Powder Technology 207 (2011) 465–469

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Short Communication

Photo-degradation of methylene blue by multi-walled carbon

nanotubes/TiO2 composites
Guohua Jiang a,b,⁎, Xiaoyan Zheng a, Yin Wang a,b, Tianwen Li a, Xinke Sun a,b
a
Department of Materials Engineering, College of Materials and Textile, Zhejiang Sci-Tech University, Hangzhou 310018, PR China
b
Key Laboratory of Advanced Textile Materials and Manufacturing Technology (ATMT), Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, PR China

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

Article history: Multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanocomposites (MWCNTs/TiO2) were
Received 6 October 2010 prepared by a liquid phase deposition method and used as a photocatalyst for degradation of methylene blue
Received in revised form 18 November 2010 (MB) in water under light irradiation. The morphology and microstructure of composites were characterized
Accepted 23 November 2010
by SEM, TEM, and XRD. It was found that the photo-degradation rate of MB under UV or visible light
Available online 1 December 2010
irradiation depended strongly on the special structure of supported catalyst, pH and electron acceptor (H2O2
used in this study). Those results showed that the MWCNTs/TiO2 composites may be used to adjust the
Keywords:
Carbides
degradation property and may extend potential applications for degradation of organic pollutants.
Composite materials © 2010 Elsevier B.V. All rights reserved.
Nanostructures
Oxidation

1. Introduction enhanced performances in the above-mentioned fields [19,20].

Carbon nanotubes (CNTs) are the most remarkable new materials
and are regarded as representatives for nanotechnology [1]. They
possess unique electrical, mechanical, and thermal properties, with
potential wide applications in the electronics, computer, aerospace, and
other industries [2–5]. To optimize the use of CNTs in various
applications, it is often necessary to assemble nanostructures onto
their surfaces. The combination of CNTs and nanoparticles are expected
to deliver exceptional performances in solar cells, catalyst, and
nanoelectronic devices [6–9]. Attaching nanoparticles onto CNTs is
also useful for the functionalization of CNTs to make coaxial nanocable,
nanoprobe, and sensor tips. Recently, attachment of various oxides onto
single-walled and multi-walled CNTs (MWCNTs), such as SiO2 [10,11],
SnO2 [12], Al(OH)3 [13] and Al2O3 [14] has been reported. However,
these methods share the common feature of synthesizing oxides onto
CNTs in a solution. Adsorption of oppositely charged polyelectrolytes
onto solid surfaces (such as CNT surfaces) in solutions can only create
very thin ion-based layers. Nanoparticle attachment onto CNTs via
electrostatic attraction in suspension has not been studied even though
it can be a simple approach to tailor the CNT surface characteristics.
TiO2 has been actively studied owing to its versatile application
potentials in optics, microelectronics, and photo-catalysis [15–18]. The
hybrid of CNTs and TiO2 nanoparticles shows unique photo-catalytic
property and electrical conductivity, and present opportunity for
Generally speaking, the common characteristics of the most of these
nanocomposites are the TiO2 nanoparticles linked or coated on CNTs.
Among the many reported methods for this binary composite, sol–gel
coating, followed by a heat-treatment at elevated temperatures, is the
most commonly adopted method to introduce the inorganic phase
onto the CNT substrate [21,22], compared to other techniques such as
chemical and physical vapor depositions [15], hydrothermal and
solvothermal syntheses [23,24], electrospinning [25], sonochemical
processing [26], self-assembly, and so forth [27,28].
Despite the significant advancement, many technical issues related
to the above process methods remain to be addressed. For instance, the
heat-treatment required in sol–gel processes often causes the phase
detachment between surface TiO2 and underneath CNTs. Furthermore,
agglomeration among neighboring TiO2/CNT cables and non-uniform
crystallite and pore sizes of the overlayer are the two major technical
drawbacks associated to the techniques that require high-temperature
treatments. In this work, we develop a facile liquid phase deposition
method that can be operated under mild reaction conditions (at 60 °C
and slightly higher than 1 atm). The anatase TiO2 has been grown
directly onto the MWCNT support. Our preliminary investigation also
indicates that the prepared MWCNTs/TiO2 composites are sufficiently
active and robust for photo-catalytic degradation of organic compounds.
2. Experimental Part

