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Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

H2SO4/HNO3/HClFunctionalization and its effect on dispersion of carbon

nanotubes in aqueous media
A.G. Osorio *, I.C.L. Silveira, V.L. Bueno, C.P. Bergmann
Ceramics Materials Laboratory, LACER, Department of Materials, Federal University of Rio Grande do Sul, Av. Osvaldo Aranha, 99, Sala 705C, CEP 90035-190, Porto Alegre, RS, Brazil

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 28 May 2008
Received in revised form 22 July 2008
Accepted 22 July 2008
Available online xxx

Chemical functionalization is a procedure used in materials science to oxidize the surface of materials.
Several researchers use this technique to improve carbon nanotubes (CNTs) interaction and dispersion.
The present article evaluates the effect of different functionalization methodologies on dispersion of
CNTs in aqueous media. Sulfuric, nitric and chloridric acids were used on the rst functionalization. For
the second procedure tested the addition of chloridric acid was eliminated; and the third
functionalization was done using only nitric acid. Experimental results obtained by Raman spectroscopy
indicated the maintenance of the structure of CNTs after all oxidations. The presence of other structures
was proved by thermogravimetry decomposition and the addition of functional groups was conrmed by
transform Fourier infrared spectroscopy. From these experimental results, we conclude that all
methodologies used showed a percentage of adsorption of functional groups on the CNTs. However,
based on dispersion analysis in aqueous media, it is observed that this adsorption showed more efciency
on the rst functionalization method, followed by the second method.
2008 Elsevier B.V. All rights reserved.

PACS:
81.07De
82.70. y
68.43Fg
Keywords:
Carbon nanotubes
Functionalization
Dispersion in aqueous media

1. Introduction
1.1. Importance of the functionalization of carbon nanotubes
Carbon nanotubes (CNTs) have attracted several researchers
because of its remarkable structural, mechanical, electrical, and
thermal properties [13]. Nowadays, the incorporation of nanotubes into ceramic and polymeric matrices is a vast area of study
and research [37]. When a reinforcement is incorporated into a
matrix, the interface between the matrix and the reinforcement
becomes, therefore, extremely important.
Carbon nanotubes present high stability on its unique structure,
only few concentrated acids are capable of breaking the bonds
between carbon atoms. Consequently, when CNTs reinforce a
composite, this high stability becomes a shortcoming at the
interaction between the matrix and the reinforcement. Another
noticeable difculty that can interfere on CNTs from becoming
commercially applicable is its uncontrolled agglomeration due to
its nanometer size. One of the routes to increase the interaction
between matrix and reinforcement is submitting CNTs to a process

* Corresponding author. Tel.: +55 51 33083637; fax: +55 51 33083405.

E-mail addresses: alice.osorio@terra.com.br, osorio.alice@gmail.com
(A.G. Osorio).

called functionalization. Functionalization is a chemical process

that inserts functional groups on the sidewall of CNTs. The
introduction of this procedure can also be helpful to obtain better
dispersion of carbon nanomaterials into relevant matrices.
1.2. Introductory study for the functionalization of CNTs
Functionalization of CNTs is often discussed in articles
reporting dispersion and interaction of CNTs with different
materials, but it is difcult to compare data between articles
because there are several different procedures and many adaptations. In these articles, acids, temperature, time, and stirring
parameters are varied. A literature review was made to clarify the
differences and advantages on three acids that were used, as well
as its procedures.
The addition of functional groups on CNTs is commonly made
by immersing it in sulfuric acid (H2SO4) and nitric acid (HNO3) in
the range 3:1 [811]. According to these researchers, this method
inserts carboxyl groups (COOH) on the surface of nanotubes.
Some researchers [12,13] increased the temperature and/or carried
out stirring to accelerate the process of oxidation. The addition of
chloridric acid (HCl) later is another method reported by some
scientists to adsorb functional groups on the CNTs [1416].
Functionalizations using only nitric acid has also been
published [17,18]. Wang et al. [17] functionalized his material

0169-4332/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.07.144

Please cite this article in press as: A.G. Osorio, et al., H2SO4/HNO3/HClFunctionalization and its effect on dispersion of carbon
nanotubes in aqueous media, Appl. Surf. Sci. (2008), doi:10.1016/j.apsusc.2008.07.144

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by immersing it in nitric acid in ultrasound at 90 8C for 4 h.

