Chemically Modified Multi-Walled Carbon Nanotubes (MWCNTS) With Anchored Acidic Groups
Chemically Modified Multi-Walled Carbon Nanotubes (MWCNTS) With Anchored Acidic Groups
Chemically Modified Multi-Walled Carbon Nanotubes (MWCNTS) With Anchored Acidic Groups
ABSTRACT
Surface functionalization of multi-walled carbon nanotubes (MWCNTs) was carried out using a gas phase treatment
in a Universal Temperature Program (UTP) reactor by flowing SO3 gas onto the CNTs while being heated at different
temperatures. The functionalized nanotubes were characterized using X-ray Fluorescence (XRF), Fourier Transform
Infrared Spectroscopy (FT-IR) and Raman spectroscopy. The amount of oxyen and sulfur containing groups was determined
by acid-base titration. The titration results were in good agreement with elemental analysis using x-ray fluorescence. FTIR
analysis showed the presence of oxygen and sulfur containing groups, S=O, C-S, C=O and -COOH. Raman spectroscopy
confirmed that oxygen and sulfur containing acidic groups covalently attached to the sidewall of the MWCNTs.
abstrak
Fungsionalisasi permukaan nanotiub karbon multi-berdinding (MWCNTs) dilakukan dengan menggunakan rawatan
fasa gas dalam reaktor Universal Temperature Program (UTP) dengan mengalirkan gas SO3 ke dalam MWCNT sambil
dipanaskan pada suhu yang berbeza. Nanotiub karbon yang difungsikan dianalisis menggunakan pendaflour sinar-X
(XRF), spektroskopi inframerah penjelmaan fourier (FT-IR) dan spektroskopi Raman. Jumlah oksigen dan kumpulan
yang mengandungi sulfur ditentukan dengan titrasi asid-alkali. Keputusan titrasi berkesesuaian dengan analisis unsur
menggunakan XRF. Analisis FTIR menunjukkan adanya oksigen dan kumpulan yang mengandungi sulfur, S=O, C-S, C =
O dan-COOH. Spektroskopi Raman mengesahkan bahawa oksigen dan sulfur adalah kumpulan asid yang diikat secara
kovalen pada dinding permukaan MWCNTs.
Introduction
the nanotubes structure is prevalent, the sidewalls are also
In recent years, a great deal of attention has been focused under strain and are attacked under prolonged oxidation
onto the application of carbon nanotubes as adsorbents which leads a dramatic increase in the amount of sp3
to remove toxic and harmful substances from wastewater carbon possessing phenol, lactone, quinine, carboxyl and
and air. The large specific surface areas, as well as the high other groups. Based on these oxygen-containing functions,
chemical and thermal stabilities, make carbon nanotubes an the subsequent organic or inorganic modification on the
attractive adsorbent for heavy metals. However, due to its CNTs surface has been reported, which demonstrated an
low dispersibility in aqueous systems caused by high Van improvement in the solubility of CNTs (Wang et al. 2009b).
der Waals forces among tubes, CNTs tend to agglomerate It is also important to develop adsorbent material that can
and form bundles in composites instead of individual tubes perform the function via two mechanisms simultaneously
(Ma et al. 2008; Zhang et al. 2007). Therefore, chemical which are chemisorptions and physisorption. Physisorption
modifications of CNTs surfaces have been a key research is the interaction when an atom or molecule is bound to
area due to their hydrophobicity properties in aqueous the surface of a solid by van der Waals forces. On the
systems. Surface functionalization can effectively improve other hand, chemisorption involves stronger forces and
the dispersibility and reactivity of the CNTs for application forms chemical bonds that involve the transfer or sharing
in aqueous systems. Nitric acid is one of the most of electrons. This occurs when an atom or molecule is
frequently used agents in the oxidation of CNTs. Initially, bound to a surface through overlapping of one or more of
oxidation begins at the tubes ends, where the distribution its electron orbitals (Clark 1974).
