Applied Surface Science 450 (2018) 122–129

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Applied Surface Science

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Full Length Article

Facile covalent functionalization of carbon nanotubes via Diels-Alder

reaction in deep eutectic solvents
Cuong M.Q. Le a, Xuan Thang Cao b, Trang T.K. Tu a, Won-Ki Lee c, Kwon Taek Lim a,⇑
a
Department of Display Engineering, Pukyong National University, Busan, South Korea
b
Faculty of Chemical Engineering, Industrial University of Ho Chi Minh City, Viet Nam
c
Department of Polymer Engineering, Pukyong National University, Busan, South Korea

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

Article history: Deep eutectic solvents (DESs), a new type of cost-effective ionic liquid analogues, were employed to
Received 5 March 2018 develop a novel and efficient method for direct functionalization of multiwalled carbon nanotubes
Revised 16 April 2018 (MWNTs) via Diels-Alder (DA) click reaction. Poly(ionic liquid)s featuring furfuryl moieties (P(F-ILs))
Accepted 18 April 2018
and butyl moieties (P(B-ILs)) were synthesized by the functionalization of poly(chloromethylstyrene-al
Available online 19 April 2018
t-maleic anhydride) with 1-methylimidazole and furfuryl amine or butylamine. Then, the polymer was
directly grafted on the surface of untreated MWNTs in choline:ethylene glycol (ChCl:EG) based DES with-
Keywords:
out any catalyst. The successful functionalization of the polymer on MWNTs was confirmed by Raman
Poly(ionic liquid)s
RAFT
spectroscopy, TGA, and XPS analysis. It was shown that the reaction proceeded in a very rapid fashion
Multi-wall carbon nanotubes (less than an hour) and the use of DESs significantly improved the grafting density (more than double)
Diels-Alder reaction as compared with the reaction in water.
Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction and sulfuric acid in order to introduce carboxylic groups on the

Carbon nanotubes (CNTs) are one type of one-dimensional car-
bon nanomaterials that have drawn much attention for their excel-
lent mechanical, thermal and electrical properties since the
discovery of them in 1991 [1]. They have been extensively applied
for a variety of applications such as catalysis materials [2], electro-
chemistry, sensors, novel nanomaterials [3,4], biomedical applica-
tion [5–7], and so on [8]. However, due to inter-tube interaction,
CNT bundles are unable to disperse in common aqueous or organic
solvents and thus limit their application. To overcome this intrinsic
drawback and take advantage of their properties, surface modifica-
tion is imperative, typically based on covalent and non-covalent
functionalization approaches [9–12]. Non-covalent functionaliza-
tion involves the formation of hydrophobic stacking and van der
Waals interactions that preserve the electronic and optical proper-
ties of CNTs. This approach is more convenient, flexible, and mild
but the desorption due to weak pi-pi stacking makes this method
inherently unstable [13]. On the contrary, covalent functionaliza-
tion ensures a high stability of CNT conjugates [14]. One of the big-
gest drawbacks of CNT covalent modification is that the procedure
usually involves an acidic oxidation with concentrated nitric acid
⇑ Corresponding author.
E-mail address: ktlim@pknu.ac.kr (K.T. Lim).
surface for subsequent modification through esterification or ami-
dation. In the covalent functionalization category, cycloaddition at
the sidewall of CNTs via Diels-Alder (DA) reaction has emerged as a
promising alternative to acidic oxidation because of its balance
between the preservation of intrinsic properties and the improve-
ment of dispersibility of CNTs. The DA reaction-based surface mod-
ification is a method of simple, facile, and without the use of
catalyst and surface pretreatment, occurring in various types of
solvents [15–22]. Thus it is essential to optimize the DA reaction
for better functionalization of CNTs.
It is well known that the DA reaction is strongly affected by a sol-
vent due to the hydrophobic effect [23,24]. In this regard, ionic liq-
uids (ILs) have been proved to be an effective reaction medium with
significantly accelerating the rate of DA reaction [25–27]. However,
the application of IL as a solvent is often limited due to the high
price and toxicity. A promising cheap and eco-friendly IL-
analogue for DA reaction named as a deep eutectic solvent (DES)
was first reported by Abbott and coworkers [28–30]. In general,
DES is obtained by mixing at least two components, a hydrogen
bond acceptor and a hydrogen donor, which are able to associate
with each other to form a new eutectic phase characterized by a
melting point lower than individual component. Because of its sim-
ilar properties with ILs, it has been extensively applied during the
last decade in many fields of chemistry, including organic synthesis,
electrochemistry, biochemistry and nanomaterials preparation

