Applied Catalysis A: General 289 (2005) 186–196

www.elsevier.com/locate/apcata

Enhancement of photocatalytic activity of mesoporous TiO2

by using carbon nanotubes
Ying Yu a,c, Jimmy C. Yu b,d, Jia-Guo Yu e, Yuk-Chun Kwok a, Yan-Ke Che f,
Jin-Cai Zhao f, Lu Ding g, Wei-Kun Ge g, Po-Keung Wong a,d,*
a
Department of Biology, The Chinese University of Hong Kong, Shatin, NT, Hong Kong SAR, China
b
Department of Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong SAR, China
c
College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China
d
Environmental Science Programme, The Chinese University of Hong Kong, Shatin, NT, Hong Kong SAR, China
e
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
f
Center for Molecular Science, Institute of Chemistry, The Chinese Academy of Science, Beijing 100080, China
g
Department of Physics, Hong Kong University of Science and Technology, Clear Bay, Kowloon, Hong Kong SAR, China
Received 25 November 2004; received in revised form 18 April 2005; accepted 27 April 2005
Available online 13 June 2005

Abstract

Titanium dioxide/carbon nanotubes (TiO2/CNTs) composites were prepared with the aid of ultrasonic irradiation. Products of different
TiO2:CNTs molar ratio were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS),
scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) adsorption analysis, thermogravimetric and differential thermal
analysis (TGA–DSC), photoluminescence (PL) and UV–vis spectroscopy measurements (UV–vis). The photocatalytic activity was
evaluated by the degradation of acetone and by the detection of the hydroxyl radical (
OH) signals using electron paramagnetic resonance
(EPR). It is found that the crystalline TiO2 is composed of both anatase and brookite phases. The agglomerated morphology and the particle
size of TiO2 in the composites change in the presence of CNTs. The CNTs in the composites are virtually all covered by TiO2. Other than an
increase of the surface area, the addition of CNTs does not affect the mesoporous nature of the TiO2. Meanwhile, more hydroxyl groups are
available on the surface of the composite than in the case of the pure TiO2. The higher the content of CNTs, there is more effective in the
suppression of the recombination of photo-generated e/h+ pairs. However, excessive CNTs also shield the TiO2 from absorbing UV light.
The optimal amount of TiO2 and CNTs is in the range of 1:0.1 and 1:0.2 (feedstock molar ratio). These samples have much more highly
photocatalytic activity than P25 and TiO2/activated carbon (AC) composite. The mechanism for the enhanced photocatalytic activity of
TiO2 by CNTs is proposed.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Carbon nanotubes; Photocatalytic activity; Organic pollutant; TiO2; Sonochemistry; Enhancement; Hydroxyl radical

1. Introduction toxicity and long-term photostability [2]. Unfortunately, the

The use of heterogeneous photocatalytic oxidation for
water and air purification and remediation is the subject of a
wide range of investigations [1]. Among various oxide
semiconductor photocatalysts, titania is the most common
one because of its strong oxidizing power, absence of
* Corresponding author. Tel.: +852 2609 6383; fax: +852 2603 5767.
E-mail address: pkwong@cuhk.edu.hk (P.-K. Wong).
photocatalytic activity of pure titania is not high enough for
industrial purposes [3]. Several methods have been reported
to improve the photocatalytic efficiency. These include
increasing the surface area of TiO2, the generation of defect
structures to induce space-charge separation, and the
modification of TiO2 with metal(s) or other semiconduc-
tor(s) [4–6]. Another method that might possibly increase
the photocatalytic efficiency of TiO2 is to add a co-sorbent
such as silica, alumina, zeolites or clay, but no apparent

