Carbon 45 (2007) 285–292

www.elsevier.com/locate/carbon

Dispersing multi-walled carbon nanotubes with water–soluble block

copolymers and their use as supports for metal nanoparticles
Zhimin Wang a, Qingchun Liu a, Hui Zhu a, Hanfan Liu a,
Yongming Chen a,*, Mingshu Yang b
a
State Key Laboratory of Polymer Physics and Chemistry, Joint Laboratory of Polymer Science and Material, Institute of Chemistry,
The Chinese Academy of Sciences, Beijing 100080, China
b
Key Laboratory of Engineering Plastics, Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, China

Received 15 May 2006; accepted 20 September 2006

Available online 3 November 2006

Abstract

Oxidized multi-walled carbon nanotubes (MWCNTs) were dispersed in aqueous and organic solvents by non-covalent modification
with a double-hydrophilic block copolymer, poly(ethylene oxide)-b-poly [2-(N,N-dimethylamino)ethyl methacrylate] (PEO-b-PDMA).
The PDMA segments were anchored onto the surface of the oxidized MWCNTs through multi-site zwitterionic interactions between
the amino and the carboxyl groups while the PEO segments formed corona to promote the solubility of MWCNTs in different solvents.
FT-IR and 1H NMR spectroscopy gave structural information on the resulting composite, supporting the successful modification. Ther-
mal gravimetric analysis showed that the grafting yield could reach 26%. UV/vis and transmission electron microscopy provided direct
evidence for the individual dispersion. The resulting modified MWCNTs could find broad spectrum of applications. As an example, Au
and Pt nanoparticles were attached on the sidewall of the modified MWCNTs by using the amino groups of PDMA segments.
Ó 2006 Elsevier Ltd. All rights reserved.

1. Introduction [4–12]. Using this strategy various organic molecules

Since their discovery, carbon nanotubes (CNTs) have
attracted extensive attention owing to their exciting poten-
tial applications in sensors, nanocomposites, molecular
devices or advanced materials with electronic and optical
properties [1–3]. However, dispersion of CNTs in solvents
and polymer matrixes is an obstacle for their further appli-
cations due to the poor solubility and processability. In this
respect, much efforts have been made on the surface mod-
ification of CNTs mainly to enhance their solubility and
processability [4,5]. Among them, covalent modifications
with small organic molecules or macromolecules utilizing
defect chemistry of oxidized CNTs through amidation
and esterification are commonly applied methodology
*
Corresponding author.
E-mail address: ymchen@iccas.ac.cn (Y. Chen).
including small molecules, linear polymers, copolymers,
dendritic and hyperbranched polymers were successfully
grafted onto the sidewall and tips of the CNTs through a
series of reaction strategies such as atom transfer radical
polymerization (ATRP), reversible addition-fragmentation
chain transfer (RAFT), ring-opening polymerization
(ROP), and so on [13–22]. In addition, directly covalent
modifications of the inert sidewall through some vigorous
reactions such as fluorination, ozonolysis, osmylation,
and azomethine ylides [5] were also applied. Though direct
modification is pithily and the multi-step reaction is
escaped, it is limited in some specific transformation reac-
tions and involves demanding experimental conditions.
Generally, the covalent modifications are often tedious
and inconvenient for further applications and always
result in the loss of the intrinsic electronic structures of
CNTs.