https://doi.org/10.1016/j.apsusc.2018.04.173
0169-4332/Ó 2018 Elsevier B.V. All rights reserved.
 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129
Fig. 1. Schematic preparation of imidazolium-based PILs functionalized MWNTs.
[31–34]. Moreover, DES is not only a solvent for organic molecules,
but also a disperse medium for inorganic materials [35]. For exam-
ple, DES has been used as a solvent for functionalization and prepa-
ration of CNT-based nanocomposites [36–42]. Nevertheless, a
traditional acid-oxidation treatment of CNTs was always preceded
before use to increase the surface activity in these methods. Hence,
it would be highly desirable to develop a method which avoids the
oxidation step for the functionalization of CNT in DESs.
Poly(ionic liquid)s (PILs) are a new type of polymeric materials
containing ILs in their repeating units. Due to the combination of
intrinsic properties of polymers with specific nature of ILs, PILs
have attracted a great attention as promising materials in the fields
of catalysis, energy devices, CO2 capture, electrochemistry, stimuli-
responsive materials and carbon materials [43–45]. Recently, PILs
have been reported as a new class of CNT modifiers [46–52] for
synthesis of nanocomposites with specific applications. Based on
fundamental researches about CNT functionalization and applica-
tion, no paper has been reported so far for the direct functionaliza-
tion of CNTs with PILs in DESs. Therefore, there is a high motivation
to utilize the advantage of DESs as reaction media for direct func-
tionalization of CNTs via DA reaction.
In this work, a novel copolymer of poly(chloromethylstyrene-
alt-maleic anhydride) (PCMA) was prepared by the reversible
addition-fragmentation chain transfer (RAFT) polymerization. The
highly reactive anhydride parts were functionalized with furfuryl
amine, and then the chloromethyl groups were subsequently
reacted with 1-methylimidazole, resulting in imidazolium-based
PILs with furfuryl pendant moieties. The PIL without furfuryl
groups was also synthesized for a control experiment. The PILs
with and without furfuryl groups were grafted on the surface of
multi-walled carbon nanotubes (MWNTs), affording PILs/MWNTs
in DESs under ultrasonication (Fig. 1)
2. Experimental details
2.1. Materials
The MWNTs (CM-95, diameter 10–15 nm, length 10–20 lm,
specific area 200 m2 g
1) were purchased from Hanwha Nanotech
(Korea). Maleic anhydride (99%) was purchased from Sigma–
Aldrich (Korea). 4-(Chloromethyl) styrene (>99%, TCI chemicals)
was passed through a neutral alumina column and 2,20 -azobis(iso
butyronitrile) (AIBN) was recrystallized in methanol prior to use.
Furfuryl amine (>98%) and 1-methylimidazole (>99%) were
obtained from TCI chemicals (Korea). Other solvents and chemicals
of analytical grade were used as received. 2-(Dodecylthiocarbono
thioylthio)-2-methylpropanoic acid (DDMAT) was synthesized
according to the previous report [53]. DESs were prepared by fol-
lowing the previously reported method [34].
123
2.2. Synthesis of poly(ionic liquid)s
The synthesis of poly(chloromethylstyrene-alt-maleic anhy-
dride) (PCMA) copolymers was performed by RAFT polymerization.
Briefly, DDMAT (0.277 g, 0.76 mmol), 4-(chloromethyl)styrene
(5.79 g, 38 mmol), maleic anhydride (3.72 g, 38 mmol), and AIBN
(62 mg, 0.38 mmol) were dissolved into 20 mL of 1,4-dioxane
placed in a glass vial. After the solution was purged with nitrogen
for 30 min, the vial was put in a preheated oil bath at 60 °C for 4 h.
The product was purified by precipitation in 300 mL of diethyl
ether. After filtration, the polymer was dried under vacuum at
40 °C to yield 7.79 g of white powder (conversion 80%).
PCMA was then functionalized with both furfuryl amine and 1-
methylimidazole as follow: PCMA (2.3 g, 8.8 mmol of anhydride
units) was dissolved in 10 mL of N,N-dimethylformamide in a 50
mL two-neck flask. Furfuryl amine (0.8 mL, 8.8 mmol) was added
dropwise into the polymer solution under stirring and the solution
was placed in a preheated oil bath at 70 °C for 1 h. Afterwards, 1
methyl-imidazole (2.7 mL, 33.6 mmol) was introduced to the reac-
tion solution and the reaction continued for another 20 h. The vis-
cous solution was diluted with methanol and precipitated in 200
mL of acetone. The solid polymer was dissolved and precipitated
in acetone once again, and finally dried under vacuum at 40 °C
for 24 h in the form of white powder (3.45 g) (denoted by P(F-
ILs)). As a control sample, the polymer without containing furfuryl
pendant groups was synthesized additionally by functionalizing
PCMA with butylamine and 1-methylimidazole in the same proce-
dure (denoted by P(B-ILs)).
2.3. Functionalization of MWNTs with furfuryl amine
In a typical Diels-Alder reaction, 1 mL of furfuryl amine (1mL)
was mixed with a solvent (8 mL) in a 10 mL vial and then 100
mg of untreated MWNTs were introduced to the solution. The mix-
ture was placed in an ultrasonic bath at 60 °C for 2 h. After the
reaction was completed, the unreacted reagent and solvent were
removed through a 0.2 mm PTFE membrane filter and the filtered
solid was washed thoroughly with 200 mL of methanol (2 times).
The product was dried under vacuum at 40 °C for 24 h.
2.4. Diels-Alder reaction between the furfuryl bearing-polymer and
carbon nanotube
PILs/MWNTs was prepared by grafting P(F-ILs) onto the surface
of MWNTs by Diels-Alder reaction under sonication. In a typical
experiment, P(F-ILs) (0.18 g) was dissolved in 8 mL of a solvent.
100 mg of as-received MWNTs were added to the solution and
the reaction was then irradiated in an ultrasonic bath at 60 °C for
2 h. The black suspension was filtered and washed with 200 mL
124 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129