0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.04.057
 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
improvement of photocatalytic efficiency is observed [7–9].
Therefore, the development of new materials for modifying
TiO2 is urgently needed to increase the photocatalytic
activity of TiO2 for organic pollutant treatment.
Carbon nanotubes (CNTs) attract considerable attention
since their discovery [10] due to their special structure, their
extraordinary mechanical and unique electronic properties
and their potential applications. Their high mechanical
strength makes them to be good candidates for advanced
composites [11]. They can either be semiconducting, semi-
metallic or metallic, depending on the helicity and the
diameter of the tube [12]. Such variety opens a promising
field in nanoscale electrodevice applications. Their large
specific surface area, hollow and layered structures indicate
that they can be ideal hydrogen storage materials [13].
Recently, researchers found that CNTs are efficient
adsorbents for dioxin, fluoride, lead and cadmium [14–
17]. Thus, CNTs can be used as a promising material in
environmental cleaning. CNTs can conduct electrons
[18,19] and have a high adsorption capacity. Anatase
TiO2 is known for its superior photocatalytic ability
compared with other photocatalysts. Therefore, the applica-
tion of CNTs to enhance the photocatalytic activity of TiO2
is proposed.
Mesoporous TiO2 is a highly photocatalytically active
photocatalyst because it has a high surface-to-volume ratio
and offers more active sites for carrying out catalytic
reactions [20]. Recently, sonochemical processing has been
proven to be a useful technique in the synthesis of
mesoporous TiO2 with high photocatalytic activity
[21,22]. In this study, mesoporous TiO2 and TiO2/CNTs
composites were prepared by the ultrasound technique. We
investigated the effect of CNTs on the microstructure,
physicochemical properties, and photocatalytic activity of
TiO2 for the degradation of air pollutant acetone by X-ray
diffraction (XRD), Raman spectroscopy, X-ray photoelec-
tron spectroscopy (XPS), scanning electron microscopy
(SEM), Brunauer–Emmett–Teller (BET) adsorption analy-
sis, thermogravimetric analysis and differential thermal
analysis (TGA–DSC), photoluminescence (PL), UV–vis
spectroscopy (UV–vis) and electron paramagnetic reso-
nance (EPR). To the best of our knowledge, this is the first
report about utilizing TiO2/CNTs composites in photo-
catalysis.
2. Experimental
2.1. Materials
CNTs (multiwall CNTs) were synthesized by the
catalytic decomposition of acetylene at 780 8C using Co
and Fe catalyst [23,24]. For the purification, 8 g of raw
CNTs were boiled in 400 mL of concentrated nitric acid
(65% HNO3, Merck, Germany) for 40 min to get oxygenated
functionalities on the nanotube surface. Then, the CNTs
187
were filtered, washed with 600 mL distilled water for five
times to remove acid, and finally dried at 105 8C in an oven
(Shel-Lab 1350 FX, Sheldon Manufacturing Inc., USA).
After treatment, most of the impurities disappear and the
surface of CNTs becomes cleaner. Moreover, the strong acid
treatment generates several types of functional groups,
including hydroxyl groups (3416 cm1), carboxyl groups
(1721 cm1) and carbonyl groups (1583 cm1) [24], on the
surface of the CNTs. The diameters of the treated CNTs
were about 10–40 nm and the lengths were several
micrometers [24].
Activated carbon (AC) (F-300) was purchased from
Calgon Carbon Corporation, its surface area is 825 m2/g.
Before use, AC was ground to fine powders with a mesh size
of about 350 mm.
2.2. Preparation and characteristic of TiO2 and TiO2/
CNTs composites
CNTs as a support were combined with TiO2 through
sonochemical and calcination methods. The treated CNTs
were used because their adsorption ability is higher than that
of raw CNTs [15–17]. To synthesize the TiO2/CNTs
composite, titanium tetraisopropoxide (TTIP, Aldrich,
USA) was used as a titanium source. Firstly, CNTs were
sonicated in 20 mL ethanol for 15 min to disperse them well.
Then, each mixture of TTIP and CNTs, with a different mole
ratio of titanium and carbon (1:0.1, 1:0.2, 1:0.5, 1:1 and 1:2,
respectively), was sonicated for 30 min to improve the
interaction between the two chemicals. After 80 mL Milli-Q
water was added, the sol samples formed by the hydrolysis
process were treated with ultrasonic irradiation in an
ultrasonic cleaning bath (Branson B2510E-MTH, USA) for
another 30 min, followed by ageing at 25 8C for 20 h in
order to further hydrolyze the TTIP and form monodispersed
TiO2 particles [21]. These samples were then dried in a
100 8C oven for 8 h. Finally, the dried mixtures were
calcinated in a 400 8C furnace (Ney VULCANTM 3-1750,
Germany) for 1 h, and the TiO2/CNTs composites, with the
color from white grey to black when increasing the amount
of CNTs, were obtained. The abbreviations of the TiO2/
CNTs composites with different molar ratios are shown in
Table 1. The actual loading amount of TiO2 in the
composites was estimated from TGA–DSC detection and
the data corrected from the content of pure TiO2 in the
sample are also present in Table 1. The preparation process
of TiO2 was similar to that of the composites, except that the
first 15 min sonication for the CNTs dispersion was skipped.
For comparison, the TiO2/AC composite was also synthe-
sized by a process similar to that used for TiO2/CNTs
composites. The molar ratio of Ti and AC was 1:0.2.
XRD patterns of the prepared TiO2 and TiO2/CNTs
composites were analyzed by a Bruker D8 Advance X-ray
diffractometer (Germany) using Cu Ka radiation at a scan
rate of 0.058. Raman spectra were detected by a Renishaw
RM3000 Micro-Raman system (UK). XPS spectra were
188 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196