0008-6223/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2006.09.025
286 Z. Wang et al. / Carbon 45 (2007) 285–292
Fig. 1. Functionalization procedure of MWCNTs with PEO-b-PDMA through multi-site zwitterionic interactions.
Non-covalent surface modifications were also developed
although the relatively weak interaction between CNTs
and the modifiers. Several approaches have been reported
through non-covalent adsorption such as small molecular
surfactants, p–p interaction utilizing pyrene-containing
molecules, non-specific or specific adsorption of protein
and DNA [23–26]. Amphiphilic block copolymers, which
can form micelles in the selective solvents, have also been
used to disperse the pristine SWCNTs utilizing the hydro-
phobic interaction in the selective solvents [27–29]. How-
ever, this method always failed to separate the modified
products from the selective solvents owing to the physical
adsorption nature, consequently, the exploration of the
solid properties and applications of the modified products
was suppressed. Haddon et al. and Wong et al. have
reported a non-covalent method through zwitterionic func-
tionalization of SWCNTs with small molecules containing
monoamine functional group [30–32]. Sun et al. also
addressed the functionalization of SWCNTs with dia-
mine-terminated oligomeric poly(ethylene glycol) through
zwitterionic interaction [20,33,34]. Although the success
of these functionalization strategies, high temperature
and long reaction time are always needed. In the meantime,
due to single anchoring site between SWCNTs and the
modifiers, the resulted products were not stable enough
comparing with the covalent strategies and sometimes
failed to exfoliate the bundles of CNTs to individual tubes
[20,33]. Despite a big progress in modification of the inert
surface of CNTs has been achieved in the last few years,
effective and simple approaches are still desperately
desired, especially for the application of the modified CNTs
in the polymer based nanocomposites, where high efficient
and scaleable requirement is the prerequisite. Zwitterionic
interaction is the simplest form of non-covalent interaction.
Zwitterionic functionalization of CNTs with a block
copolymer containing multiple reactive sites can effectively
increase the interaction between CNTs and the modifiers.
Non-binding segment would enhance the solubility of the
tubes and perform some useful functions. Therefore, block
copolymer modification may impart significant advantages
to the resulted CNTs such as for preparing CNTs-based
nanocomposites, serving as a catalyst support, directing
nanoparticle assembly or using as biosensor. To the best
of our knowledge, there is no report on modification of oxi-
dized CNTs based on multiple zwitterionic interactions
with well-defined double-hydrophilic block copolymer.
Poly(ethylene oxide)-b-poly[3-(N,N-dimethylamino-
ethyl) methacrylate] (PEO-b-PDMA) is a water soluble
block copolymer that has several functions. On the one
hand, PDMA contains pendent tertiary amines, which
may interact with acids and metal ions. On the other hand,
PEO is a prototypic biocompatible polymer and has very
important application in biotechnologies and pharmaceu-
tics since it resists protein adsorption and cell adhesion
[35–37]. In this paper, we report a simple and effective
method to modify multi-walled carbon nanotubes
(MWCNTs) using a well-defined PEO-b-PDMA block
copolymer via multiple zwitterionic interactions. Com-
pared with other reported strategies for CNTs modifica-
tion, several advantages could be found by using this
method, such as mild experiment conditions, environmen-
tal benign solvent involved, ambient temperature, shorter
reaction time and free of sonication. The resulting
MWCNTs could be individually dispersed not only in
water but also in some organic solvents. In the mean-
time, the modified MWCNTs could be used as the one-
dimensional template for metal nanoparticle assembly
using those amino groups of PDMA block free from zwit-
terionic interaction. Furthermore, non-covalent modified
MWCNTs coated with PEO corona could serve as promis-