of methanol through a 0.2 mm PTFE membrane filter to discard free

polymers and the solvent. The modified MWNTs was then redis-
persed in 200 mL of methanol under sonication for 30 min and fil-
tered again to remove trace of unreacted polymer and the solvent.
The final product was dried under vacuum at 40 °C for 24 h for fur-
ther characterization. MWNTs mixed with P(B-ILs) as a control
sample were prepared by applying the same procedure as above.

2.5. Characterization

1
H NMR spectra were recorded on a JNM-ECP 600 MHz (JEOL)
instrument. The molecular weight of polymers was analyzed using
gel permeation chromatography (GPC; Agilent 1100) with a refrac-
tive index detector and PL gel columns (5 mm; 104, 103, and 102 Å).
The system was calibrated with polystyrene standards in N-N0 -
dimethylacetamide at 50 °C and a flow rate of 1 ml/min. Raman
spectroscopy was performed on a JASCO NRS-5000 spectrometer
with a 532-nm diode laser. Thermogravimetric analysis (TGA) Fig. 3. GPC graph of PCMA polymer.

was conducted with a Perkin-Elmer Pyris 1 analyzer (USA) within

the temperature range of 50–700 °C at a heating rate of 10 °C
min
1 under air flow. X-ray diffractions were collected on a Philips
X’pert-MPD diffractometer (Netherlands) with Cu Ka radiation.
The X-ray photoelectron spectroscopy (XPS) experiments were
performed at a Thermo VG Multilab 2000 in an ultra-high vacuum
with Al Ka radiation.
3. Results and discussion
3.1. Synthesis of imidazolium-based poly(ionic liquid)s
Fig. 2 shows the synthesis of imidazolium-based poly(ionic liq-
uid)s. The precursor copolymer of PCMA with the desired molecu-
lar weight and molecular weight distribution was first synthesized
via RAFT copolymerization of p-chloromethylstyrene and maleic
anhydride in dioxane using DDMAT as a chain transfer agent. The
polymerization reaction was stopped at 80% conversion, yielding
a unimodal and low dispersity polymer (Ð = 1.30) as confirmed
by GPC (Fig. 3). 1H NMR analysis was used to confirm the chemical
structure of PCMA. As shown in Fig. 4A, the characteristic peaks of
PCMA at 4.7 and 6.2–7.2 ppm are assigned to chloromethyl (f) and
phenyl (d, e) protons, respectively. The repeating unit can be calcu-
lated by comparing the peak area of benzylic peaks at 4.7 ppm and
n-alkyl peaks of the RAFT moiety at 1.2 ppm. Copolymers of styr-
ene and maleic anhydride have form alternating structures [54],
and PCMA is expected to have alternating composition as well.
Therefore, the degree of polymerization for PCMA was evaluated
as 40 (Mn(NMR) = 10,400 g mol
1).
The ionic polymers with pendant imidazolium and furfuryl
groups were obtained via post-polymerization of PCMA with 1-
methylimidzole and furfuryl amine. After functionalization, the
1
H NMR spectrum of P(F-ILs) (Fig. 4B) displayed the new peaks of
furfuryl (l, m, n, k) at 6.3, 6.15, 7.69, and 4.11 ppm and imidazolium
(g, h, i, j) at 3.8, 9.5 ppm, and 7.47–7.7 ppm, indicating the success-
ful functionalization of copolymers. Furthermore, the characteris-
tic benzylic peak at 4.7 ppm disappeared and another peak
appeared at 5.4 ppm, indicating that the substitution reaction of
chloromethyl was complete. On the other hand, the 1H NMR spec-
trum of P(B-ILs) (Fig. 4C) showed the presence of butyl peaks in the
region 0.5–2 ppm instead of furfuryl peaks.
3.2. Diels-Alder reaction between furfuryl moiety and carbon
nanotubes
The Diels-Alder reactions between furfuryl amine and MWNTs,
in which MWNTs acts a dienophile and furfuryl amine does as a
diene, were performed either in bulk or in a solvent as a dispersed
medium under ultrasonication. For a typical reaction, 100 mg of
untreated MWNTs, 1 mL of furfuryl amine and 8 mL of a solvent
were mixed in a 10 mL vial. After 2 h of sonication at 60 °C, the
mixture was diluted and washed with a copious amount of metha-
nol. After drying, the amount of reacted furfuryl amine was calcu-
lated by the weight loss between 100 °C and 600 °C in TGA
analysis. The results are summarized in Table 1. Based on the
weight loss and grafting ratio, it was clear that the reaction in
water gave the lowest grafting ratio, meanwhile the reaction in

Fig. 2. Synthetic scheme for preparation of imidazolium-based poly(ionic liquid)s.

