Sensors and Actuators A 207 (2014) 32–38

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Sensors and Actuators A: Physical

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

Solid-based titrimetry as a straightforward method for simultaneous

detection of hydroxyl and carboxylic functional groups during
evaluation of the acidity of nanocarbons
Mohammad Mahdi Doroodmand a,b,∗ , Zahra Shafie a
a
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
b
Nanotechnology Research Center, Shiraz University, Shiraz 71454, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A novel method has been proposed based on solid-based titrimetry for detection of –COOH and –OH
Received 9 September 2013 functional groups in nanocarbons during direct evaluation of the acidity and functionality of carbon
Received in revised form 4 December 2013 nanostructures. In this technique, a known amount of carbon nanostructure is homogeneously mixed
Accepted 4 December 2013
with NaCl powder as solid media with optimized ratio (1:8, w/w). Then the mixture is put on a vibrating
Available online 14 December 2013
spatula for addition to a NaOH standard solution (0.05 M) to get two distinct end points (EPs) in the titra-
tion curve for carbon nanostructures such as multi-walled carbon nanotubes (MWCNTs). The first EP is
Keywords:
correlated to the simultaneous neutralization of –COOH and –OH with known equivalent of a standard
Solid-based titrimetry
Nanocarbons
basic solution during evaluation of the total amounts of both –COOH and –OH presented in nanocar-
Acidity bons. Whereas, the other EP is related to the reaction between added MWCNT–COOH and MWCNT–O− ,
Activation generated during the first EP. Relative standard deviation of the solid-based titrimetry for four replicate
analyses is evaluated to 3.02%. The reliability of the observed trends is finally evaluated by estimation of
the acidity of an initial standard material, followed by comparison with back-titration method.
Published by Elsevier B.V.

1. Introduction Common techniques, usually used for characterization of car-

Carbon nanotube (CNT) is considered as one of the most impor-
tant allotropes of carbon. CNTs are low in weight. They have high
strength and a high aspect ratio (long length compared to the small
diameter). Due to the intrinsic properties of CNTs, they are consid-
ered as ultimate in carbon fibers [1]. But, despite from high potential
of carbon nanostructures, CNTs have shown some severe limita-
tions regarding manipulation of the raw material in terms of high
hydrophobicity, very poor solubility, and formation of bundles due
to inter-tube van der Waals interactions [2]. Functionalization of
CNTs using either non-covalently- or covalently-based strategies
has promoted the dispersion and solubility of CNTs [2–4]. Oxidation
of either single-walled or multi-walled CNTs (SWCNTs, MWCNTs)
has attracted a huge interest within the scientific community,
which is considered as an essential step for lots of applications
[5–11]. Activation of CNTs is used for purposes such as purification
from amorphous carbon or metal catalyst [11,12], excess solubil-
ity in water [13], conjugation with biomolecules like proteins [14],
opening the ends of CNTs and filling with various nanomaterials
[15].
∗ Corresponding author. Tel.: +98 711 6137152; fax: +98 711 2286008.
E-mail address: doroodmand@shirazu.ac.ir (M.M. Doroodmand).
bon nanostructures include UV–Vis spectrometry [16], electron
microscopy [17], thermogravimetric analysis [11], X-ray photoelec-
tron spectroscopy (XPS) [16], and Raman spectrometry [9,11,17].
Besides high cost and also unavailability of these instrumenta-
tion methods, these techniques cannot differentiate the defect sites
of nanostructures. For instance, spectroscopic methods such as
infrared (IR) spectrometry approach to measure the total number
of defects sites with considerable error (∼50%) from sample to sam-
ple [16]. Therefore, a simple method such as titrimetry is needed
to characterize the carbon nanostructures.
Compared to the semi-quantitative instrumentation techniques
such as XPS and IR, various applications of carbon nanostructures
usually need accurate quantitation of the –COOH and –OH func-
tional groups [5,6]. Some of these applications include catalytic
behavior of H+ of CNTs in the synthesis of organic compounds,
evolution of the acidity of carbon nanomaterials, prediction of the
mechanism of some organic reactions, and/or quantifying the edge
planes in the CNT matrix [51–12].
To estimate the quantity of –COOH and –OH functional groups
in the oxidized CNT matrix, Boehm titration is considered as sim-
pler technique [17]. In Boehm titration, briefly known amount of a
basic solution such as NaOH, Na2 CO3 , or NaHCO3 is pipette slowly
into a vial containing oxidized CNTs. After sealing the vial, the
nanocarbons are placed in a shaking incubator for ∼24 h. Then,