⁎ Corresponding author. Department of Materials Engineering, College of Materials
and Textile, Zhejiang Sci-Tech University, Hangzhou 310018, PR China. Tel.: +86 571
86843527.
E-mail address: polymer_jiang@hotmail.com (G. Jiang).
2.1. Materials
Multi-walled carbon nanotubes MWCNTs (outer diameter is 20–
50 nm, length 200 nm–2 μm, purity N95%) was supplied by Chengdu

0032-5910/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2010.11.029
466 G. Jiang et al. / Powder Technology 207 (2011) 465–469
Organic Chemistry Co., China and was used as received without
further purification. Butyl titanate, isopropanol, sulfuric acid and
nitrous acid were purchased from Shanghai Chemical Co., Ltd.
2.2. Preparation of CNTs/TiO2 composites
MWCNTs were modified as following procedure: 1.0 g MWCNTs
were suspended in 40 mL concentrated sulfuric acid and concentrated
nitric acid (H2SO4 HNO3 = 3 1), sonic-treated for 2 h, refluxed for 8 h
in oil bath at 100 °C, then filtered (by Millipore 0.45 μm membrane
filter) and washed with deionized water until its pH value is adjusted
to about 7; then put into 100 mL acetone, and used in synthesis of
MWCNTs and TiO2 nanocomposites.
The mixture of 6.0 mL butyl titanate and 20 mL isopropanol was
dropwise added into the MWCNT solution. 1 mL 50% sulfuric acid was
added into the solution used as the catalyst for the hydrolysis process
and then heated in oil bath at 60 °C for 24 h. After cooling down to
room temperature, the mixture was filtered by Millipore 0.45 μm
membrane filter and then washed with deionized water until its pH
value equals to about 7. The gray MWCNTs/TiO2 nanocomposite
samples were obtained after dried at 105 °C for 6 h and calcined at
450 °C for 2 h in an atmosphere ambient.
2.3. Photo-catalytic degradation property of CNTs/TiO2 composites
The photo-degradation experiments were carried out in a closed
box, whose UV radiation source is 100 W high-pressure mercury
lamp, its wavelength range is 290–450 nm, the peak intensity is
365 nm (Model OCRS-I, Kaifeng Hxsei Science Instrument Factory,
China); a photo-reactor is installed on the inside. 80 mL aqueous MB
solution and photo-catalyst suspension was magnetically stirred in a
100 mL beaker. No pure oxygen was supplied because it has enough
oxygen for oxidation photo-degradation under continuously stirring
in atmosphere in a previous experiment [29,30].
The initial methylene blue (MB) concentration (ρ) was 30 mg/L,
the photo-catalyst concentration was 1 g/L, and the pH of the solution
was adjusted to 1.7, 7.0 and 10.3 with ammonia and nitric acid
solution. Before the mercury lamp is switched on, the mixture
solution of MB and photocatalyst was sonic-treated for 5 min and
then magnetically stirred in a dark condition for 30 min to achieve
adsorption balance, then the mercury lamp was turned on and the
clear solution concentration (ρ0) was measured by JASCO V-570 UV/
Vis/NiR spectrophotometer at λmax = 546 nm wavelength; the ρ0 was
considered as the beginning concentration after dark adsorption. The
samples were withdrawn regularly from the beakers. The MB
concentrations (ρi) in different times were obtained and the
degradation rate could be expressed as following formula.
Fig. 1. SEM images of MWCNTs/TiO2 nanocomposites.
Degradation rate:
R = ðρ0 −ρi Þ = ρ0 × 100%:
2.4. Characterization
The morphology and microstructure of MWCNTs and samples of
MWCNTs/TiO2 nanocomposites were characterized with SEM (scan-
ning electron microcopy, HITACHI S-4800 instrument, Japan). The
XRD pattern was analyzed by using X-ray diffractometer (i.e. SIEMENS
Diffraktometer D5000, Germany) using Cu Kα radiation source at
35 kV, with a scan rate of 0.02°. The crystallite size of anatase TiO2 can
be determined from the line broadening by using Scherrer's formula.
The UV–Vis spectra were measured by a JASCO V-570 UV/Vis/NiR
spectrophotometer (made by JASCO Corporation, Japan). The Bru-
nauer–Emmett–Teller (BET) specific surface areas (SBET) of the
samples were determined by a high speed automated area and
pore-size analyzer (F-Sorb 3400, China).
3. Results and discussion
The SEM images of MWCNTs/TiO2 nanocomposites are given in
Fig. 1A. The outer surface of CNTs/TiO2 nanocomposites is not smooth
and displays many crinkle-like surface aligned in the longitudinal
direction of MWCNTs, as shown in Fig. 1B. It is indicated that the new
layer substrate has been covered onto the MWCNT surface.
For further exploring the surface structure of CNTs/TiO2 composite,
TEM technology was used to investigate the morphology of MWCNTs
and MWCNTs/TiO2 nanocomposites. The different magnifications of
MWCNTs and MWCNTs/TiO2 nanocomposites are shown in Fig. 2.
MWCNTs have a smooth outer wall which indicated that no particles
are absorbed on their surface, as shown in Fig. 2A and B. However, the
outer surface of MWCNTs/TiO2 nanocomposites was covered uni-
formly with many overlapping “worm-like” structures of TiO2, as
shown in Fig. 2C and the blue line area in Fig. 2D. The mean size of TiO2
is around 20–30 nm. This is due to the surface oxidation of MWCNTs
under the acid treated process and formation of defect at the oxidated
sites. The TiO2 precursor molecules, butyl titanate, were quickly
adsorbed and reacted with the functional groups (especially carboxyl)
on the MWCNT surface and water molecules subsequently generated
from condensation reaction. This led to the tight anchor of the
molecules on the host surface, forming a uniform guest coating. Upon
calcinations, the water molecules generated from condensation
reaction were removed, giving rise to the anatase TiO2 adsorbed
onto the MWCNT surface. Fig. 3 shows the reaction scheme for
preparing MWCNTs/TiO2 nanocomposites.
 G. Jiang et al. / Powder Technology 207 (2011) 465–469 467