ing non-biofouling materials for applications in biosensor
and biotechnology, where non-specific or specific adhesions
of proteins or cells must be avoided [37]. Fig. 1 outlines the
strategy used for multiple zwitterionic modification of
MWCNTs with the PEO-b-PDMA.
2. Experimental
2.1. Materials
The MWCNTs used in this paper obtained from two different sources:
the oxidized MWCNTs, MWCNT–COOH (90 wt% pure CNTs and
5 wt% carboxylic acid groups; 8–15 nm in diameter and hundreds of nano-
meter in length, Timesnano, Inc., Chengdu), were synthesized by chemical
vapor deposition and used as received, and labeled as MWCNTs(CD).
For comparison, the pristine MWCNTs (purity 90%, 10–15 nm in diame-
ter and several micrometers in length, Shenzhen Nanotech Port Co., Lt.)
were oxidized according to the reported method, [38] and labeled as
MWCNT(SZ). The carboxylic acid groups of the oxidized MWCNTs were
confirmed by FT-IR spectroscopy (Supporting Information, Fig. S1).
Most of the experiments were conducted with MWCNTs supplied by
Timesnano except the specific denotation. Monomethoxy capped
poly(ethylene oxide)s (PEO–OHs) with molecular weight 750, 2000, and
5000, were purchased from Aldrich and used as received. 2-(N,N-dimeth-
ylamino)ethyl methacrylate (DMA) obtained from Aldrich was passed
 Z. Wang et al. / Carbon 45 (2007) 285–292
through a basic alumina column, then vacuum-distilled over CaH2 prior to
use. 2-Bromoisobutyl bromide, N,N,N 0 ,N00 ,N00 -pentamethyldiethylenetri-
amine (PMDETA), HAuCl4 Æ 3H2O and NaBH4 were purchased from
Aldrich and 2 wt% water solution of HAuCl4 were prepared prior to
use. Pt colloids (1.96 mM, stabilized by glycol) were prepared in our lab-
oratory according to the published method [39]. Dichloromethane and
anisole purchased from Beijing Chemical Reagents Ltd. were distilled over
CaH2 prior to use. All other chemical reagents were used directly without
further purification.
2.2. Synthesis of mono-2-bromoisobutyryl PEO macroinitiator
(PEO–Br)
PEO–Br was synthesized as follows: A solution of 2-bromoisobutyl
bromide (12 mmol) dissolved in 40 mL dichloromethane was added drop-
wise to an ice-cooled solution of PEO–OH (10 mmol) and triethylamine
(12 mmol) in dichloromethane (200 mL) over 1 h under nitrogen. The mix-
ture was warmed to room temperature and stirred for 24 h. After remov-
ing the precipitates produced during evaporation of dichloromethane by
filtration, yellow oil-like crude product was obtained, which was washed
with distilled water for three times and extracted with dichloromethane.
After dried over anhydrous magnesium sulfate, the desiccant was filtered.
PEO–Br was obtained by precipitation of the filtrate into excess of
petroleum ether for three times, and then dried under vacuum at 30 °C
for 24 h.
2.3. Synthesis of double-hydrophilic block copolymers
(PEO-b-PDMA)
A group of block copolymers, PEOm-b-PDMAn, used in this work
were synthesized by ATRP using PEO–Br as initiator, PMDETA and cop-
per (I) bromide as catalyst at ambient temperature. The composition and
characteristic features of the block copolymers concerned in this paper
were listed in Table 1. A representative experimental procedure for the
block copolymer was described as follows: to a 25 mL Schlenk flask
equipped with a magnetic stirring bar, PEO–Br (0.1 mmol) and CuBr
(0.1 mmol) were charged, followed by adding DMA (5 mmol) and
degassed anisole (5 mL). The mixture was stirred at room temperature
for 10 min, after which it was degassed by three freeze-pump-thaw cycles.
Finally PMDETA (0.1 mmol) was added via a nitrogen-purged syringe.
The reaction was allowed to proceed with constant stirring for 12 h under
room temperature. The polymerization was terminated by exposing the
reaction vessel to air, and then 10 mL of THF was added. The solution
was passed through a basic alumina column and eluted with additional
100 mL of THF. After being concentrated in a rotary evaporator, the solu-
tion was poured into petroleum ether to precipitate the polymer, and then
dried under vacuum at 30 °C for 24 h. Size exclusion chromatography
(SEC) provided the number-average molecular weights and the polydis-
