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Functionalization of carbon nanotubes by potassium permanganate assisted with phase

transfer catalyst

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2002 Smart Mater. Struct. 11 962
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INSTITUTE OF PHYSICS PUBLISHING

SMART MATERIALS AND STRUCTURES

Smart Mater. Struct. 11 (2002) 962965

PII: S0964-1726(02)55164-8

Functionalization of carbon nanotubes by

potassium permanganate assisted with
phase transfer catalyst
Nanyan Zhang, Jining Xie and Vijay K Varadan
Center for the Engineering of Electronic and Acoustic Materials and Devices, Pennsylvania
State University, University Park, PA 16802, USA

Received 24 June 2002

Published 4 November 2002
Online at stacks.iop.org/SMS/11/962
Abstract
An improved process is presented to functionalize carbon nanotubes by
potassium permanganate with the help of phase transfer catalyst (PTC). The
PTC helps to extract potassium permanganate from the solid phase to an
organic solvent phase and improves the efficiency of nanotube oxidation.
The higher reaction efficiency as well as mild reaction conditions leads to a
higher yield of functional nanotube preparation. X-ray photoelectron
spectroscopy confirms the functional groups attached to the nanotube
surface. A preliminary comparison is given of the potassium permanganate
oxidation of nanotubes with and without PTC. This method is believed to be
a potential economic method for large-scale functional nanotube
preparation.

1. Introduction
It is well known that carbon nanotubes have been expected
to have versatile potential applications due to their novel
structures and remarkable mechanical, thermal and electrical
properties [1, 2]. Unfortunately, experimental confirmation
of these applications has been hindered mainly by the poor
processibility of carbon nanotubes. Because of the pure
carbon element and their stable structure, carbon nanotubes
are insoluble in any organic solvents, which makes it
extremely difficult to explore their properties and applications.
For example, carbon nanotubes are regarded as promising
filler materials for a new generation of high performance
nanocomposites because of their exceptionally high Young
modulus [3], bending strength and low density. However, this
composite processing is still limited to bench-top processing
and has been hampered by high viscosity of available matrix
materials, lack of dispersion and excessive porosity.
To overcome this problem, chemical modification on
the carbon nanotube surface is regarded as the best method.
Chemical functionalization of carbon nanotubes is expected
to play an essential role in tailoring the properties of
material. After functionalization, with the help of functional
groups attached to the surfaces, carbon nanotubes could react
readily with other chemical reagents and form homogenous
dispersions or even well aligned materials.

Graphite will undergo fluorination and oxidation

completely under certain conditions, which leads to the loss
of its most interesting properties. To meet the requirement
of nanotube functionalization, chemical reaction occurring on
the surface must be controlled in a particular manner. In other
words, we need the chemical modification of nanotubes as well
as their initial properties. In this case, a reagent is desired to
selectively attack some of the -bonds without bringing a total
destruction of the graphene structures of the nanotubes.
It is well documented that the chemistry of the fullerenes
is characterized by addition reactions. The fullerenes undergo
such reactions with relative ease because the conversion of
trigonal carbon atoms to tetrahedral carbon atoms serves
to release the tremendous strain present in the spheroidal
geometry [4]. For carbon nanotubes, because of the greater
curvature, the caps are the sites of preferential reactivity. This
is the reason why many researchers have used reactions to open
the caps and insert various species into the nanotubes. As for
chemical functionalization, functional groups are attached to
the caps much more easily than to the walls. Therefore, the
nondestructive attachment of functional groups to the walls of
nanotubes presents a further challenge to experiment.
Permanganate has been used for decades as an oxidizer
in organic chemical manufacturing [5]. The primary redox
reaction under low pH for permanganate is given as MnO
4 +
8H+ + 5e Mn+2 + 4H2 O. With excess permanganate,

0964-1726/02/060962+04$30.00 2002 IOP Publishing Ltd Printed in the UK

962

Functionalization of carbon nanotubes by potassium permanganate assisted with phase transfer catalyst