of pentagons entails greatest lattice strain, leading to tip In this study, we investigated the optimum
opened CNTs (Wang et al. 2009a). As a high curvature in conditions needed to functionalize MWCNTs with high
604
amounts of acidic sides while achieving a porous Characterization of the modified CNTs
material with high surface area. The aim of modification Surface acidic determination. The amount of acidic
is to introduce oxygen and sulfur containing functional sites in the treated MWCNTs was determined by direct
groups as well as to increase its dispersibility in aqueous titration with 0.01 M NaOH solution. A weighed amount
environment. of treated Baytubes (0.1 g) was transferred into 100 mL
Erlenmeyer flask. Fifty milimeter of the solution of 10-3
EXPERIMENTAL METHOD M KCl was added into the flask. The flask was shaken at
400 rpm for 24 hours under vigorous magnetic stringing
to ensure equilibrium was reached. The solution was
Materials then directly titrated with 0.01 M NaOH solution. The
MWCNTs prepared by catalytic chemical vapor deposition titration was carried out using Mettler DL25 Autotitrator.
(CCVD) process were supplied by Bayer MaterialScience This equipment is equipped with titrator DL25, automatic
AG, Germany. The CNTs have a purity >95% and the burette 20 mL, stirrer and was connected to a computer,
diameter of tubes averages 13 – 16 nm with outer mean which controlled the equilibrium condition and titrant
diameter about 13 nm, inner mean diameter about 4 nm delivery. The dynamic dosing of the titrant in increments
and length of > 1µm according to the supplier. of 0.1 mL to the suspension samples and the pH of the
solution was measured every 10 second.
Modification of CNTs
In this study, functionalization process was carried out by Elemental and structural characterization
gas phase treatment in a Universal Temperature Program The structural defects of MWCNTs were investigated
(UTP) reactor by flowing SO3 gas onto the CNTs while being using Raman Spectroscopy, respectively. The Raman
heated to different end temperatures, see Table 1. The spectrograph used in this study was HORIBA Jobin Yvon
gas phase reaction was carried out in a horizontal quartz spectrometer and the light source used was 632.8 nm with
tube reactor heated by a UTP reactor. A weighed sample 10x objective. The extent of sulfonation of the MWCNTs
of CNTs (~3 g) was placed in the horizontal quartz tube was determined using X-ray Fluorescent (XRF) of Bruker
reactor fitted with gas inlet and the outlet was connected P4 engine. The surface functional groups of sulfonated
to trapping system. A multi-neck flask containing 20% SO3 CNTs was determined using a Fourier Transforms Infrared
in concentrated H2SO4 fitted with gas inlet/outlet tubes was Spectroscopy (FT-IR). The IR spectra of the functionalized
connected to reactor tubes. Argon stream was used to carry samples were recorded using a Perkim Elmer Spectrum 100
SO3 vapor into the quartz tubes. series equipped with Universal ATR sampler accessories.
The scanning range of the experiment was 600 – 2500 cm-1
and during the test, the number of scanning with the air as
background is kept constant.
RESULTS AND DISCUSSION number of acidic sites in the samples. As shown in Table 1,
the first acid dissociation constant (pKa1) of B6, B7 and B8
Surface Acidity have values of 3.34, 3.50 and 4.02, respectively which can
be assigned to dicarboxylic a acid group which is one of
The results presented in Figure 1 and Table 1 show the carboxylic members. These pKa values were in very good
titration profile of the functionalized samples. The profile agreement with values reported by Murakami et al. (2003),
of the titration curves for samples B7 and B8 are almost where the acid dissociation constant of dicarboxylic acid
similar. The B6 sample, which was treated at 100oC, was about 3.8 which were assigned as carboxyl groups. The
clearly contains two distinctive peaks that were detected first and second acid dissociation constants of dicarboxylic
in NaOH filtrate. This implies the presence of two types acid are 1.7 – 4.5 and 4.1 – 5.8, respectively (Murakami
of functional groups. In contrast, B7 and B8 (treated at et al. 2003). The B6 sample showed the second acid
200 and 300oC, respectively) show two peaks that cannot dissociation constant (pKa2) value of 5.98 which might
be resolved well, possibly due to degree of oxidation at be related to high numbers of lactone groups. The second
high temperature which generates molecular oxidation acid dissociation constant (pKa2) of 7.0 for B7 and 7.1
debris on the carbon surfaces. The oxidative treatment of for B8 can be assigned as phenolic and lactone groups,
CNTs leads to erosion of their structure (Figure 4). It was
respectively. The results show acidic sites created with
observed that as the shortening and thinning of the CNT different acid dissociation constants (Ka) values. The
layer occurs, carbonaceous debris was produced (Wang magnitudes of the Ka and pKa values of different acid give
et al. 2009). From the first derivative order of the titration the comparison of their relative strength.