Table 1
Summary of the physicochemical properties of TiO2 and TiO2/CNTs composites
Material TiO2 ratio in Material Anatase Brookite SBET Pore Pore volumef
composites (wt.%)a abbreviations Crystalline Content (%) c content (%) c (m2/g) d sizee (nm) (mL/g)
sizeb (nm)
TiO2 100 TiO2 8.3 83.7 16.3 127 7.05 0.32
TiO2/CNTs (1:0.1)g 97 Ti/C-1 – – – 137 8.46 0.33
TiO2/CNTs (1:0.2)g 95 Ti/C-2 8.3 85.0 15.0 142 9.14 0.35
TiO2/CNTs (1:0.5)g 91 Ti/C-3 8.2 88.0 12.0 147 8.23 0.37
TiO2/CNTs (1:1)g 85 Ti/C-4 – – – 161 9.68 0.39
TiO2/CNTs (1:2)g 75 Ti/C-5 7.6 89.9 10.1 168 8.04 0.42
a
Estimated from the data of TGA–DSC measurement and corrected from the content of pure TiO2 in the sample.
b
Calculated by the Scherrer formula.
c
Calculated using the formula in Ref. [28].
d
BET surface area calculated from the linear part of the BET plot.
e
BJH desorption average pore diameter (4V/A).
f
Single point total pore volume of the pores at P/P0 = 0.97.
g
The mole ratio of TiO2 and CNTs.