Mn2+ can be oxidized subsequently as 3Mn+2 + 2MnO

4 +
2H2 O 5MnO2 (s) + 4H+ . Permanganate oxidation of many
organic compounds can be achieved without cleavage of the
carbon framework.
In 1995, Hiura et al [6] reported the functionalization
of carbon nanotubes during the purification process. In that
experiment, potassium permanganate was used as the oxidant
in the presence of sulfuric acid. This oxidation changes
the chemical make-up of the reactive edge of the tips and
perhaps even the outer (and the inner) layer of the nanotube.
X-ray photoelectron spectroscopy (XPS) was used to studied
the surface modification and indicated that about 15% of the
carbon constituting the nanotubes is bound to either hydroxy or
carboxy groups. Clearly, not only the tips but also the surface
of the outer layer were found to be covered with these species.
Besides potassium permanganate, other oxidant reagents
were tried to attach functional groups to nanotube surfaces by
Satishkumar and his group in India [7], such as concentrated
HNO3 , concentrated H2 SO4 , aqua regia, superacid HF/BF3 ,
aqueous OsO4 , OsO4 NaIO4 etc. The concentration of the
surface acid groups was found to be in the range of 2 1020
10 1020 acid sites per gram of nanotubes, as shown in table 1.
Liu et al [8] reported a functionalization method for singlewalled nanotubes by using a mixture of concentrated sulfuric
and nitric acids as the oxidant. Another purpose of this process
is to cut nanotubes into short pieces. They also assumed the
open ends to be terminated with many carboxylic acid groups.
However, the methods mentioned above all suffered
from low yield of the functionalization process. In this
paper, we present an improved procedure to functionalize
carbon nanotubes by potassium permanganate with the help
of phase transfer catalyst (PTC). The higher yield of this
functionalization process is the major advantage.

2. Experiment
The nanotube source used in this experiment was gained from
the microwave CVD method. This method is based on the
pyrolysis of acetylene by microwave heating on nano-sized
cobalt particles embedded in zeolite, which serves as a catalytic
support. The average diameter of these multi-walled carbon
nanotubes ranges from 20 to 30 nm [9]. After hydrofluoric
acid treatment and air oxidation, the as-prepared nanotubes
were purified and ready for the functionalization process.
For comparison, the functionalization of nanotubes by
potassium permanganate without PTC was also performed.
Reaction 1. 0.12 g of purified nanotubes were dispersed
in 20 ml of 0.5 M sulfuric acid by ultrasonic vibration in a
two-necked flask equipped with a condenser and a dropping
funnel. The suspension was refluxed in an oil bath at 120 C
with magnetic stirring. Meanwhile, 1.98 g of potassium
permanganate was dissolved in 20 ml of 0.5 M sulfuric acid
and this solution was added to the flask drop by drop. Then
the reaction was kept at 120 C for 3 h. After that, the
resulting suspension was filtered, washed with concentrated
hydrochloric acid and deionized water and then dried.
Reaction 2. 0.12 g of purified nanotubes and 25 ml
dichloromethane (CH2 Cl2 ) were added to a 100 ml flask and
the suspension was vibrated ultrasonically for 0.5 h. About
1.0 g of phase transfer agent (Aliquat 336, from Aldrich) was

Figure 1. Micrograph of SEM of carbon nanotubes after

functionalization.

added, followed by 5 g of powdered potassium permanganate

in small portions during a period of 2 h. 5 ml of acetic acid was
also added. The mixture was then stirred vigorously overnight
at room temperature. As the final step, the resulting material
was gained after filtering, concentric HCl acid treatment, water
washing and drying.
A Hitachi 3000N scanning electron microscope (SEM)
was used to investigate the morphology of the materials after
functionalization. X-ray photoelectron spectroscopy (XPS)
spectrum of f-CNTs was obtained by using a Kratos Analytical
XSA800 pci under 108 109 Torr vacuum.

3. Results and discussion

In the functionalization reaction, the colour of the suspension
changes from dark purple to dark brown, indicating the
The functionalized
transformation of Mn+7 to Mn+4 .
nanotubes gained from both methods are dark in colour.
The yield of the functionalized nanotubes in the reaction
without PTC is about 3540% in terms of the total weight of
starting material, which is consistent with the result reported
by Hiura [6]. For the reaction with PTC, the yield of
functionalized nanotubes is about 6570%, much higher than
the yield of reaction 1.
Scanning electron microscopy was used to investigate the
carbon nanotube sample before and after functionalization. As
shown in figure 1, the morphology of carbon nanotubes after
functionalization preserves. No destruction was observed,
which means carbon nanotubes are strong enough to withstand
the functionalization process.
We also found that the functionalized nanotubes from both
methods could be well dispersed in many common organic
solvents, such as ethanol, methanol, methyl ethyl ketone
(MEK), dichloromethane, toluene etc. This phenomenon of
uniform nanotube dispersion in solvents is one of the properties
of functionalized nanotubes. It has been reported that due to
the nanoscale size, the high surface energy of nanotubes gives
them a strong tendency to agglomerate. Even with the help of
ultrasonic vibration, the untreated nanotubes may not remain
in any solvent in quiescent suspension. However, appropriate
functionalized nanotubes can dramatically raise the stability
of suspensions [10]. The functionalization process induces a
negatively charged surface, particularly through the ionization
of acidic surface groups. The resulting electrostatic repulsion
leads to the stable uniform colloidal dispersion.
963