0924-4247/$ – see front matter Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.sna.2013.12.009
 M.M. Doroodmand, Z. Shafie / Sensors and Actuators A 207 (2014) 32–38
Fig. 1. Instrumentation system of solid-based titrimetry.
the sample is filtered and a certain volume of the basic solution
is titrated with a standard acid solution [18–24]. This procedure
usually leads to have only one end point (EP), resulting to detect
total amounts of acidic functional groups in the oxidized CNTs.
Recently, this EP has been theoretically attributed to the solubil-
ity of atmospheric carbon dioxide and formation of HCO3 − /CO3 2−
[13]. However, detection of two EPs using Boehm titration method
has been correlated to the –COOH and phenol groups of some kinds
of carbon nanostructures that form polycyclic aromatic substrates
such as fulvic acids during the oxidation [25]. Therefore, no reliable
method is available for direct detection of each hydroxyl or car-
boxylic functional group in the CNT matrix. These challenges reveal
the importance of introduction of a reliable method to detect the
acidic functional groups in nanocarbons. For this purpose in this
work, a new method is introduced based on solid-based titrime-
try for simultaneous determination of –COOH and –OH functional
groups in nanocarbons such as CNTs.
2. Experimental
2.1. Materials
Carbon nanostructures such as MWCNTs with 99.1% purity per-
centage and 20–50 internal diameter were synthesized by catalytic
carbon vapor deposition (CCVD) process according to the proce-
dure reported in the previously reported research [26]. To activate
carbon nanostructures, ozone was generated using an ozone gener-
ating system (Ozone Services OL80). Nitric acid (63%), sulfuric acid
(96%), NaOH and sodium borohydrate (NaBH4 ) were from Merck.
Electrolytes such as NaCl, KCl, KBr, or NaBr powder were also pur-
chased from Merck in their analytical grades.
2.2. Instrumentation
The solid-based titrimetric instrumentation system is com-
posed of a Mettler AT261 Delta range balance (Mettler, Greifensee,
Switzerland) with weight capacity equal to 200 g, a resolution
of 0.001 mg over the entire range and a movable fine range
with a resolution of 0.001 mg. Detail of the instrumentation
system has been investigated in the previous research [27]. Briefly,
a Mettler LV3 vibrating spatula is fixed to the pan of the balance. The
speed and the time duration of the vibration of the spatula are also
controlled through remote radio frequency (RF) transmitter and
receiver. For this purpose, the remote-receiving circuit with weight
equal to ∼5.0 g is positioned on the vibrating spatula. This remote
receiver is then triggered and controlled through the remote trans-
mitter using an electronic circuit. Fig. 1 shows the schematic of the
33
instrumentation system. A “Lutron” pH meter is also adopted to
record the pH values. All parts of the system including the electronic
circuit, pH meter and microbalance are managed by a program
written in Visual Basic 6 through Rs-232 port.
2.3. General procedure
To activate carbon nanostructures, ∼1.0 g of each carbon nano-
material such as MWCNT was treated with 50 ml of sulfuric/nitric
acid (3:1, V/V) and refluxed at ∼90 ◦ C for ∼8 h. After acid treat-
ment, the mixtures were left to cool down to the room temperature.
Also, after filtration of carbon nanostructures using a 0.2 ␮m
polytetrafluoroethylene (PTFE) membrane, each CNT sample was
sequentially washed with basic solution (0.05 M) for several times
for separation from any probably formed poly aromatic groups.
Activated CNTs were finally washed with ether and dried with
sunlight.
Oxidized nanotubes were also prepared by dispersing purified
CNTs in dimethylformamide (DMF) media to form suspension equal
to ∼3.25 g l−1 [28]. For this purpose, briefly the suspended car-
bon nanostructure was homogenized by sonication for ∼30 min to
achieve a good suspension before introducing ozone (O3 ). Ozone
was generated by passing an O2 stream through an ozone genera-
tor to generate an approximate ozone concentration of ∼4000 parts
per million. The O3 was then bubbled into the carbon nanomate-
rial suspension in a sealed three-neck flask for more than 2 h to
avoid from any selective etching [21] and also to minimize the for-
mation of any hazardous ozonide intermediates. After ozonolysis,
the system was suspended into a solution containing 0.01 M NaBH4 .
Then, the mixture was left to settle for 30–60 min and then filtrated
through a 0.2-␮m PTFE membrane. Finally the functionalized CNTs
were sequentially washed with a basic solution (0.05 M) for sev-
eral times. The ozonized CNTs were finally washed with ether for
several times under vacuum condition at temperature to ∼80 ◦ C for
12 h.
To dilute the activated carbon nanostructures, each CNT sam-
ple was individually mixed with various kinds to the electrolytes