Fig. 2. TEM images of pure MWCNTs (A), MWCNTs/TiO2 nanocomposites (C) and their corresponding higher magnification TEM images (B and D).

Fig. 3. Reaction scheme for preparing MWCNTs/TiO2 nanocomposites.

In general, the amorphous TiO2 has poor photocatalysis activities. MWCNTs with a semiconductor nature can be expected to serve as
However, if it was calcined at 450 °C in air, a part of them would electron acceptors from an excited semiconductor photocatalyst [33].
change into anatase and maybe used to be a photocatalyst [31]. The In order to study the photo-catalytic property of nanocomposites
presence of a crystalline anatase TiO2 component in the heteroge- (MWCNTs/TiO2), the degradation of methylene blue (MB) in water
neous nanostructures after calcination is further supported by XRD
measurements, as shown in Fig. 4. The strong diffraction peaks at
2θ = 25.44, 37.89, 48.25, 54.44, 63.12, 70.25 and 75.37 can be indexed
to the (101), (004), (200), (211), (204), (220) and (116) tetragonal
crystal planes of the anatase phase of TiO2 (PDF card 21-1272, JCPDS).
However, traces of an extra phase, identified as rutile, are also present
as far as a peak at 2θ = 41.34° reveals. In addition to these peaks, there
also exists a sharp peak centered on at 2θ = 25.6° that can be indexed
to the (002) plane of MWCNTs.
Specific surface area is a significant surface parameter for the
MWCNTs or MWCNTs/TiO2 nanocomposite. MWCNTs were pur-
chased without further purification with a specific surface area of
98.2 m2 g− 1. Pure TiO2 (P-25, Degussa AG, Germany has the specific
surface area with 35.9 m2 g− 1. Interestingly, titanium dioxide
nanocomposites (MWCNTs/TiO2) prepared by a liquid phase deposi-
tion show the higher specific surface area with 142.0 m2 g− 1. The
presence of MWCNTs helps to enlarge the specific surface area of
MWCNT-supported TiO2 samples significantly which leads to their
higher adsorptive ability [32]. Fig. 4. XRD pattern of MWCNTs/TiO2 nanocomposites after calcination.
468 G. Jiang et al. / Powder Technology 207 (2011) 465–469
Fig. 5. The percent of degradation of methylene blue (MB) at UV light or sunlight
irradiation for 30 min over TiO2 or MWCNTs/TiO2 with the presence (CH2O2 = 10 wt.%)
or absence of H2O2. CMB = 30 mg/L, Ccatalyst = 1 g/L (A: TiO2, UV light irradiation and
H2O2; B: TiO2, UV light irradiation and no H2O2; C: TiO2, Sunlight irradiation and; D:
TiO2, Sunlight irradiation and no H2O2; E: MWCNTs/TiO2, UV light irradiation and H2O2;
F: MWCNTs/TiO2, UV light irradiation and no H2O2; G: MWCNTs/TiO2, Sunlight
irradiation and H2O2; and H: MWCNTs/TiO2, Sunlight irradiation and no H2O2).
under light irradiation was investigated. The percent of degradation
rate (R) of methylene blue (MB) at UV light or visible light irradiation
over TiO2 or MWCNTs/TiO2 with the assistance of H2O2 or not is
shown in Fig. 5. The MWCNTs/TiO2 shows higher degradation capacity
at the neutral and alkaline environment, which has some connection
with its special structure, but has poor removal rate at the acidic
solution. Comparing the histograms of the photo-catalytic degrada-
tion of MB over TiO2 or MWCNTs/TiO2 (Fig. 5A and E), the MWCNTs/
TiO2 composites have a higher degradation rate than pure TiO2,
because the MWCNTs/TiO2 composites are more active than pure TiO2
nanoparticles for adsorption of organic substance for their higher
specific surface area. The photo-catalytic degradation property of MB
was also investigated with the assistance of H2O2 or not. It is clear
from the figure (Fig. 5A and B) that the rate of the photo-catalytic
degradation of MB was higher under the assistance of H2O2. At