recorded on a PHI Quantum 2000 XPS system (USA) with a
monochromatic Al Ka source and a charge neutralizer. BET
surface areas (SBET) and porous structure were determined
by using a Micromeritics ASAP 2010 nitrogen adsorption
apparatus (USA). All samples were degassed at 180 8C
before the measurements. The microstructures of the
samples were determined by using a field emission SEM
(JEOL JSM-6700F) (Japan). TGA–DSC was recorded on a
NETZSCH STA 449C (Germany) thermal analysis instru-
ment and the scan rate was 108/s at air atmosphere. The PL
emission spectra of the samples were measured using the
following procedure: firstly, at 261 8C, a 325 nm He–Cd
laser was used as an excitation light source; then the light
from the sample was focused into a spectrometer (Spex500)
and detected with a photo-multiplier tube (PMT); and
finally, the signal from the PMT was input into a photon
counter (SR400) before being recorded by a computer. A
Varian Cary 100 Scan UV–vis system (USA) equipped with
a Labsphere diffuse reflectance accessory (USA) was used to
obtain the reflectance spectra of the samples over a range of
200–800 nm. A Labsphere USRS-99-010 was employed as a
reflectance standard. EPR signals of radicals spin-trapped
with 5,5-dimethyl-pyrroline-N-oxide (DMPO) were
recorded with a Bruker EPR 500 E spectrometer (Germany).
The irradiation wavelength of the laser exciter is 355 nm.
The settings for the EPR spectrometer were: center
field = 3486.70 G; sweep width = 100.0 G; microwave fre-
quency = 9.82 GHz; power = 5.05 mW.
2.3. Measurement of photocatalytic degradation of
acetone
Acetone (CH3COCH3) is a common chemical that is used
extensively in a variety of industrial and domestic
applications. For example, acetone is frequently used as a
solvent in the printing industry and in analytical labora-
tories; it is a major constituent of many common household
chemicals [25]. Therefore, we selected it as a model
contaminate chemical. Photocatalytic oxidation of acetone
is based on the following reaction [25]:
CH3 COCH3 þ 4O2 ! 3CO2 þ 3H2 O (1)
The photocatalytic activity experiments on TiO2 and TiO2/
CNTs powders for the oxidation of acetone in air were
performed at ambient temperature using a 7000 mL reactor.
The photocatalysts were prepared by coating an aqueous
suspension of sample powders onto two dishes with dia-
meters of 7.0 cm. The weight of the photocatalyst used for
each experiment was kept at about 0.1 g. For TiO2/CNTs
composites, 0.1 g is the total amount of TiO2 and CNTs. The
photocatalysts were pretreated in an oven at 100 8C for about
2 h and then cooled to 25 8C before use. After the dishes
coated with these powder photocatalysts were placed in the
reactor, a small amount of acetone was injected into the
reactor. The reactor was connected to a dryer containing
CaCl2 that was used for controlling the initial humidity in
the reactor. The analysis of acetone, carbon dioxide, and
water vapor concentration in the reactor was conducted with
a Photoacoustic IR Multigas Monitor (Model 1312,
INNOVA Air Tech Instruments, Denmark). The acetone
vapor was allowed to reach adsorption equilibrium with
the catalyst in the reactor prior to each experiment. The
initial concentration of acetone after the adsorption equili-
brium was about 400 mg/L. This value remained constant
until a 15 W 365 nm UV lamp (Cole-Parmer Instrument,
USA) in the reactor was switched on. The initial concentra-
tion of water vapor was 1.20  0.01 vol.%, and the initial
temperature was 25  1 8C. During the photocatalytic reac-
tion, we observed about a 3:1 ratio of carbon dioxide
products to acetone destroyed, and the acetone concentration
decreased steadily with increase in UV illumination time.
Each reaction was followed for 60 min.
The photocatalytic activity of the samples can be
quantitatively evaluated by comparing the apparent reaction
rate constants. The photocatalytic degradation generally
follows a Langmuir–Hinshelwood mechanism [26] with the
 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
rate r being proportional to the coverage u:
kKc
r ¼ ku ¼ (2)
1 þ Kc
where k is the true rate constant which includes various
parameters such as the mass of catalyst and the intensity of
light, and K is the adsorption constant. Since the initial
concentration is low (c0 = 400 mg/L = 4.29  103 mol/L),
the term Kc in the denominator can be neglected with respect
to unity and the rate becomes, apparently, first order:
dc
r¼ ¼ kKc ¼ ka c (3)
dt
where ka is the apparent pseudo-first order rate constant. The
integral form c = f(t) of the rate equation is
c0
ln ¼ ka t (4)
c of anatase and brookite in the TiO2 of composites are shown
3. Results and discussion
3.1. Characterization of the prepared TiO2 and TiO2/
CNTs composites
To characterize the crystalline structure of the samples,
the XRD patterns of TiO2 and TiO2/CNTs composites
(Fig. 1) are obtained. If one compares these with the pattern
of pure CNTs (Supplementary data), one finds that there is
no apparent peak in these composites at the positions of 26.0
and 43.4, which are the characteristic peaks for CNTs [27].
Only anatase (JCPDS no. 21-1272) and brookite (JCPDS no.
29-1360) phases attributed to TiO2 are present. The reason
may be that the main peak of CNTs at 26.0 is overlapped
with the main peak of anatase TiO2 at 25.4 since their
positions are so close. Moreover, the crystalline extent of
CNTs is much lower than that of TiO2, leading to the
shielding of the peaks of CNTs by those of TiO2. The phase
Fig. 1. XRD patterns of TiO2 and TiO2/CNTs composites: A denotes
anatase; B denotes brookite.
189
content of TiO2 in a sample can be calculated from the
integrated intensities of anatase (1 0 1), rutile (1 1 0) and
brookite (1 2 1) peaks with the following formulas [28]:
kA AA
WA ¼ (5)
k A AA þ A R þ k B AB
AR
WR ¼ (6)
k A AA þ AR þ k B AB
kB AB
WB ¼ (7)
k A AA þ AR þ k B AB
WA, WR and WB represent the weight fractions of anatase,
rutile and brookite, respectively. The other symbols AA, AR
and AB are the integrated intensities of anatase (1 0 1), rutile
(1 1 0) and brookite (1 2 1) peaks, respectively. The vari-
ables kA and kB are two coefficients; their values are 0.886
and 2.721, respectively [28]. The calculated phase contents
in Table 1. It can be seen that with the increase of the amount
of CNTs, the size for anatase crystalline becomes smaller,
the anatase content in the composites increases and corre-
spondingly the brookite content becomes detrimental gra-
dually. It is well known that only anatase phase in TiO2 has a
highly photocatalytic activity. Thus, the composites with
high CNTs level may have a good photocatalytic activity.
Raman spectroscopy was applied to unambiguously
discriminate the local order characteristics of TiO2 [29,30].
The technique is capable of elucidating the photocatalyst
structural complexity as peaks from each material are clearly
separated in frequency, and therefore the phases are easily
distinguishable. Fig. 2 shows the comparison of the Raman
spectra of TiO2 and the TiO2/CNTs composites. A well-
resolved TiO2 Raman peak is observed at about 145 cm1
for all the samples. This peak is attributed to the main Eg
anatase vibration mode. Furthermore, vibration peaks at
400 cm1 (B1g), 517 cm1 (A1g) and 640 cm1 (Eg) are
present in the spectra, indicating that the anatase crystallites
in the materials are the major species [29]. Meanwhile, there
are two weak peaks at 246 and 322 cm1, which are
attributed to A1g and B1g vibration modes for the brookite
phase of TiO2 [31]. No peak assigned to rutile phase is
observed in Fig. 2. Thus, the prepared TiO2 is composed of
anatase phase and brookite phase, which corresponds to the
results shown in Fig. 1. For the spectra of Ti/C-2 and Ti/C-4
in the wave number range between 1200 and 1700 cm1,
there is a broad and weak peak shown at 1600 cm1 in Ti/C-
2. However, the intensity of the peaks at 1332 cm1 and
about 1600 cm1 in the sample of Ti/C-4 is high. The peak at
1332 cm1 is assigned to the ill-organized graphite, the so-
called D-line in CNTs [32]. The broad peak at around
1600 cm1 is an unresolved Raman triplet identified with
tangential carbon atom displacement modes, which is
related to the E2g mode in graphite at 1582 cm1 [33]. With
the increase of the content of CNTs in the composites, it is
reasonable that the peaks attributed to CNTs become strong.
Thus, the peak at about 1340 cm1 in the sample Ti/C-2 is so
190 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196

