
/Fe(CN)63- redox couple has been used. The
voltammogram was run in 5 mM K4[Fe(CN)6] in 0.1
M KCl at a scan rate of 50 mV/s.
3
First, the electrochemical kinetics of the Fe(CN)64-
/Fe(CN)63- redox reaction on the glassy carbon coated
carbon nanotube film was compared to those of a
glassy carbon electrode. Figure 5a shows a cyclic
voltammogram obtained at the working electrode of
the carbon nanotube film. The voltammogram
obtained using a polished glassy carbon disk electrode
is also shown. The cyclic voltammograms in Fig. 5
show that the current-potential profiles for both of
these electrodes are different, which suggests that the
electroactive surface area for the two electrodes are
different. The peak-potential separation ∆Ep for the
glassy carbon electrode is about 100 mV and while
that of the carbon nanotube film is about 70 mV.
These results are indicative of the electrocatalytic
activity for the Fe(CN)64-/Fe(CN)63- redox reaction,
which is clearly evidenced by the significantly low
peak-potential separation ∆Ep and high peak currents
(ipa, ipc) for the electrodes. The results also indicate
that the carbon nanotube film has better
electrocatalytic activity for the kinetics of Fe(CN)64-
/Fe(CN)63- redox reaction than that of the glassy
carbon electrode. The peak current density for the
carbon nanotube film electrode is also very higher
than that for the glassy carbon electrode, which might
be owing to the higher surface roughness and hence a
higher effective surface area. The electron transfer
reaction of Fe(CN)64-/Fe(CN)63- takes place at both the
outer surface and also the interior surface of the
carbon nanotube electrode. The smallest ∆Ep of the
synthesized carbon nanotubes indicates fast electron
transfer (highest heterogeneous charge transfer rate
constant). The larger background current is due to the
capacitance. This is in good agreement with the larger
capacitance feature reported before29. The higher
electrochemical response and fast electron transfer
kinetics of the carbon nanotube electrode are because
of high electrochemical surface area than the other
electrodes due to high porosity and tubular
morphology.
Conclusions
Polyparaphenylene is a highly efficient polymer
precursor for synthesis of carbon nanotubes and the
adopted template method is very much effective for
the synthesis of well-aligned carbon nanotubes. A
carbon nanotube with good packing density has also
been achieved. The morphology of the well-aligned
nanostructures has been verified by SEM, TEM and
4 INDIAN J CHEM, SEC A, APRIL 2006
AFM. Raman spectroscopic studies show a higher
degree of crystallinity. The electrochemical behavior
of the carbon nanotube film-coated glassy carbon
electrode was investigated and the synthesized carbon
nanotube electrode showed fast electron transfer and
higher current response. This newly synthesized
carbon nanotube material can be a potential candidate
in electrochemistry as electrodes for lithium-ion
batteries and fuel cells.
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Figure captions
Fig. 1 — Typical Scanning electron micrograph images of the
carbon nanotubes: (a) top view of the nanotubes (low
magnification), (b) Side view of the vertically aligned nanotubes
(high magnification), and (c) Lateral view of the nanotubes (high
magnification); (d) TEM images of the carbon nanotubes
Fig. 2 — A Typical AFM image of the part of a long nanotube on
a silicon substrate
Fig. 3 — Raman spectrum of the carbon nanotubes
Fig. 4 — Cyclic voltammograms in 1 M H2SO4 aqueous solution
at: (a) Glassy carbon coated carbon nanotube electrode, (b)
Glassy carbon coated vulcan electrode, and (c) Glassy carbon
Fig. 5 — Cyclic voltammograms in 5 mM K4Fe(CN)6/0.1 M KCl
redox electrolyte at scan rate 50 mV/s for (a) Glassy carbon
coated carbon nanotube electrode, and (b) Glassy carbon