Afterwards, he stirred the material until it reached the ambient
temperature.
Alternative acids were also studied and used to oxidize CNTs.
Xie et al. [19] used a mixture of H2SO4/HNO3 (3:1) and H2O2 to
obtain carboxyl and hydroxyl groups. The use of isolated H2O2 is
also an option to obtain carboxyl groups [17].
It is also possible to read in the literature review about using
other acids to oxidize CNTs. Choi et al. [21] used 5-phenoxyisophthalic acid, phosphorous pentoxide (P2O5), and polyphosphoric
acid (PPA) to graft functional groups onto the surface of CNTs.
Shanmugharaj et al. [22] added sulfuric acid and potassium
dichromate and placed it at 80 8C for 30 min for the adsorption of
COOH, OH, and O. In addition to the above mentioned methods,
there are still other methodologies that function as alternative
routes to functionalize CNT [23].
Despite the chemical functionalization mentioned above, there
are other techniques to oxidize the surface of CNTs. Xia et al. [18]
functionalized the CNTs using nitric acid and oxygen plasma. He
concluded that nitric acid added carboxylic and phenolic groups,
whereas the oxidation by plasma inserted a vast amount of
carbonyl groups.
1.3. Aim of the paper
Several researchers use the chemical processes mentioned
above to evaluate the dispersibility of CNTs in aqueous media
[8,10,20]. Because of the large surface area, CNTs exhibit a strong
tendency to form agglomerates. The effect of dispersion of CNTs in
aqueous media is a method that is used to qualify and compare the
efcacy of functionalization procedures.
The main goal of this article is to evaluate different procedures
of chemical functionalization of CNTs to study the differences and
efciency obtained on these functionalization methods, as well as
its effect on the dispersion of CNTs in aqueous media.
2. Experimental
2.1. Materials
Pristine CNTs were synthesized in the laboratory by catalytic
vapor deposition (CVD) using Mo/Fe as catalyst and puried with
chloridric acid in air to remove metals used as catalyst during the
synthesis. The solution with chloridric acid and CNTs was stirred at
room temperature for 1 h. Nitric, sulfuric, and chloridric acids were
purchased from Quimex, F.Maia, and Synth laboratories, respectively. Ammonium hydroxide was supplied by Synth laboratory.
2.2. Functionalization
The oxidation methodologies mentioned in fourteen articles
were analyzed, and based on this literature review [923], three
methodologies to functionalize CNTs were chosen to be tested
using acids that are described in Table 1.
In the rst procedure (CNTsnc), CNTs were immersed in a
mixture of H2SO4/HNO3 (3:1) at room temperature. After that,

CNTs were treated in an ultrasound bath for 2 h and upheld for

15 h. The chloridric acid was, then, added to the solution.
Subsequently, this solution was neutralized with ammonium
hydroxide and ltered with a 0.22 mm cellulose acetate membrane. The CNTs were washed several times using deionized water
until the pH 5.5 was reached. The second procedure (CNTsn) had
the same process; however, the addition of HCl was eliminated. For
the last functionalization (CNTn), in spite of the mixture of acids,
only HNO3 was added to the CNTs.
2.3. Characterization
Transmission electron microscopy (TEM) and Raman spectroscopy were carried out to characterize CNTs; and thermogravimetry, Fourier transformed infrared spectroscopy (FT-IR), and
dispersion analysis were carried out to characterize the efciency
of functionalization on nanotubes.
The morphology of CNTs was analyzed using TEM Jeol JEM
2010. Images were recorded with an accelerating voltage of 200 kV
by placing a drop of the samples dispersed in isopropanol on
copper grids coated with carbon. This technique certicates the
type of CNTs present in our specimens.
Four specimens were prepared for Raman spectroscopy:
pristine and functionalized CNTs (CNTsnc, CNTsn, and CNTn).
The spectrometer used was an Acton Spectral pro 500 at 632.8 nm
(HeNe laser).
Thermal studies were carried out using TGA/SDTA 851e Mettler
Toledo analyzer. The specimens were scanned within the
temperature ranging from 70 to 850 8C at a ramp rate of 5 8C/
min, under continuous air ow. This technique was carried out to
investigate the thermal stability of the nanotubes.
Four samples of KBr with 0.5% by weight of CNTs were prepared
for FT-IR spectrometer. To obtain these samples, CNTs were
mechanically mixed to the KBr powder and pressed into discs
shape. FT-IR was used to analyze the changes in the surface
chemical bonding and structure in the frequency range of 4000
400 cm 1. Spectrometer used was a PerkinElmer model Spectrum
1000.
To compare the suspension stability of the CNTs obtained,
solutions with functionalized and nonfunctionalized CNTs were
prepared. Four milligrams of CNTs were dispersed in 36 ml of
deionized water via sonication for 15 min. These solutions were
upheld for 20 days.
3. Results and discussions
3.1. Transmission electron microscopy (TEM)
Photos taken on TEM (Fig. 1) show two types of CNTs:
multiwalled nanotubes (MWNTs) and single-walled nanotubes
(SWNTs). A higher amount of MWNTs than SWNTs can be
observed. Photos also indicate that there was little damage to
the surface of CNTs after chemical treatment (CNTsn). Hence, the
presence of a different material around nanotubes can be noticed
on functionalized nanotubes.
3.2. Raman spectroscopy