(media) such as NaCl, KCl, KBr, or NaBr powder with weight ratio
equal to 1:8 (w/w). Afterward, the mixture was homogenized using
a pounder, followed by sonication for several minutes inside a
sonication bath (model: CD4820) at 500 kHz frequency. Then, the
mixture was put on the vibrating spatula for addition to a standard
solution of NaOH (0.05 M) through the solid-based titrimetry.
3. Results and discussion
To control the purity, solubility, defect and also the morphology
of carbon nanomaterials for a special applicable purpose, oxida-
tion process with oxidants such as strong acids, oxygen or O3
creates functional groups, resulting to severe degradation of the
originally desirable properties of CNTs [5–11]. Treatment of CNTs
with strong acid usually breaks down the carbon–carbon bonds
and provides –COOH and –OH functional groups [29]. Also, O3
as a strong oxidizing agent with high standard reduction poten-
tial (Eo = 2.07 V vs. standard hydrogen electrode, SHE) cleavages
carbon–carbon bonds for selective formation of –OH functional
groups [29,30]. Consequently, these processes lead to have vari-
ous defects for nanocarbons during oxidation [29,30]. In this study,
physical defects at the center’s walls of the synthesized MWCNTs
were also evaluated by transmission electron microscopy (TEM) as
shown in Fig. 2. Compared to the TEM image of untreated MWCNT
(Fig. 2A) and that treated by O3 (Fig. 2B), bending walls are clearly
observed during acid treatment (Fig. 2C).
The effects of activation process on the morphology of car-
bon nanostructures are also evidenced with spectroscopic methods
34 M.M. Doroodmand, Z. Shafie / Sensors and Actuators A 207 (2014) 32–38
Fig. 2. TEM images of (A) raw MWCNT and that treated with (B) acid and (C) ozone.
Fig. 3. Raman spectra of (A) untreated MWCNT and that treated with (B) ozone and
(C) acid.
such as Raman and fourier transform-infrared spectrometry (FT-
IR). Defect of MWCNTs are also estimated based on the ratio of
G-band at ∼1580 cm−1 and D-band at ∼1350 cm−1 of the Raman
spectrum. As shown (Fig. 3), untreated MWCNTs (Fig. 3A) and O3 -
treated MWCNTs (Fig. 3B) demonstrate significantly lower G- to D-
band ratio (∼0.982 and 1.12, respectively) in comparison with that
evaluated for acid (4.27, Fig. 3C). This phenomenon points to the
strong dependency of the structure of nanocarbons to the activation
process.
Fig. 4 also shows the FT-IR spectra of MWCNTs treated with
ozone and acid. As clearly is shown according to the FT-IR spectra
(Fig. 4), strong peak positioned at 3448 cm−1 is related to the for-
mation of OH functional groups for both hydroxyl and carboxylic
functional groups (Fig. 4A and B). Moreover, formation of carbonyl
group (C=O) is evidenced based on the absorption peak situated at
∼1600 cm−1 [18–21]. Also, peaks situated at 1380, 1460, 1750 and
3500 cm−1 correspond to C–O, C=C, C=O, O–H bonds, observed after
carbon nanomaterials were treated with acid or O3 [18–21]. Major
reduction in the intensity of the absorption peaks at ∼1600 cm−1
clearly reveals the specificity of advanced ozonation for formation
Table 1
Comparison between the proposed method and other titrametric methodsa .
Analytical technique NOH (mmol g−1 ) NCOOH (mmol g−1 )
Solid-based titration 0.4096 0.2154
Back-titration – –
Boehm titrationc – –
a
Data are the average of 4 replicate analyses.
b
Vs. Back-titration as reference method.
c
Titrated according to the procedure reported in [10].
Fig. 4. FT-IR spectra of (A) untreated MWCNTs and MWCNTs treated with (B) ozone,
and acid for (C) ∼9 h and (D) 24 h.
of –OH (Fig. 4A). Whereas, significant enhancement in the peak
absorption of C=O points to the effective role of acid treatment and
reflux time in the activation of carbon nanostructures and forma-
tion of –COOH functional groups (Fig. 4B and C). These significant
differences strongly expose the necessity of a reliable method for
detection of active cite such as carboxylic acids and hydroxyl func-
tional groups.
Titration (titrimetry) is a common laboratory method of quan-
titative analysis that is used to determine the concentration of an
identified analyte. This method often leads to just one equivalent
point [20]. But, in spite of the simplicity of titrimetry, the applica-
tion of this technique is still limited due to insolubility of materials,
the dilution error and also long time needed for sample analysis. For
instance in this study, direct Boehm titration on activated MWCNTs
leaded to evaluate unacceptable value for relative standard devi-
ation (RSD, 25.42%, for n = 4) and a large relative error percentage
(123.24%) vs. a reference technique such as back-titration method
(Table 1).
NTotal (mmol g−1 ) RSD (%, n = 4) Relative errorb (%)
0.625 3.02 10.03
0.568 10.36 0.0
1.2680 25.4180 123.24
 M.M. Doroodmand, Z. Shafie / Sensors and Actuators A 207 (2014) 32–38 35