Fig. 2. Raman spectra for TiO2, Ti/C-2 and Ti/C-4. Inset is the fitting curve of E2g mode of graphite with Lorentzian equation. The superscript A denotes anatase
phase of TiO2; B denotes brookite phase of TiO2; and C denotes CNTs.

weak that it can hardly be observed. By fitting the inset
figure with a Lorentzian equation, we find that the peak at
around 1600 cm1 is split into two peaks at 1582 and
1612 cm1, respectively. Although E2g mode in graphite can
be split into A1g, E1g and E2g three modes [34], Raman
spectrum of pure CNTs has no peak at 1612 cm1. Thus, the
appearance of the new peak at 1612 cm1 indicate that there
is a strong interaction between TiO2 and CNTs through
chemical adsorption of carboxyl acid group on the surface of
the oxidized CNTs onto the surface of TiO2 by the formation
of ester-like linkages [35].
Fig. 3 shows the effect of CNTs amount on the N2
adsorption–desorption isotherm and pore size distribution of
TiO2. The effect of BET surface areas, average pore
diameter and pore volumes is listed in Table 1. For the N2
adsorption–desorption isotherm for TiO2, it is type IV with
H2 hysteresis-loop, characteristic of mesoporous materials
[36]. The pore size distribution of the sample is narrow and
the pore size changes in the range 2.5–12.5 nm. When CNTs
are composited with TiO2, the N2 adsorption–desorption
isotherm and pore size distribution of TiO2 do not change
greatly. The composites still have mesoporous structures
although the shape of these hysteresis-loops changes slightly
with the increase of CNTs content. However, the pore size
distribution of the sample Ti/C-5 becomes broader. The pore
size is in the range 2.5–17.5 nm. Moreover, with the increase

Fig. 3. BJH pore size distribution plot and N2 adsorption–desorption isotherm (inset) of TiO2 and the TiO2/CNTs composites with different mole ratios.
 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
of CNTs content in the composites, the SBET and pore
volume of the composites increase gradually. CNTs have a
larger surface area of 292 m2/g and their pore size
distribution is broader (Supplementary data). It is reasonable
that the presence of CNTs in TiO2 leads to the increase of
SBET and the presence of a large amount of CNTs results in
the broader pore size distribution of this composite Ti/C-5.
The mesoporous structure of these samples is formed by
the agglomeration of TiO2 nanoparticles under high-intensity
by ultrasound irradiation. Slow hydrolysis under high-
intensity ultrasound irradiation promotes the formation of
monodispersed TiO2 sol particles. Thus, the mesoporous TiO2
with a relatively narrow pore size distribution is produced by
the ultrasound induced agglomeration of the monodispersed
TiO2 sol particles [22]. The reason for the fact that the
presence of CNTs does not destroy these mesoporous
structures may be the presence of ethanol in the sol samples
before the strong hydrolysis. The evaporation of ethanol in
high temperature leads to the formation of pores, in which
ethanol once was present. Here, the functions of ethanol are
not only as a dispersing solvent but also as a soft template.
The field emission SEM images of the samples TiO2, the
composites Ti/C-2 and Ti/C-4 are shown in Fig. 4. All
samples have pores in their structures, which are connected
Fig. 4. SEM images of TiO2 and the TiO2/CNTs composites: (a) TiO2, (b) Ti/C-2, and (c) Ti/C-4.
191
randomly and lack discernible long-range order in the pore
arrangement. It is also found that, with the increase of the
amount of CNTs, the morphology of TiO2 changes from
spherical particles (Fig. 4a), big agglomerated particles
(Fig. 4b) to bulk (Fig. 4c) and there are more and more CNTs
observed in the composites. Thus, CNTs have an effect on
the agglomerated morphology of TiO2. Meanwhile, the
agglomeration of monodispersed TiO2 particles can be
clearly observed in the SEM image with a higher resolution
(Supplementary data). The spherical TiO2 particles with the
size of about 40 nm (Fig. 4a) composed of the nanoparticles
with the diameter of about 10 nm, which is basically in
accordance with the crystalline size calculated from their
XRD patterns. A similar phenomenon is found in the
composite Ti/C-4. The bulk TiO2 in the composite is
composed of smaller particles with the size of several
nanometers (Supplementary data). Thus, CNTs also affect
the size of TiO2 crystallites. The CNTs in the composites are
well dispersed and almost covered by TiO2 (Fig. 4b and c) so
that it can be speculated that under ultrasound irradiation,
CNTs and TTIP contact with each other. When the
hydrolysis of the sol samples starts, CNTs gradually interact
with TiO2 through strong chemisorption [35] (Fig. 2). Due to
the interaction between TiO2 and CNTs and with the
192 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196