N Zhang et al

Table 1. The concentration of the surface acid groups in the nanotubes opened by different oxidants [7]
HNO3
2.5 10

H2 SO4
20

6.7 10

20

Aqua regia

KMnO4 (acid)

KMnO4 (alkali)

OsO4 NaIO4

7.6 10

8.3 10

10 10

5.2 1019

20

(a)

(b)

Figure 2. XPS spectra of functionalized nanotubes. (a) XPS

spectrum of functionalized nanotubes from reaction 1; (b) XPS
spectrum of functionalized nanotubes from reaction 2.
(This figure is in colour only in the electronic version)

XPS, as one of the surface analytical techniques, is capable

of readily providing information about chemical bonding on
the surface. XPS was performed on each functionalized
nanotube sample to get the information of functional groups on
the nanotube surface. Thus, the C 1s main peak was scanned
in high resolution. In the curve fitting, the overall peak in the
range of 283289 eV can be fitted by a superposition of four
peaks. The main peak (284.7 eV) is attributed to the C 1s,
while the other three peaks are assigned to CO (286.1 eV),
C=O (287.5 eV) and COO (288.8 eV) respectively. The
XPS spectra are shown in figure 2.
As the qualitative result, XPS spectra show that both
functional nanotubes have functional groups. The semiquantitative analysis gives the rough atomic concentration of
carbon atoms functionalized. Table 2 gives the comparison of
semi-quantitative analysis of functional nanotubes.
For f-nanotubes from reaction 1, the result indicates that
about 12% of carbon atoms are bonded with an OH group
and 7.45% with a COOH group. The f-nanotubes from reaction 2 have a higher concentration of OH groups (23%) and
964

20

20

a lower concentration of COOH groups (3.8%). It is necessary to point out in this paper that this quantitative analysis
of functional groups attached to nanotubes is at best semiquantitative. These values can only give us rough information
about the functional groups. The concentrations of the OH
group are higher than the values reported [6]. The reason may
be the energy-loss tail in the C 1s peak. Also the trace amount
of zeolite material in the purified nanotube material may be related to the higher concentration of OH groups. Much more
accurate quantitative analysis of functionalized nanotubes is
going to be performed in the near future.
The higher yield of functionalized nanotubes is the major
advantage of oxidation by potassium permanganate with PTC.
Untreated nanotubes are hydrophobic and do not disperse
well in aqueous solvent. On the other hand, potassium
permanganate is water soluble. In reaction 1, the hydrophobic
property of nanotubes leads to the low efficiency of contact
between nanotubes and potassium permanganate dissolved in
water. Thus high reaction temperature, 120 C, is necessary
to increase the reaction rate of functionalization. However, at
high temperature, potassium permanganate is a strong oxidant,
which may destroy nanotube structure. This may be the reason
for the low yield of functionalization.
Phase transfer catalysis is based on the ability of catalytic
amounts of the transfer agents to increase the rate of a chemical
reaction between reagents located in different phases of a
reaction mixture [11]. In reaction 2, potassium permanganate
could be extracted into organic solvent (dichloromethane,
where the nanotubes were suspended) by phase transfer agent.
This process could substantially increase the reaction rate and
efficiency. Therefore, the functionalization can be carried out
under mild conditions. Fewer nanotubes being destroyed leads
to higher yield. The function of acetic acid in the reaction is
to neutralize the hydroxide ions formed to promote a more
complete reaction [12]. We observed that without acetic acid,
the resulting suspension is still dark purple after reaction and
the quality of functionalized nanotubes is not acceptable.

4. Conclusion
Carbon nanotubes should be functionalized to explore their
unique properties and potential applications. In this paper,
potassium permanganate is used as an oxidant to functionalize
multi-walled carbon nanotubes derived from the microwave
CVD method. Unlike the conventional oxidation, PTC
is introduced into the functionalization reaction, which
drastically increases the efficiency of oxidation by potassium
permanganate. The yield of functionalization is improved from
35 to 65%. XPS confirms the functional groups attached to
the nanotube surface. This improved oxidation with the help
of PTC could be a potential economic method to prepare high
quality functional nanotubes on a large scale.

Functionalization of carbon nanotubes by potassium permanganate assisted with phase transfer catalyst

Table 2. Semi-quantitative analysis of functionalized nanotubes. (Reaction 1, functionalization reaction by potassium permanganate
without PTC; reaction 2, functionalization reaction by potassium permanganate with PTC.)
f-nanotubes from reaction 1

f-nanotubes from reaction 2

Peak

Position (eV)

Atomic conc. (%)

Position (eV)

Atomic conc. (%)

C 1s
COH
COOH
C=O

284.66
286.33
289.00
287.62

75.96
12.63
7.45
3.96

284.71
286.12
288.91
287.54

68.35
23.60
3.82
4.23

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