Fig. 6. Titration curves showing the effect of different concentrations of NaOH solu-
tion.
Fig. 5. Titration curves of KHP powder with 0.05 M NaOH solution.

But, the use of solid reagents would eliminate problems such As this titration is based on the direct reaction between activated
as dilution effects and requires only a balance, which is standard carbon nanostructures as an acidic analyte and a base as titrant,
equipment in every laboratory. In addition, the technique offers therefore to have sharp EP, it is necessary to select a strong base
the possibility of employing substances that are so unstable in as standard solution. In this study, NaOH solution was adopted as
solution. Compared to the volumetric titration, general solid-based standard media. To optimize the concentration of the base, 3.0 ml of
titrimetry has various advantageous such as (a) freedom from vol- NaOH solution with different concentrations ranging from 0.005 to
ume changes during reaction of titrant with analyte, (b) solvent 0.075 M was individually selected and treated with MWCNTs/NaCl
free technique, (c) simple matrix of titrant, and (d) high accuracy (weight ratio: 1:6,w/w) as shown in Fig. 6. As clearly shown, two
and precision [31]. Therefore, proposal of selective methods based independent EPs with acceptable sharpness were observed. In this
on solid-based titrimetry seems to be considered as reliable and study, to consume fewer amounts of MWCNTs as well as to have
applicable analytical technique for direct detection of carboxylic maximum sharpness for the titration curves, 0.05 M–NaOH was
and hydroxyl functional groups, during evaluation of the acidity as selected as optimum concentration.
well as the functionality of nanocarbons. Due to the lack of any control in the homogeneous addition
of nanocarbons to the basic standard solution, therefore another
parameter having important effect on the sharpness of the titration
3.1. Analytical figures of merits
curve is the selection of a suitable reagent with maximum solubil-
ity. This reagent is considered as dilutent that is homogeneously
To evaluate the reliability of the solid-based titrimetry for deter-
mixed with MWCNTs to control the amounts of analyte directly
mination of the acidity of CNTs, the response of the system was
added to the standard basic solution. For this purpose, different
tested using an initial standard material such as potassium hydro-
electrolytes such as KCl, NaCl, NaBr, and KBr powders were indi-
gen phthalate (KHP). For this purpose, KHP powder as solid reagent
vidually mixed with MWCNTs (weight ratio: 1:8, w/w) and titrated
was initially mixed and homogenized with NaCl powder with 1:9
with the strong base according to the titration curves shown in
weight ratio, followed by putting on the vibrating spatula for addi-
Fig. 7. Based on the titration curves (Fig. 7), the RSD% for differ-
tion to the bucker containing known amount of a strong base i.e.
ent kinds of electrolytes was evaluated to 3.02%. The same value
3.0 ml of NaOH standard solution (0.05 M).
was also estimated during at least five replicate titrations of acti-
As shown based on the titration curve (Fig. 5), one EP was
vated MWCNTs/NaCl powder (weight ratio: 1:6, w/w). As clearly
observed after addition of 0.23 ± 0.01 mg of NaCl/KHP powder, dur-
shown (Fig. 7), no significant change was observed in the sharp-
ing the neutrization of the carboxylic acid of KHP with NaOH.
ness as well as the situation of the EPs when using different kinds
The RSD of the solid-based titrimetry for at least five repli-
of salts. This points to the lack of effective influence of the type
cate analyses was evaluated to 5.05%. This value, in comparison