very stable since there is only a slight weight loss (about

3.6%) appears in the range of 100–200 8C, which
corresponds to the removal of the adsorbed water and
may include the evaporation of a small amount of ethanol
(Fig. 5a). The composite Ti/C-2 is not as stable as TiO2
(Fig. 5b). In the range of the measured temperatures, the
total weight loss is 8.5%, larger than that of TiO2.
Meanwhile, there are two observed weight losses: the first
one, in the range of 100–300 8C, corresponds to the removal
of adsorbed water and ethanol, measuring to about 3.5%, the
second one corresponds to a larger endothermic peak at
545 8C, which is resulted from the removal of CNTs in the
composites since the materials start to evaporate at 500 8C
(Supplementary data). Meanwhile, there are no exothermic
peaks at around 450 8C appearing in either of the curves
(Fig. 5a and b) so that there is no transformation of brookite
to anatase phase in these prepared samples [22]. One
possible reason is that the samples have been calcinated in
400 8C for 1 h and the brookite phase has thus become more
stable. The TiO2/CNTs composite is thermally stable, which
is good for the practical applications.
Fig. 6 shows the high-resolution XPS spectra for the O 1s
region for TiO2 and the composite Ti/C-2. The O 1s region is
composed of two peaks. One peak is attributed to the Ti–O in
TiO2 and the composite, while the other one is assigned to
the hydroxyl group. Table 2 lists the results of curve fitting of
XPS spectra for the two samples. The contribution of each

Table 2
Results of curve fitting of high-resolution XPS spectra with Gaussian
equations for the O 1s region of the sample TiO2 and the composite Ti/
C-2
Fig. 5. TGA–DSC curves of TiO2 (a) and Ti/C-2 (b). Materials O 1s (Ti–O) O 1s (OH)
TiO2
Eb (eV) 530.7 531.8
limitation of CNTs, TiO2 crystalline particles may not grow Area 3960 3131
larger and it is not easy for the TiO2 small particles to be ri (%) 55.85 44.15
assembled in an orderly way to form monodisperse spherical Ti/C-2
big particles [37]. Eb (eV) 530.8 531.5
The TGA–DSC curves of the samples of TiO2 and Ti/C-2 Area 2402 2148
are presented in Fig. 5. It is found that the obtained TiO2 is ri (%) 52.79 47.21