persity index. The polymerization degree of the PDMA block was deter-
mined by 1H NMR spectrum.
2.4. Modification of MWCNTs by zwitterionic interaction
A typical experiment was performed by mixing oxidized MWCNTs
(20 mg), PEO43-b-PDMA32 (200 mg) and deionized water (20 mL) in a
100 mL flask, followed by stirring at ambient temperature. After reaction
Table 1
Characteristic features of the block copolymers used for MWCNT modification
PEO17-b-PDMA15b PEO43-b-PDMA32b PEO43-b-DMA116b
Mna 14300 11500 36400
Mw/Mna 1.39 1.42
a
Mn was determined by SEC.
b
The length of PDMA block was estimated by 1H NMR spectra.
287
for 30 min, the mixture became a homogeneous black solution. The mix-
ture was stirred for another 90 min to complete the interaction. After a
centrifugation, the modified nanotubes were recovered by filtration with
a membrane with a pore diameter of 0.45 lm and washed with distilled
water, tetrahydrofuran, and ethanol cycles in order to eliminate the free
copolymers completely; subsequently the product was vacuum-dried at
45 °C for 24 h. To examine the applicability of this strategy, a group of
copolymers with different compositions were applied under the same
conditions. Furthermore, the minimum concentration of the saturated
grafting yield for modification was determined to be 10 mg/mL according
to the TGA results from three different concentrations employed. There-
fore, this concentration was used to conduct the rest of the experiments.
2.5. Attachment of metal nanoparticles onto MWCNTs
Attachment of gold nanoparticles onto the surface of MWCNTs was
made by an in-situ method; the detail was described as follows: Oxidized
MWCNTs (1 mg), PEO43-b-DMA32 (10 mg) and 1 mL of distilled water
were added to a 5 mL capped-flask. After stirring for 2 h, the oxidized
MWCNTs were dispersed and formed a black homogeneously solution,
0.5 mL of 2% water solution of HAuCl4 was added and the solution
was stirred for another 12 h, and then 10 mg (10 equiv to Au3+) of sodium
borohydride was added. The reaction was finished after another 12 h
stirring.
For attachment of Pt nanoparticles, the preformed Pt colloids, stabi-
lized by glycol, was used directly. In this case, the modified MWCNTs
(1 mg) were redispersed in 1 mL water by stirring for 30 min, and then
0.5 mL Pt colloids were added to the stirring solution and continued for
12 h. The resulted solutions containing Au and Pt nanoparticles supported
by MWCNTs were directly used to conduct the TEM observation. For
comparison, the oxidized MWCNTs without block copolymer were
employed to examine attachment of the Au and Pt nanoparticles under
the same conditions.
2.6. Characterization
All 1H nuclear magnetic resonance (1H NMR) spectra were recorded
using a Bruker 300 MHz spectrometer. PEO–OH and PEO–Br were ana-
lyzed in CDCl3. PEO-b-PDMA and modified MWCNTs were analyzed in
D2O. Molecular weights and molecular weight distributions of block
copolymers were determined by SEC using a Waters 515 pump and
Waters 2414 differential refractive index detector at 35 °C. The columns
were calibrated with polystyrene standards. THF containing 1% triethyl-
amine was used as a mobile phase at a flow rate of 1.0 mL/min. The
UV–Vis spectra and absorbance were acquired on a Shimadzu UV-
1601PC spectrophotometer. The wavelength was set in the range of 200-
800 nm for all the measurements. Grafting efficiency and the amounts of
block copolymer anchored to the MWCNTs were determined using a
NETZSCH4 TGA instrument at a 50 mL/min flowing rate of nitrogen
atmosphere. The temperature was increased from 20 to 900 °C at a rate
of 10 °C/min. TEM observations were conducted on a JEM-100 electron
microscope at an acceleration voltage of 100 kV. The sample was prepared
by dropping the water solution of modified MWCNTs or nanoparticle
attached MWCNTs onto copper grids coated with Formvar and carbon
film. The FT-IR spectra of the PEO43-b-PDMA32 modified MWCNTs,
free copolymer and purified MWCNTs were obtained by using Nicolet
Avator 230 spectrometer. The samples were prepared with KBr.
PEO43-b-DMA218b PEO113-b-PDMA93b
45900 –
1.31 1.23 –
288 Z. Wang et al. / Carbon 45 (2007) 285–292