of electrolyte, mixed with carbon nanomaterials. Therefore in this
with other analytical methods such as IR spectrometry [16] reveals
work, NaCl powder was selected as a suitable diluent for mixing
more reproducibility and higher precision of the proposed classi-
with MWCNTs.
cal method for direct determination of the acidity of solid reagents.
As in solid-based titrimetry, the equivalent of carbon nanoma-
Also, based on the relative error percentage calculated using the
terials added into the basic solution is determined; therefore the
result of the solid-state titrimetry during titration of KHP, respect to
homogeneity of nanocarbons and NaCl powder is very important.
that evaluated by back-titration method as an acceptable method,
To reach this purpose, mixture of MWCNTs and NaCl powder should
the accuracy of this technique was calculated to only 3.43%, which
again is not comparable with the error percentage (∼50%), esti-
mated by other analytical techniques such as IR spectrometry [16].
For detection of the acidity of nanocarbons, MWCNT was
selected as active nanomaterial. For this purpose, the activated
MWCNTs were initially washed with basic solution for several
times to remove any probably formed poly aromatic groups during
the oxidation process according to the procedure reported in Ref.
[10]. Parameters having effective influence on the accuracy as well
as the precision of the proposed method for direct detection of the
–OH and –COOH functional groups in the carbon nanostructure’s
matrix are: kind and ratio of the electrolyte, the equivalent of base
inside the bucker, the delivery rate (the speed of the vibration of
the vibrating spatula) and the rate of introduction of the solid-based Fig. 7. Titration curves representing the effect of different kinds of electrolytes
material as solid analyte. mixed with MWCNTs in titration with 0.05 M NaOH.
36 M.M. Doroodmand, Z. Shafie / Sensors and Actuators A 207 (2014) 32–38
Fig. 8. Titration curves revealing the effect of the different ratios of MWCNT/NaCl
in titration with 0.05 M NaOH.
be homogenized by mixing inside a pestle and subsequently son-
ication for several minutes inside a soniaction bath at frequency to
500 kHz.
However the size of aggregated CNTs reaches up to ∼150 nm
according to the TEM image (Fig. 2A), but aggregation of CNTs
does not cause any significant deviations in the results. This is
due to (i) mechanical sonication of CNTs in the vibrating spatula
with frequency of ∼450 kHz, (ii) stirring nanocarbons inside the
basic solution and (iii) high ionic strength of the basic solution that
separates the CNTs during adsorption process. But owing to the
significant difference between the morphologies of CNTs and NaCl
powder as two-dimensional and spherical (zero dimensional) mor-
phologies, respectively, mixtures of CNT/NaCl are separated inside
the vibrating spatula during mechanical sonication. For this pur-
pose, it is recommended to use NaCl particles as small as possible.
Based on the results, significant deviation (∼12.24%) was evaluated
between MWCNT, diluted with salts with particle size higher than
∼200 ␮m in comparison with that (∼3.21%) diluted with particles
lower than ∼10 ␮m.
To evaluate the degree of the dilution of MWCNTs, different
ratios of MWCNTs to NaCl powder including 1:5, 1:6, 1:7, 1:8,
1:9 and 1:10 (w/w) were individually selected and titrated with
0.05 M NaOH. As exhibited based on the titration curves (Fig. 8),
distinct EPs were observed from ratio equal to 1:6. Observation of
two distinct EPs at this condition is correlated to the time interrupt
between the introductions of nanocarbons that provides enough
time for complete interaction of nanocarbons with the basic solu-