Fig. 6. High-resolution XPS spectra of O 1s region of TiO2 and the composite Ti/C-2.
 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
type of oxygen is expressed by ri (%). It is noted that the
hydroxyl content in the composite is higher than that in
TiO2, which indicates that the amount of the hydroxyl group
from the chemisorption of water molecules on the surface
TiO2 [38] is enhanced by the presence of CNTs with large
surface area. Although some H2O is easily adsorbed on the
surface of the samples, the physically adsorbed water on the
samples is desorbed under the ultra-high vacuum condition
of the XPS system. Therefore, XPS spectra only show
chemisorbed H2O. The increase in hydroxyl content on the
surface of the composite can enhance the photo-induced
super-hydrophilicity and photocatalytic activity [39,40].
3.2. Photocatalytic activity on the oxidation of acetone
of TiO2 and TiO2/CNTs composites
The photocatalytic activities of TiO2 and TiO2/CNTs
composites were evaluated by using the oxidation of acetone
in air. For comparison, the activity of commercial
photocatalyst, P25, and synthesized TiO2/AC composite
were tested under the same conditions. Fig. 7 shows the
comparison of the apparent rate constants ka for the different
photocatalysts. The value of ka for TiO2 is slightly larger
than that for P25, which is attributed to the porous structure
and large surface area of TiO2 prepared by the sonochemical
method. The photocatalytic activity of TiO2 is larger than
that of TiO2/AC composite, which indicates that AC cannot
enhance the photocatalytic activity of TiO2 for the
degradation of acetone under the experimental conditions.
When a small amount of CNTs are present in the
composites, the value of ka increases greatly and rapidly.
However, with the increase of the CNTs content in the
composites, the photocatalytic activity decreases gradually.
The optimum content of CNTs in the composites is 0.1–
0.2 mol/1 mol of TiO2 (feedstock ratios). The photocatalytic
activities of the samples Ti/C-1 and Ti/C-2 are much higher
than those of P25 and the TiO2/AC composite. Therefore,
CNTs can greatly enhance the photocatalytic activity of
TiO2.
Fig. 7. Photocatalytic activity comparison of the samples of TiO2, Ti/C-1,
Ti/C-2, Ti/C-3, Ti/C-4, Ti/C-5, P25 and TiO2/AC. The molar ratio of Ti and
AC for the TiO2/AC composite is 1:0.2.
193
Fig. 8. UV–vis spectra of the samples of TiO2, Ti/C-1, Ti/C-2 and Ti/C-4.
The results in Table 1 show that the anatase phase content
in TiO2/CNTs composites increases with the increase of the
amount of CNTs. Here, the photocatalytic activity of the
composites with high CNTs content is much lower,
especially for the samples Ti/C-4 and Ti/C-5. Are these
two aspects contradictory? The reason that more CNTs
inhibit the photocatalytic activity of TiO2 may be explained
by the UV–vis absorbance spectra of the samples of TiO2,
Ti/C-1, Ti/C-2 and Ti/C-4 (Fig. 8). It is found that, with the
increase of the CNTs content, the absorption of UV light by
the composites decreases greatly. When the molar ratio of
carbon and titania in the composite is 1:1 (sample Ti/C-4),
there is no absorption at all for the composite. The color of
CNTs is black so that they can shield the UV light for the
absorption by TiO2. If there is no UV absorption for TiO2,
the sample cannot show any photocatalytic activity. Thus,
when the CNTs content in 1 mol of TiO2 is more than
0.5 mol (feedstock ratio), the photocatalytic activity of the
composites will be lower than that of the pure TiO2, i.e. no
enhancement effect of the photocatalytic activity of TiO2 by
CNTs. For a photocatalyst, light absorption is the most
critical factor.
3.3. Mechanism for the enhancement of the
photocatalytic activity of TiO2 by CNTs
Activated carbon (AC) has been reported to facilitate the
photocatalytic efficiency of TiO2 for the removal of phenolic
series organic pollutants as a co-adsorbent due to its very
high surface area (more than 800 m2/g) [41–44]. The surface
area of CNTs is much less than that of AC. Thus, adsorption
will not be the only factor for the enhancement of the
photocatalytic activity of TiO2 by CNTs. CNTs have 1D
carbon-based ideal molecule with the nanocylinders, which
can conduct electricity at room temperature with essentially
no resistance. This phenomenon is known as ballistic
transport [45–47], where the electrons can be considered as
moving freely through the structure, without any scattering
from atoms or defects. While the electrons formed by the
194 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
Fig. 9. Photoluminescence (PL) spectra: comparison of the samples of
TiO2, Ti/C-1, Ti/C-4 and CNTs.
UV irradiation migrate to the surface of TiO2, it is easy for
the electrons to transport in CNTs which are bound with
TiO2. Thus, the high rate of e/h+ pair recombination, which
reduces the quantum yield of the TiO2 process, can decrease.
This can be confirmed by photoluminescence (PL) spectra of
the composites.
The PL emission spectra have been widely used to
investigate the efficiency of charge carrier trapping,
immigration and transfer, and to understand the fate of
e/h+ pairs in semiconductor particles [2]. In order to study
the effect of CNTs on the recombination of e/h+ produced
by TiO2, the PL spectra are detected for the composites
(Fig. 9). TiO2 powder shows a broad PL emission band,
which is similar to the results of a previous study [48]. The
emission band corresponding to the peak position of about
525 nm is for anatase powder [49]. Compared with the
spectrum of TiO2, it is found that the PL spectra of the
composites Ti/C-1 and Ti/C-4 in the same range of
wavelength are much lower than that of pure TiO2,
especially for sample Ti/C-4, little photoluminescence is
observed. Since the observed PL spectrum in TiO2 can be
attributed to the radiative recombination process of self-
trapped excitations [2,48,50], the reduction of PL intensity
in the sample Ti/C-1 and Ti/C-4 indicates the decrease of the
radiative recombination process. Thus, with the assistance of