pH = 7.0, more than 80% of MB has been photo-degraded in the
presence of H2O2, and only about 20% with the absence of it. These
observations were due to the electron acceptor behavior of H2O2,
which reacted with conduction band electrons to generate hydroxyl
radicals, required for photo-catalytic degradation of organic pollu-
tants [30].
Fig. 6. The photo-catalytic degradation of MB against residence time (A, CMB = 30 mg/L, Ccatalyst = 1 g/L) and digital illumination photographs of the MB aqueous solution under UV
light irradiation at different pH values (B).
Fig. 6A shows the photo-catalytic degradation of MB against
residence time. It is clear from the figure that the rate of photo-
catalytic degradation of MB is higher at the neutral and alkaline
environment. 50% photo-degradation of MB can be observed at τ1/2 =
7.0 and 12.4 min for pH at 10.3 and 7.0, respectively. However, in the
acidic condition, only 42.5% of MB has been photo-degraded under UV
light irradiation for 60 min. Fig. 6B shows the digital illumination
photographs of the MB aqueous solution under UV light irradiation at
different pH values. At pH = 10.3 and 7.0, the color of the solution
fades gradually with the extension of irradiation time. While, it has
almost no great change in color at pH = 1.7. The reason for this is the
pH influences the adsorption property of organic compounds and
their dissociating state in the solution. The surface charge properties
of TiO2 are also changed with the changes in the pH value due to
amphoteric behavior of semi-conducting TiO2. The point of zero
charge (pzc) for titanium dioxide is at pH 6.5. The TiO2 surface is
positively charged in the acidic solution and negatively charged in the
basic solution. Since MB is a cationic dye, it is conceivable that at a
higher pH value, its adsorption is favored on a negatively charged
surface [31].
4. Conclusion
In summary, we developed a facile liquid phase deposition method
that could be operated under mild reaction conditions (at 60 °C and
slightly higher than 1 atm). The anatase TiO2 has been grown directly
onto the MWCNT support. Furthermore, high specific surface area,
uniform crystallite size, and narrow single-modal pore-size distribu-
tion have been achieved with this wet chemical process. The
morphology and microstructure of composites were characterized
by SEM, TEM, and XRD. Our preliminary investigation also indicates
that the prepared TiO2/CNTs are sufficiently active and robust for
photo-catalytic degradation of organic compounds. The photo-
degradation rate of MB under UV or visible light irradiation depended
strongly on the special structure of supported catalyst, pH and
electron acceptor (H2O2 used in this study). Those results showed that
the MWCNTs/TiO2 composites may be used to adjust the degradation
property and may extend potential applications for degradation of
organic pollutants.
Acknowledgements
This work was financially supported by the TORAY Research Fund
(0901056-J), the Qianjiang Talents Project of Zhejiang Province
(2010R10023), the Scientific Research Foundation for the Returned
 G. Jiang et al. / Powder Technology 207 (2011) 465–469
Overseas Chinese Scholars, State Education Ministry (1001603-C), the
Natural Science Foundation of Zhejiang Province (Y4100045), the
Foundation of Zhejiang Province New Textile Research & Develop-
ment Emphasised Laboratory (2009FZD001), the Key Bidding Project
of Zhejiang Provincal Key Lab of Fiber Materials and Manufacturing
Technology, Zhejiang Sci-Tech University (S2010002) and the
Program for Changjiang Scholars and Innovative Research Team in
University (PCSIRT: 0654).
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