3. Results and discussion
3.1. Modification of the purified MWCNTs
When PEO43-b-PDMA32 copolymer was mixed with the
oxidized MWCNTs in water under continuous stirring, the
initial amount of the black solid suspension decreased con-
siderably as the tubes dissolved. The resulted MWCNTs
modified by the PEO43-b-PDMA32 could be separated eas-
ily and redissolved in water or some organic solvents. A
series of analytic technologies were employed to character-
ize the structure and properties of the modified products in
detail. Fig. 2(a) shows the photos of the modified
MWCNTs redissolved in different solvents. The modified
tubes could form stable transparent and colored solutions
in water, ethanol, and chloroform (from dark brown to
essentially black depending on the concentration) without
MWCNTs precipitation for at least several months. But
the modified tubes could not dissolve in N,N 0 -dimethyl-
formamide (DMF). It is known that zwitterionic interac-
tions are pH dependent. In order to confirm the
modification was zwitterionic interaction rather than phys-
ical adsorption or covalent bonding, the pH of the solution
was decreased by adding the aqueous solution of HCl. As
shown in Fig. 2(b), decreasing pH of the solution led to
the precipitation of MWCNTs. This phenomenon can be
ascribed to the neutralization of the amino groups of
PDMA blocks, which destroyed the zwitterionic interac-
tion between the copolymer and the MWCNT. This pH
dependent property can be useful for purification of CNTs
and for drug delivery application.
To examine the dispersion state of the modified
MWCNTs in solutions, one drop of the water solution with
redissolved modified MWCNTs (1 mg/mL) was dropped
onto a copper grid coated with carbon film for TEM
analysis. For comparison, a different tubes, MWCNT(SZ),
was also modified under the same conditions and exam-
ined by TEM analysis. As demonstrated by Fig. 2(c)
[MWCNT(SZ)] and Fig. 2(d) [MWCNT(CD)], the two
kinds of MWCNTs can all be dispersed individually in
water solution, well indicating the efficacy and the applica-
bility of this approach.
In order to confirm the homogenous dispersion of the
modified MWCNTs in solutions, UV/Vis absorption spec-
tra of the functionalized MWCNTs dissolved in ethanol at
different concentrations were collected and shown in Fig. 3.
The intensities of absorption spectra had a linear relation
with the concentration of the MWCNTs (Fig. 3, inset),
i.e. following Lambert–Beer’s law [12,40–42].
To verify the success of functionalization with the
copolymer, 1H NMR spectrum of the modified MWCNTs
in deuterated water solution was compared with that of the
block copolymer precursor as shown in Fig. 4. As expected,
the proton resonances of the free block copolymer were
found in the modified MWCNTs. The proton resonances
of the anchored block copolymers were somewhat broader