Table 1
Identication of specimens of functionalized CNTs
Code

Functionalization

CNT
CNTsnc
CNTsn
CNTn

H2SO4/HNO3/HCl
H2SO4/HNO3
HNO3

Fig. 2 shows the Raman Spectrum of CNTs. Raman spectroscopy

is a technique frequently used to characterize CNTs. This technique
provides an important characterization tool for carbon-based
materials, showing different characteristic spectra for sp3, sp2, and
sp carbons, as well as for disordered sp2 carbons, fullerenes, and
CNTs [24]. In the high-frequency region of spectrum, two bands
were observed showing the characteristics of CNTs; these bands

Please cite this article in press as: A.G. Osorio, et al., H2SO4/HNO3/HClFunctionalization and its effect on dispersion of carbon
nanotubes in aqueous media, Appl. Surf. Sci. (2008), doi:10.1016/j.apsusc.2008.07.144

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Fig. 1. TEM images of (a) pristine and (b) functionalized carbon nanotubes.

point the graphite band (G band) and the disorder and defects of
the structure, named D band. The ratio between the intensity of the
D band and the G band, noted ID/G, is related to the degree of
disorder of the nanotube. An increase in ID/G value corresponds to a
higher proportion of sp3 carbon, which is generally attributed to
the presence of more structural defects [25].
In the low-frequency part of spectrum, there is a second region
characteristic of CNTs, this region is named Radial Breathing Mode
(RBM). This region at 100300 cm 1 is very visible to CNTs that
present diameter sizes lower than 3 nm [25]. Bands on RBM region
may not exist in cases when the diameter size is higher than 3 nm.
Moreover, the diameter size of CNTs can be estimated studying the
RBM region [2527].
As can be observed in Raman spectrum, the characteristic peaks
of CNTs, named the D band at 1330 cm 1 and the G band at
1580 cm 1, approximately, are identied. When oxidation of
nanotubes was performed, these characteristic peaks can still be
identied, proving that the acid treatment does not damage the
structure of CNTs. Comparing the ratio ID/G values of functionalized
and nonfunctionalized CNTs, it is observed that after functionalization, the ratio values increase as expected. The oxidation of
CNTs breaks some of its bonds and inserts chemical groups that can
be interpreted as defects on the structure. Comparing types of
functionalization, all processes show a relevant change on the
intensity of band D. These results indicate certain insertion of
defects and/or break on the structure of nanotubes.

Fig. 2. Raman spectra of CNTs.

3.3. Thermogravimetric analysis (TGA)

As shown in Fig. 3 by TGA, the oxidized CNTs started
decomposing earlier than nonoxidized CNTs. It can be attributed
to the presence of functional groups on the tubes. The weight loss
at 230 8C should be due to the decomposition of the grafted
carboxylic groups [9]. Comparing types of functionalization, it can
be noticed that functionalization CNTn started decomposing later
than the other two methodologies used to oxidize nanotubes. It can
indicate certain inefciency on the adsorption of chemical groups
on CNTs.
Results obtained on TGA analysis showed good agreement with
results of Raman spectroscopy. The indication of an early
decomposition of functionalized CNTs agrees with the increase
on ratio ID/G values for these specimens. The adsorption of
functional groups increases the number of defects in the structure
of nanotubes, increasing the ratio ID/G values and providing the
early decomposition of CNTs.
3.4. Fourier transformed infrared spectroscopy
Fig. 4 shows the FT-IR spectra of pristine and functionalized
CNTs. Infrared spectrum measures the quantity of radiation
absorbed versus its frequency. When CNTs are submitted to an
infrared radiation, the difference of charge state between carbon
atoms induce the formation of an electric dipole; the appearance of

Fig. 3. TGA thermograms obtained for CNTs.