CNTs, the recombination of e/h+ excited by TiO2 under UV
light can be detrimental. The capacity of e transport for
CNTs has been widely used for the composition with p-
conjugated polymers for the application of light-emitting
diodes, field effect transistors and photovoltaic devices [51].
It has been confirmed that photo-induced charge transfer
occurs in the electronic interaction between the polymer
chains and CNTs [51]. Since there is a strong interaction
between TiO2 and CNTs (Fig. 2) and they connect well with
each other (Fig. 4), we propose that e transfer also happens
in the TiO2/CNTs composites [52], leading to the reduction
of the e/h+ recombination and the increase of the photon
efficiency. Although more CNTs can greatly inhibit e/h+
recombination, the sample Ti/C-4 cannot absorb UV light
efficiently, leading to less e and h+ production. Thus, the
photocatalytic activity of this sample is still lower.
Meanwhile, when CNTs are composited with TiO2, the
absorption edge shifts to shorter wavelength, which is a blue
shift (Fig. 8). The band gaps determined by the linear
extrapolation of the steep part of the UV–vis light absorption
toward the baseline [53] for TiO2, Ti/C-1 and Ti/C-2 are
3.17, 3.35 and 3.54 eV, respectively. The band gap of TiO2 is
clearly less than those of the composites. It is commonly
accepted that a larger band gap corresponds to more
powerful redox ability [22]. Because the photocatalytic
process system can be considered to be similar to that of an
electrochemical cell, the increase in band gap results in an
enhanced oxidation–reduction potential [54], the effect of
which is the same as the suppress reaction of the
recombination of electron and hole pairs [22]. Thus, the
result of UV–vis spectra is in accordance with that of PL.
Moreover, XPS results (Fig. 6) show that there are more
hydroxyl groups provided by chemisorbed water on the
surface of TiO2/CNTs composite due to the higher
adsorption ability (Table 1), which is also advantageous
to the increase of photocatalytic activity. The more hydroxyl
group on the surface of photocatalyst, the more hydroxyl
radicals (OH) will be produced by the oxidation of h+ [55].
Fig. 10 shows EPR spectra of the DMPO-OH spin
adducts produced in the systems of TiO2 and the composite
Ti/C-1 as easily identified by the classical 1:2:2:1 spectral
signature of spin-trapped OH [56]. It can be seen that, under
the same conditions, the intensity of the 1:2:2:1 spectral
signature of the DMPO-OH spin adducts for the composite
Ti/C-1 as a photocatalyst is obviously stronger than that with
TiO2. Therefore, Ti/C-1 is photocatalytically more active
than TiO2 because there are more OH radicals produced by
Fig. 10. The hydroxyl radical (OH) EPR spectra of TiO2 and the composite
Ti/C-1 formed in aqueous dispersions in a Pyrex vessel containing about
20 mg sample after 162 s irradiation by laser light (l = 355 nm). In the
systems, the concentration of DMPO is 0.4 mol/L and the added support
Rhodamine B is 2  105 mol/L. The control spectrum for the samples is
obtained without the laser irradiation.
 Y. Yu et al. / Applied Catalysis A: General 289 (2005) 186–196
the TiO2/CNTs composite under UV irradiation, which
further support the results of PL, UV–vis and XPS.
Based on all results mentioned above, CNTs do not only
play the role to prevent e/h+ pairs from recombination but
also may provide a large surface area to lead to more
hydroxyl group on the surface of the TiO2/CNTs. Therefore,
the addition of appropriate amount of CNTs can greatly
improve the photocatalytic activity of TiO2.
4. Conclusions
The effect of oxidized CNTs on the crystalline phase and
composition, the materials morphology and the physico-
chemical properties of TiO2 is investigated using XRD,
Raman spectroscopy, BET, SEM, TGA–DSC, XPS, PL,
EPR and UV–vis spectroscopy. The results show that the
crystalline part of the obtained TiO2/CNTs composites is
composed of anatase and brookite phases, similar to that of
the TiO2. CNTs can affect the agglomerated morphology
and the particle size of the TiO2. Meanwhile, CNTs in the
composites are all covered by the TiO2 through the
formation of ester-like linkage and there is more hydroxyl
group on the surface of the TiO2/CNTs composite.
Moreover, with the increase of the amount of CNTs, the
surface area of the prepared TiO2/CNTs composites
becomes larger although the pore size distribution almost
remains constant. Both the prepared TiO2 and the TiO2/
CNTs composite are thermally stable.
The comparison of the photocatalytic activity of TiO2
and TiO2/CNTs composites for acetone degradation in air
indicates that the presence of a small amount of CNTs can
enhance photocatalytic activity of TiO2 greatly. However,
excess amount of CNTs also shield TiO2 from absorbing
UV. CNTs can enhance the photocatalytic activity of TiO2
because the presence of CNTs can prevent the e/h+ pairs
produced by TiO2 under UV light from recombination.
That is, electrons excited by TiO2 may easily migrate to
the nanostructure of the CNTs because of the strong
interaction between TiO2 and CNTs. Meanwhile, CNTs
raise the band gap of TiO2, which can make the e/h+ pairs
recombination less likely to occur. Moreover, the abundant
hydroxyl groups adsorbed on the large surface of the
composites can lead to the formation of more OH
radicals. Therefore, through the two aspects, i.e. the
decrease of the e/h+ pairs recombination and more
hydroxyl group on the surface of the composites, the
photocatalytic activity of TiO2 can be greatly enhanced by
the presence of CNTs.
Acknowledgements
This work was supported by a RGC research grant (No.
CUHK4325/03M) of the Hong Kong SAR Government to
P.K. Wong and a NSFC research grant (No. 20207002) to Y.
195
Yu. The authors thank Dr. Z. Jia and Mr. X.X. Ding, Institute
of Nano Science and Technology, Central China Normal
University, for the kind provision of carbon nanotubes and
for SEM measurements, respectively.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/
j.apcata.2005.04.057.
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