profile, the two indistinctive peaks can also be assumed to As reported by Barkauskas and Dervinyte (2004), the
be due to the presence of two different functional groups surface functional groups were divided into carboxyl (pKa
on the surfaces of the samples. The equivalent point was = 2.0- 4.0), lactone (pKa = 4.0 – 7.0) and phenol (pKa
reached when the moles of base added equals the moles of =7.0 – 10.0). The acidic sites with pKa < 8 corresponded
acid in the samples. This point can be use to determine the
to carboxylic or lactone and acidic sites with pKa > 8 of phenol which usually adsorbs strongly in the range
corresponded to phenolic groups (Puziy et al. 2001). of 3650 – 3584 cm-1 region (Nyouist 2001). This is in
They also reported that the acidic sites with pKa value contrast with the intermolecular hydrogen bonded OH:OH
around 3.5 – 3.9 can be assigned to carboxylic groups, the frequency which occurs at lower frequency 3200 – 3400
groups with pKa value around 7.7 – 8.0 can be connected cm-1 (Naseh et al. 2009; Nyouist 2001). The broad weak
to phenolic groups and the groups with pKa around 5.3 – line at 3175 and 3365 cm-1 might be due to the presence
5.9 can be assigned to hydroxyl groups. From the results, of intermolecular hydrogen bonding. The B7, B8 and B6
the samples treated at 200oC (B7) showed the lowest pka1 showed strong, medium and weak transmittance band at
and highest pka2 values as compared to B6 and B8 which 2353 cm-1. This indicated the presence of CO and CO2
been treated at 100 and 300oC. This might be due to the groups. Apparently, a CO and CO2 group originally exhibit
high degree of oxidation which created high amount of the spectrum in the range of 2100 to 2400 cm-1 (Owens &
carboxylic functional group on the carbon surfaces and the Poole 2008). The IR spectrum of B7 showed a strong peak
high value of pka2 results from a small amount of phenolic at 1702 cm-1 while B6 and B8 showed a weak and medium
group which was created on the surfaces. Thus, stronger peak, respectively. This line spectrum was assigned to the
acidic groups need higher volume of NaOH to neutralize C=O stretching mode of the –COOH groups (Naseh et al.
the surfaces. Since, the B7 sample consume higher volume 2009). The strong transmittance band observed from the B7
of NaOH for neutralization, the amount of acidic sites sample might be due to the strong oxidation by SO3 vapour
were significantly higher than other treated samples of that created more carboxylic groups on the carbon surfaces
6.05 × 10-4 mol g-1. The amount of acidic sites for the B6 at treatment temperature of 200oC. In contrast, the weak
sample was 4.36 × 10-4 mol g-1. This is lower than B7 due peak was observed for the B6 sample. This is possibly
to the low treatment temperature, implying less number of due to the low number of carboxylic group created on the
functional groups created on the surfaces. Samples treated sidewall of functionalized sample that was treated at 100oC.