 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129
Fig. 4. 1H NMR spectrum of PCMA (A), P(F-ILs) (B) and P(B-ILs) (C) in DMSO-d6.
Table 1
Functionalization of MWNTs in different solvents.
Entry Solvent Weight loss
no. wt.%
1 Water 1.82
2 Ethylen glycol (EG) 2.12
3 Furfuryl amine (bulk) 2.06
4 Choline chloride:Maloinic acid 2.3
(ChCl:MA = 1:1)
5 Choline chloride:Ethylene glycol 3.78
(ChCl:EG = 1:2)
ethylene glycol (EG) or even in bulk furfuryl amine did not much
improve the grafting ratio. However, the reactions in the ChCl:EG
solvent showed a significantly improved grafting ratio, roughly
two times higher than others. The result could be explained that
MWNTs forms a stable dispersed mixture in DESs, leading to more
homogenous DA reaction. In this case, DESs not only serve as dis-
persed media to enhance the interaction between furfuryl groups
and the surface of MWNTs but also act as a catalyst, accelerating
the rate of the DA reaction [55]. In contrast, MWNTs are readily
aggregated to form sediment in other solvents like water and ethy-
lene glycol (Fig. 5). Due to the high efficiency of DA reaction in
DESs, the ChCl:EG was selected as the solvent for grafting poly
(ionic liquid)s onto the surface of MWNTs.
3.3. Grafting of poly(ionic liquid)s onto MWNTs via Diels-Alder
reaction
The reactions between furfuryl functionalized poly(ionic liquid)
s (P(F-ILs)) and MWNTs were conducted at 60 °C under ultrasoni-
cation, resulting in the products of PILs/MWNTs. The products
were isolated and characterized by TGA to determine the grafting
ratio. The TGA graph and its first derivative thermogravimetric
analysis (DTG) are presented in Fig. 6. The TGA showed that
MWNTs remained stable until 600 °C whereas PILs/MWNTs (1)
125
Grafting ratio
mmol g
1
0.19
0.22
0.22
0.24
0.40
Fig. 5. Dispersity of MWNTs in water, EG, ChCl:MA, ChCl:EG after 3 days.
and P(F-ILs) started to decompose from 150 °C to 600 °C. Therefore,
the amount of the polymer degraded in the range 150–600 °C was
used to calculate the grafting ratio. Grafting ratios were calculated
by the method in the previous report [21] and summarized in
Table 2.
The grafting of functional polymers without furfuryl moieties (P
(B-ILs)) resulted in a low amount of physically absorbed polymers
on MWNTs (Table 2, entry No. 1), possibly due to the cation-p inter-
action between imidazolium ILs in the copolymer and carbon nan-
otubes [56]. On the other hand, the polymer with furfuryl groups
formed stable covalent bonds on the surface of MWNTs through
DA reaction. It is clearly revealed that the presence of the DA reactive
groups resulted in a significantly improved grafting ratio, roughly
three times higher than P(B-ILs) (Table 2, entry No. 2). Besides, the
use of DESs achieved ca. 50% improvement of grafting ratio as com-
pared to the functionalization reaction in water (Table 2, entry No.
5). More interesting, the DA reaction time could be considerably
reduced to 30 min without losing the grafting efficiency (Table 2,
entry No. 3 and 4). The results are in agreement with those obtained
by functionalization with furfuryl amine in Table 1. Therefore, DESs
could be employed as novel and high-performance solvents for the
functionalization of carbon nanotubes.
126 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129
Fig. 6. TGA and DTG curves of MWNTs, P(F-ILs), and PILs/MWNTs composites.
Table 2
Grafting ratios of functionalized MWNTs.
Entry no. Polymer Solvent
1 P(B-ILs) ChCl:EG
2 P(F-ILs) ChCl:EG
3 P(F-ILs) ChCl:EG
4 P(F-ILs) ChCl:EG
5 P(F-ILs) Water
*
Grafting density was calculated by the method in the previous report [21].
For further clarification of the formation of covalent bonds on
the surface of MWNTs, a model composite, which is simulated