tion. But, as time is considered as another important factor in
titrimetry, therefore minimum acceptable ratio of MWCNT to the
NaCl powder, i.e. 1:8 (w/w), was considered as optimum value for
having the sharpest titration curve. At this condition, the time dura-
tion needed to complete this titration is estimated to maximum
∼30 min.
3.2. Proposed mechanism
As clearly observed based on the titration curves (Figs. 6–8), two
distinct EPs were observed, when MWCNTs were directly reacted
with a standard basic solution. To interpret the behavior of carbon
nanostructures, some analytical evidences are considered in detail.
- Since in this experiment, weak acids such as hydroxyl or car-
boxylic acid are reacted with high concentration of a strong
base such as NaOH, therefore it is obvious that, NaOH does not
differentiate weak acids such as –COOH or –OH. Consequently
according to the mass balance equation, whole amount of –COOH
and –OH is in equivalent with total mole of NaOH. In addition, the
acidic pH (∼6.5) at the end of this calibration curve clearly points
to complete consumption of the basic standard solution before
considering the reaction related to the second EP. This process
Fig. 9. Titration curves related to the interaction between MWCNTs/NaCl pow-
der (1:8, w/w) with (A) water as blank solution and (B) suspension of
CNT–COO− /CNT–O− .
was also confirmed based on the observation of only one EP when
spiking known amount of KHP to the oxidized MWCNTs.
- At the second EP, added carbon nanostructures react with the
MWCNT–O− , produced at the first EP. For more confidence about
this idea, a known amount of activated MWCNTs (∼0.02 g) was
initially refluxed inside a basic solution with 0.05 M concentra-
tion for ∼3 h, at temperature to ∼90 ◦ C to provide CNT–COO− and
CNT–O− . After washing the MWCNTs with distilled water for sev-
eral times, the base-treated MWCNTs were suspended into 3.0 ml
of distilled water and sonicated for 10 min at 100 MHz frequency
to provide MWCNT–O− . Afterward, the MWCNT–O− containing
suspension was titrated with the MWCNTs/NaCl powder. Based
on the titration curve (Fig. 9), only one sharp EP was observed
at pH equal to ∼4.2 during the interaction between activated
MWCNTs and CNT–COO−/CNT–O− .
Moreover, significant decrease was observed in the amount
of MWCNTs needed for complete reaction with the suspension,
in comparison with that evaluated based on Figs. 7 and 8. This
event simply approves the interactions between activated MWC-
NTs and the CNT–O− , generated at the first part of the titration
curve. This phenomenon also points to the significant difference
between pKa values of MWCNT–COOH and MWCNT–OH.-Attention
to the pH values clearly reveals strong dependency of the first EP
to the reaction between NaOH and –COOH/–OH functional groups,
presented in the MWCNT matrix.-Solid-based titration between
ozone-oxidized MWCNTs (MWCNT–OH) and 0.05 M NaOH majored
to the observation of only one EP (Fig. 10) that corresponds to
the second EP of the curve shown in Fig. 8 at pH ∼4. The reac-
tion related to this EP is simply correlated to the proposed reaction
between MWCNT–COOH and MWCNT–O− as the latter produced
reagent during the first EP. According to the mentioned evidences,
the first and second EPs are proposed according to Eqs. (1) and (2),
respectively. As clearly shown according to Eqs. (1) and (2), the
limit of mass of the nanocarbons as well as the time duration for
having complete reaction with the base solution are correlated to
Fig. 10. Titration curve of ozonized MWCNTs with 0.5 ml of 0.05 M NaOH solution.
 M.M. Doroodmand, Z. Shafie / Sensors and Actuators A 207 (2014) 32–38 37