at higher temperature of 300oC showed lower number of At low temperature of acid treatment, the low degree of
acidic site created on the carbon surface. acid dissociation created low number of acidic sites on
the surface of functionalized samples. It was reported that
Functional group Identification refluxing or sonicating CNTs in nitric acid and another
strong oxidant such as sulfuric acid opens the ends of the
Attenuated Total Reflectance Infrared (ATR-IR) spectroscopy CNTs and introduces carboxylic groups at the open ends
was carried out to identify the functional groups present and at defect sites on the CNTs. Meanwhile, the medium
on the sidewall of the functionalized samples. The IR peak observed for B8 might be due to the decomposition
transmittance bands of all functionalized samples are of carboxylic group at higher temperature of 300oC. It
shown in Figure 2. Samples treated at 200oC (B7) and is well documented that the carboxylic acids groups are
100 oC (B6), 300 oC (B8) showed medium and weak least stable and typically decompose at temperatures
line at 3720 and 3785 cm-1, respectively. This indicated below 600oC (Tessonnier et al. 2009). Generally, it is well
the presence of unbound or free hydroxyl group (–OH)
known that the carboxylic groups with strong acidity have impurities present in the MWCNTs samples. The second
tendency to appear at lower wavenumbers (Murakami et al. feature with a frequency range from 1550 to 1600 cm-1 is
2003). The peak at 1540 cm-1 refers to the C=C stretching referred to as the graphite (G) band. In graphite, the G band
mode which originates from the backbone of carbon exhibits a single peak at 1582 cm-1 related to tangential
nanotubes. A similar feature of transmittance band was mode vibration of the carbon atoms (Haris 2009). The
reported by Naseh et al. (2009) and Yu et al. (2008). The degree of functionalization was quantified using the D to
sample that has been treated at 200oC, B7, showed a strong G band intensity ratio (ID/IG) ratio which is the intensity
line at 1125 cm-1 indicating SO2OH groups representing of the disorder mode at 1360 cm-1 divided by the intensity
the SO2 symmetric stretching mode. This line probably of graphite mode at 1600 cm-1. In this study, the ID/IG
results from the formation of sulfonate groups on carbon ratio (Table 3) values is 1.51, 1.59 and 1.53 for sample
surfaces (Silverstein & Bassler 1991). There was almost B6, B7 and B8, respectively. The B7 showed the highest
no transmittance band at 1125 cm-1 for samples B6 and of ID/IG ratio values of 1.59 as compared to B6 and B8
B8. This might be due the low number of acidic site and samples. Generally, an increase in the ID/IG ratio indicates
sulphur molecules created on the functionalized carbon an increase in the number of defects on the sidewall of the
surfaces. The weak transmittance band at 1110 cm -1 MWCNTs (Jeong et al. 2010).
detected by B7 is C-O stretching mode possibly due to It is also interesting to note that the band
the presence of phenol group (Serp & Figueiredo 2009). frequency for all samples showed noticeable shifts in
This result is consistent with the pKa value obtained from certain characteristic vibrational modes. All functionalized
titration method. Samples also showed a peak at 860 cm-1 samples showed the shifted D and G band frequency of
which can be assigned to S-O-C stretching groups. In low upshift and downshift about 1 to 3 cm-1. The B6 and B8
frequency range, the peak at 770 cm-1 and 695 cm-1 were had almost the same D band frequency about 1327.94
related to C-S stretching mode suggesting the existence of and 1327.15 cm-1, respectively. The D band frequency
sulfonic acid groups. The C–S group is less polar than the for B7 is 1328.74 cm-1. The sample B7 showed slight
C–O group and has a considerably weaker bond. Therefore, upshift of D band frequency as compared to B6 and B8.
the band is not intense and reduced at lower frequencies. The shifting of the D band frequency might be due to the
In fact the stretching vibration assigned to C-S linkage chemical charge transfer of the functionalized samples at
occur in the region of 700 – 600 cm-1 (Silverstein & Bassler different temperature treatment (Dresselhaus et al. 2004).
1991). The introduction of bulky sulfur-containing functional
groups on the surface of CNTs induces the strains on the
Raman spectroscopy nanotubes walls and thereby results in the shifting of the
peaks. This explains why the B7 was shifted than the other
Raman spectra of the functionalized samples and the two samples. These results are also in good agreement with
quantitative results are summarized in Figure 3 and Table the XRF and titration data where B7 has the highest acidic
1. Raman spectra of functionalization samples contain functional group and sulfur molecule content. In addition,
two domains in the range of 1000 – 2000 cm-1. The first the G band frequency for all samples also shows the same
one located at ~1340 cm-1 is denoted as D band, as it is features of upshifting and downshifting of peaks.
related to scattering from defects and amorphous carbon
FIGURE 4. The TEM images of MWCNT sample (a) raw MWCNTs (b) purified MWCNTs shows reduced thickness amorphous carbon
layer (c) Purified MWCNTs after Sulfonation showing carbon debris and defects due to erosion by the chemical treatment
X-ray Fluorescence
providing all instrumentation facilities. The authors also
The functionalized samples were also quantified by XRF would like to thank colleagues from Fritz Haber Institute
analysis to determine carbon and sulfur content. The (FHI), Germany for their support and guidance.
number of molecules for carbon and sulfur was calculated
to quantify the changes of sulfur loading. Compositional
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