the sample entry No. 2 in Table 2 (known as PILs/MWNTs(1)),
was prepared by grinding the mixture of P(F-ILs) and MWNTs at
the weight ratio of 33:67 at room temperature. The composite
was denoted as PILs/MWNTs(2) and characterized by TGA. As dis-
played in Fig. 6, the DTG analysis show a similar degradation step
for both sample PILs/MWNTs(1) and PILs/MWNTs(2). However, the
degradation peaks of PIL/MWNTs(2) shifted to higher temperature
10–25 °C, which could suggest that the DA reaction occurred first
and subsequently the retro-DA took place on this sample, leading
to the delayed degradation of the P(F-ILs). In contrast, the polymer
on PILs/MWNTs(1) directly underwent the retro-DA stage so that
the polymer started to degrade sooner and slower as compare with
PILs/MWNTs(2). Therefore, this results could be used to corrobo-
rate the presence of covalent bonds due to DA reaction on the sur-
face of composite PILs/MWNTs(1).
Long time exposure of MWNTs under ultrasonication could
damage and shorten the length of MWNTs, which impair their
intrinsic properties. The use of DESs leads to reduce the exposure
time under sonication. Hence, the structural integrity of MWNTs
was confirmed by Raman spectroscopy and XRD analysis (Fig. 7).
The Raman spectra of PILs/MWNTs(1) showed an increasing inten-
sity of defect-induced D-band after Diels-Alder ‘‘click” reaction
(Fig. 7a). D-band is usually used to estimate the presence of amor-
phous or sp2 hybridized disordered carbons in MWNT samples and
the D/G band intensity ratio (ID/IG) reflects the degree of ‘‘disorder”.
Herein, it was found that the ID/IG ratio increases from 0.82 in pure
MWNTs to 0.92 in PILs/MWNTs(1), implying the formation of side-
Reaction time Grafting ratio*
h wt% mmol g
1 chain nm
2
2 13.1 0.009 0.026
2 32.6 0.027 0.082
1 29.3 0.023 0.071
0.5 24.6 0.019 0.056
2 23.7 0.018 0.053
wall defects. Furthermore, the slight shift to higher wavenumber of
the G band evidences changes in the graphite structure of MWNTs
due to the grafting process. On the other hand, the ID/IG ratio of the
model composite (PILs/MWNTs(2)) was nearly identical with pris-
tine MWNTs. This indicates that without DA reaction and the effect
of ultrasonication, the structure of the MWNTs is maintained in the
PILs/MWNTs(2) composite. In Fig. 7b, the XRD patterns of MWNTs
and PILs/MWNTs(1) present a main diffraction peak at 26.1° and a
weak peak at 43° corresponding to the (0 0 2) reflection of the
hexagonal graphite structure and the diffraction of the (1 0 0)-gra
phite base, respectively. The result demonstrates that the graphitic
structure of carbon nanotubes is still maintained after functional-
ization with polymers.
The chemical bond formation of PILs/MWNTs was further inves-
tigated by XPS analysis (Fig. 8). Before functionalization, the C1s
core-level spectrum of MWNTs with four peaks at binding energies
of 285, 287, 288.8, and 291.1 eV implied to C@C/CAC, CAO, C@O
bonds, and the p-p⁄ transition level, respectively. The N1s core-
level spectrum was not visualized due to the absence of nitrogen
in pure MWNTs (Fig. 8a). After Diels-Alder reaction, the curve fitted
C1s core-level showed a new peak at the binding energy of 286 eV,
indicating the CAN bond formation (Fig. 8b). In addition, the inten-
sities of the signal from C-O and C@O bonds were remarkably
increased. The increased intensity of the C@O peak at 532 eV in
the O1s signal and the appearance of the N1s signal at 402 eV
demonstrated the successful grafting of P(F-ILs) onto the MWNTs.
On the contrary, the XPS spectrum of PILs/MWNTs(2) composite
(Fig. 8c) without featuring DA covalent bonds did not show the
presence of C-N or C@N bonds in C1s and N1s ranges, meanwhile
 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129 127