Fig. 2. (a) Photographs of functionalized MWCNT dispersed in (1) water, (2) ethanol, (3) chloroform, and (4) DMF. Sample 1 and 2 were taken after
standing for one month; 3 taken after standing for one week; 4 taken after standing for one day. (b) Defunctionalization of soluble MWCNTs before (left)
and after (right) adding 1 M of aq. HCl until the value of pH was ca. 2. (c) and (d) TEM image of modified MWCNT(SZ) and MWCNT(CD) in water.
 Z. Wang et al. / Carbon 45 (2007) 285–292 289

Fig. 5. FT-IR spectra of MWCNT–COOH, functionalized MWCNTs

Fig. 3. UV/vis absorption spectrum of modified MWCNTs in ethanol
solution for different relative concentration (1, C0; 2, 0.75 C0; 3, 0.5 C0; 4,
0.25 C0; 5, 0.1 C0). C0 denote the saturated concentration of modified
MWNTs in ethanol solution. Shown in the inset is Lambert–Beer’s plot
for the absorption at 350 nm.
and precursor block copolymer PEO-b-PDMA.
band at 1701 cm1 was assigned to carbonyl of the carbox-
ylic acid group. The derivation with PEO43-b-PDMA32
resulted in broad C–H stretches at 2800–3000 cm1 and a
shift in the location of carbonyl group from 1701 to
1720 cm1. Comparing the spectra of the modified
MWCNTs with that of the free copolymer, the similar
patterns could be observed. In the meantime, due to the
interaction between amino and carboxyl groups the band
of C–N bond present at 1342 cm1 in free copolymer
shifted to 1385 cm1. The results supported the successful
modification of the oxidized MWCNTs by the non-cova-
lent interaction.
Further evidence for zwitterionic functionalization of
the MWCNTs was provided by TGA. Fig. 6 shows the
thermograms of MWCNT–COOH, MWCNT/PEO43-
b-PDMA32, and PEO43-b-PDMA32 in range of 25–600 °C.
The modified MWCNTs had significant weight loss com-
paring to the oxidized tubes below 600 °C. Comparing