Table 2
Evolution of the reliability of proposed method for determination of COOH and OH functional groups in MWCNTs.a

Mixture of MWCNT samples b

NOH (mmol g−1 ) b
NCOOH (mmol g−1 ) Tolerance ratio of OH:COOH (w/w) NTotal (mmol g−1 ) Absolute errorc (%)
b
Expected value Detected value

Sample 1 0.409 0.215 1:3 1.054 1.081 −2.7

3:1 1.442 1.407 3.5
Sample 2 0.319 0.164 1:5 1.139 1.116 2.3
5:1 1.759 1.791 −3.2
a
The reliability of the prosed methods was also confirmed via comparison between the quantity of a mixture of two MWCNT samples with different ratio.
b
Evaluated according to the proposed procedure for solid-based titrametry.
c
Absolute error was defined as (the difference between expected and detected values) × 100.

the quantity of –OH and –COOH functional groups presented in the
CNT matrix, which are variable depending on the temperature, time
duration and kind of activation process.
CNT − COOH + OH− CNT − OH−  CNT − COO− + CNT − O−
CNT − COOH + CNT − O−  CNT − COO− + CNT − OH
3.3. Detection of –COOH and –OH in carbon nanostructures
Eq. (3) is simply governed for –COOH and –OH detection, dur-
ing considering NOH and NCOOH as number of mmol of each –OH
and –COOH functional groups per one gram of activated nanocar-
bons (mmol g−1 ). In these equations, W1 and W2 are the weights of
consumed MWCNTs in the first and second EPs, respectively. These
equations are finally adopted for estimation of NOH and NCOOH of
an activated MWCNT, as shown in Table 1. No significant change
is also evaluated during comparison between the quantities of a
mixture of two MWCNT samples with different ratio, each with
known quantity of –COOH and –OH functional groups that were
previously standardized by the solid-based titration method. The
results are shown in Table 2. These results are therefore consid-
ered as another proof for the reliability of the proposed interactions
(Eqs. (1) and (2)) between oxidized MWCNTs and basic standard
solution. Based on comparison with methods such as back-titration
and direct Boehm, good correlation is also observed between total
amount (sum) of NOH and NCOOH and that estimated by back-
titration method.
NTotal = NCOOH + NOH
W 
1
NCOOH = NTotal ×
W2
  W 
1
NOH = NTotal × 1−
W2
Fig. 11. Theoretical titration curve of activated MWCNTs titrated with 0.05 M NaOH.
3.4. Modeling
In this experiment, the accuracy of the proposed mechanism
for detection of the acidity of nanocarbons was also approved
(1) by theoretical evaluation of the behavior of the proposed reac-
tion at the first EP according to the mass balance equations as
shown in Fig. 11. Based on the theoretical calculations on the mass
(2) and charge balance equations, the equivalent of the strong base
is the same as total no of –COOH and –OH. Observation of good
correlations between the experimental results (Table 1) and the
theoretical data (Fig. 11) again reveals the accuracy and reliability
of the proposed mechanism for detection of the acidity of nanocar-
bons.
4. Conclusions
In this study, a simple, fast, non-destructive and accurate
method is proposed based on solid-based titrimetry for detection
of –COOH and –OH functional groups in nanocarbons. To the best
of our knowledge, this is the first report that directly detects the
amount of –COOH and –OH functional groups in carbon nanostruc-
tures. The detection of oxygen-containing functional groups such
as carboxyl and hydroxyl groups on the CNT’s surface is essential
feature, which seems to be attractive for many branches of science
such as medicine, biosensors or polymer composites.
Acknowledgment
The authors wish to acknowledge the support of this work by
the Shiraz University Research Council.
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