Fig. 7. Raman spectra (a) and XRD pattern (b) of PILs/MWNTs and MWNTs.

Fig. 8. High-resolution XPS spectra of MWNTs (a), PILs/MWNTs(1) (b) and PILs/MWNTs(2) (c).

the O1s spectrum exhibited a quite similar behavior with the one
in MWNTs. The XPS analysis revealed the difference between
PILs/MWNTs with and without DA reaction. Therefore, it could be
confirmed that the DA grafting reaction between P(F-ILs) occurred
on the surface of MWNTs.
4. Conclusion
In this study, choline-based DESs were employed as environ-
mentally friendly reaction media for grafting of novel PILs onto
MWNTs via DA reaction. The approach offered the mild reaction
128 C.M.Q. Le et al. / Applied Surface Science 450 (2018) 122–129
condition, catalyst free, short reaction time and high grafting effi-
ciency. DESs plays an important role in dispersing MWNTs and cat-
alyzing for DA reaction, leading to a significant improvement in the
grafting density of PILs on MWNTs and their reaction time as com-
pared with the reaction in water. Furthermore, the presence of
covalent anchoring groups originated from furfuryl moieties in P
(F-ILs) resulted in three times higher grating density than the poly-
mer sample without furfuryl in P(B-ILs). The covalent functional-
ization of P(F-ILs) on the surface of MWNTs was confirmed by
Raman spectroscopy, XRD, XPS, and TGA, which revealed the excel-
lent balance between the preservation of the carbon lattice and the
maximization of CNT functionalization. Due to the high functional-
ity of the precursor polymer, the polymer could be functionalized
with a diverse structure of ionic liquids for grafting on carbon nan-
otubes, which has high potential for application in the field of
catalysis, electrochemistry or composite materials. Moreover, it
would provide a facile route for tailoring surface properties of car-
bon nanostructures as all graphitic carbon materials tend to
undergo DA reactions.
Acknowledgment
This work was supported by the National Research Foundation
of South Korea (NRF) Grant funded by the Ministry of Education
(NRF- 2015R1D1A3A01019109).
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