Fig. 4. 1H NMR spectrum of (a) the functionalized MWCNTs and (b) the
precursor block polymer PEO-b-PDMA in D2O solution.

and weaker than those of the free block copolymer. It was

noteworthy that the peaks of protons a,b and c, which were
close to the nitrogen shifted downfield. This phenomenon
is attributed to the interaction between amino groups and
carboxylic acids. The signal from the protons f of PEO
block was broadened and split compared with the free
block copolymer, demonstrating the carboxyl groups of
MWCNTs had an influence to the PEO blocks as well.
These results prove the block copolymers have been
attached onto the surface of MWCNTs.
As shown in Fig. 5, FT-IR spectra of MWCNT–COOH,
MWCNT/PEO43-b-PDMA32, and the free block copoly- Fig. 6. TGA traces (heating rate 10 °C /min in continuous nitrogen
mer were compared. The oxidized MWCNTs have three flow) of (a) MWCNT–COOH, (b) MWCNT-PEO43-b-PDMA32, and
characteristic bands at 1701, 1622, and 1578 cm1. The (c) PEO43-b-PDMA32 for MWCNT(CD).
290 Z. Wang et al. / Carbon 45 (2007) 285–292
the thermogram of the modified MWCNTs (b) with that of
the free block copolymer (c), it was notable that the two
thermograms have the similar two-step decomposition pro-
cess, corresponding to relevant block of the copolymer.
Moreover, the weight loss ratios of the two decomposition
processes in (b) and (c), as indicated in Fig. 6, were very
close to each other, indicating the lost mass in the modified
MWCNTs was the grafted copolymers. Further, it was of
note that the onset temperature of modified MWCNTs
was lower than pure PEO43-b-PDM32 about 50 °C. This
may be ascribed to the influence of zwitterionic interaction
between the oxidized MWCNTs and amino moieties of
PEO43-b-PDMA32. According to the TGA traces, the poly-
mer grafting yield for the oxidized MWCNTs was approx-
imately 26 wt%. Based on this data we can estimate the
molar ratio of amino and carboxylic acid groups on the sur-
face of the modified MWCNTs was around 1.4. So there
were excessive amino groups relative to the carboxylic acid
groups on the surface of the MWCNTs. The presence of
free amino groups is reasonable because of the restriction
of polymer backbone. These amino groups can be used to
capture metal nanoparticles as shown in followed section.
For the comparison, the modified MWCNT(SZ) from dif-
ferent supplier was also examined under the same experi-
mental conditions (Fig. S2 in Supporting Information).
Similar results were obtained except for the difference in
grafting yields. This may be arisen from the different
amounts of carboxylic acid groups on two MWCNTs,
which are related not only to the preparation methods but
also to the oxidizing conditions.
The influence of the block copolymer concentration on
the grafting yields was also explored. For dissolving a given
amount of oxidized MWCNTs (1 mg/mL), three different
concentrations of PEO43-b-PDMA32, 5, 10 and 20 mg/
mL, were employed to modify MWCNTs. The TGA
results (Fig. S3 in Supporting Information) showed that
the similar grafting yields were obtained at the concentra-
tion of 10 and 20 mg/mL, indicating the grafting was satu-
rated at certain concentration.
Fig. 7. TEM images of Au (a) and Pt (b) nanoparticles attachment on the modified MWCNTs.
Besides the PEO43-b-PDMA32 copolymer, four other
block copolymers with different composition (listed in
Table 1) were prepared and examined under the similar
conditions for confirming the applicability of the strategy.
For a given amount of MWCNTs (1 mg/mL), these four
copolymers could disperse the MWCNTs and form black
solutions during the given reaction time. TGA analysis of
the modified tubes collected by filtration showed that these
block copolymers could be adsorbed onto the carbon tubes
(Fig. S4 and Fig. S5 in Supporting Information).
3.2. Attachment of metal nanoparticles onto the modified
MWCNTs by using grafted block copolymer
Owing to the high aspect ratio, CNTs were regarded as a
good one-dimensional template to assembly inorganic
nanoparticles. As a result, nanotube/nanoparticle hybrid
materials can be obtained which may have useful properties
for developing new materials such as photoelectrochemical
cells, fuel cells, sensor devices, [43] or heterogeneous cataly-
sis [44–46]. Recently many papers have been published
in this field by using different strategies to support
inorganic nanoparticles [26,47–51]. Shin et al. have deco-
rated the nanotube surface with Ag nanoparticles by
using poly(vinylpyridine-b-styrene) copolymer [29]. The
MWCNTs covalent modified with poly(2-vinylpyridine)
have been applied to support metal nanoclusters [52]. The
CNTs wrapped with polymers by layer-by-layer technique
were also employed for the deposition of silica-coated gold
nanoparticles [53]. Considering the amino groups append-
ing on the surface of the modified MWCNTs, it is interest-
ing to use present modified MWCNTs as templates to
support the Au and Pt nanoparticles, which are important
in fuel cells and catalysis.
Au nanoparticles supported on the MWCNTs were con-
ducted in situ in the solution of the modified MWCNTs, in
which the aqueous solution of HAuCl4 was added and fol-
lowed by a reduction reaction. As shown in Fig. 7a, the Au
nanoparticles in range of 5–20 nm were attached onto the
 Z. Wang et al. / Carbon 45 (2007) 285–292
Fig. 8. UV–Vis spectroscopy of (a) Au nanoparticles stabilized by PEO-b-
PDMA block copolymer and (b) MWCNT/Au nanoparticles hybrids in
water.
sidewall of the MWCNTs. It is interesting to note that the
hybrid composite could form homogeneous solution in
water. UV–Vis spectra of the MWCNT/Au nanoparticle
hybrids and the Au nanoparticles stabilized by the copoly-
mer in water solution were compared in Fig. 8. The absorp-
tion of the Au nanoparticles stabilized by the free
copolymer, curve (a), exhibited a peak at 528 nm. The tube
supported Au particles, curved (b), showed a relatively
weak absorption band near to 505 nm due to the interac-
tion between MWCNTs and Au nanoparticles. This obser-
vation was in accord with the former reported result [54].
Furthermore, preformed Pt nanoparticle colloids were
mixed with the copolymer modified MWCNTs in aqueous
solution. As demonstrated in the TEM image (Fig. 7b), the
tube surfaces were densely covered by Pt nanoparticles.
Above examples indicate that the PEO-b-PDMA
copolymer can efficiently immobilize metal nanoparticles
besides stabilizing the tubes. Since excess amino groups
existed on the surface of MWCNTs, some amines of the
copolymer may have no carboxyl groups to bind, instead,
to complex with the metal nanoparticles. As comparison,
the oxidized MWCNTs without coated block copolymer
were also employed to examine attachment of the Au and
Pt nanoparticles under the same conditions. However, no
attachment of nanoparticles occurred from the TEM
observation.
4. Summary
In conclusion, we presented a facile and efficient
approach to graft a well-defined double-hydrophilic block
copolymer to the surface of oxidized MWCNTs via multi-
ple zwitterionic interactions. The PDMA blocks containing
amino groups interacted with the COOH groups of
MWCNTs and tethered onto the MWCNT surface while
the PEO segment formed a corona to enhance the solubil-
291
ity. This interaction between the polymers and the
MWCNTs should be very strong due to the multiple
anchoring sites along one polymer chain. The modified
MWCNTs can be individually dissolved in various solvents
and form homogenous solutions. Furthermore, the block
copolymer can play another function: capturing metal
nanoparticles. As examples, Au and Pt nanoparticles were
successfully attached onto the surface of the modified
MWCNTs. Beside these properties, the CNTs stabilized
by this block copolymer modifier may find potential appli-
cation in biotechnology because the PEO segment can
effectively resist the specific or non-specific adsorption of
proteins on the surface of MWCNTs. Therefore, modifica-
tion of CNTs with present block copolymer has unique
advantages comparing with small molecular amine.
Acknowledgement
Financial support from the 973 program of MOST
(G2003CB615605), NSFC (20534010) and the Chinese
Academy of Sciences (KJCX2-SW-H07) is greatly
acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can
be found, in the online version, at doi:10.1016/j.carbon.
2006.09.025.
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