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Fig. 4. FT-IR spectra of CNTs.

these dipoles generate signals that are detected [28]. Atoms

involved in stretch and bending vibrations usually determine the
frequencies of absorption. FT-IR is mainly used to identify the
presence or absence of functional groups. Region below 1400 cm 1
is named ngerprint region and is hardly used to identify compounds due its complexity.
The high symmetry presented on pristine CNTs generates very
weak infrared signals due to the weak difference of charge state
between carbon atoms. The weak difference of charge state leads to
very small induced electric dipole, providing a silent spectrum. The
peak related to C C bonding at approximately 1600 cm 1 is not
seen in the spectrum of pristine CNTs, this effect can be explained
by the very low formation of electric dipoles. This characteristic
peak, however, can clearly be noticed on CNTsnc and CNTsn. The
functionalization breaks the symmetry of nanotubes, which
enhances the generation of induced electric dipoles and signs as
detected.
Peaks between 2800 and 3500 cm 1 (Fig. 4) are the characteristic stretching vibrations of CH and OH bonds. These peaks can
be related to hydroxyl and carboxylic groups. The peak appearance
of CNTsnc in this region indicates that stretching OH is
preferentially from hydroxyl groups while the peak appearance
of CNTsn in the same region indicates the stretching OH from

carboxylic groups. Acid treatment also results in the appearance of

a peak approximately at 1475 cm 1, which corresponds to the CO
stretching indicating the introduction of carboxylic groups due to
surface oxidation [29]. These peaks are, however, barely noticeable
in the functionalization CNTn. Very small peaks, nevertheless,
approximately at 3500 and 1400 cm 1 can be observed indicating
some oxidation of CNTs.
Two peaks, at approximately 1100 and 620 cm 1, can be seen
on the region named ngerprint on CNTsnc and CNTsn. The
information taken from this region cannot be conrmed, unless a
second analysis is performed. A sample of CNTs was then
submitted to X-ray uorescence technique to conrm whether
the peak at 1100 cm 1 indicates a sulfonate group or a CO
vibration. The presence of sulfur was then conrmed and this peak
at 1100 cm 1 is assumed as a sulfonate group. The second peak
seen on the ngerprint region at 620 cm 1 can indicate a bending
vibration of CH bonding.
In addition, the broad shoulder band in the 28003500 cm 1
region is attributed not only to the presence of hydroxyl and
carboxylic groups but also to the traces of water in the KBr discs
that was used for the analysis, which is inaccessible to be fully
removed.
FT-IR is in good agreement with results showed on TGA and
Raman spectrometry. The presence of functional groups conrmed
with FT-IR agrees with the early decomposition of functionalized
CNTs and the higher ratio ID/G, proving the addition of functional
groups on the nanotubes.
3.5. Dispersion analysis
Figs. 5 and 6 show the dispersed states of CNTs samples in
aqueous media, at the moment of dispersion and approximately
24 h and 20 days later. When a surface suffers oxidation, chemical
elements are adsorbed, forming functional groups. These groups
are positive or negatively charged. In this case, hydroxyl and
carboxylic groups are inserted on the nanotubes surface, these
groups are equally charged. The presence of same-sized charged
particles on the surface of CNTs enables the CNTs to repel from
each other, keeping the solution dispersed. Evaluating the
sedimentation, it is possible to estimate the amount of functional
groups adsorbed on the surface of CNTs.
Results show a good dispersion of CNTs in an aqueous media,
indicating that mostly hydrocarbons same-sized charged are

Fig. 5. Dispersion in aqueous media of CNT and CNTsnc: just dispersed; 24 h and 20 days after.

Please cite this article in press as: A.G. Osorio, et al., H2SO4/HNO3/HClFunctionalization and its effect on dispersion of carbon
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Fig. 6. Dispersion in aqueous media of CNTsn and CNTn: just dispersed; 24 h and 20 days after.

inserted on the surface of nanotubes. The aqueous media does not

interfere on the reactions among CNTs.
Comparison of dispersion analysis photographs indicate that
the suspension stability of the pristine CNT and CNTn were poor as
they easily sediment. This sedimentation could be because of the
agglomeration of nanotubes and lack of hydrogen bonding.
Moreover, CNTsnc and CNTsn showed signicantly better stability.
Nevertheless, CNTsnc presented the best stability, concluding a
higher percentage of functional groups absorbed.
4. Conclusions
Chemical functionalization of the surface of CNTs was
investigated using different acid treatments, and its characterization was carried out using various characterization tools.
The results obtained by Raman spectroscopy indicated the
maintenance of the structure of CNTs after oxidation. The presence
of other structures was proved by TGA decomposition. The
addition of carboxyl and hydroxyl groups was conrmed by FT-IR.
From the experimental results obtained for different acid
treatments, it is possible to conclude that all methodologies used
showed a percentage of adsorption of functional groups on the
CNTs. However, based on dispersion analysis in aqueous media, it
is possible to conclude that this adsorption showed more efciency
on CNTsnc, followed by CNTsn.
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Please cite this article in press as: A.G. Osorio, et al., H2SO4/HNO3/HClFunctionalization and its effect on dispersion of carbon
nanotubes in aqueous media, Appl. Surf. Sci. (2008), doi:10.1016/j.apsusc.2008.07.144