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Applied Surface Science 296 (2014) 17

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Applied Surface Science
j our nal homepage: www. el sevi er . com/ l ocat e/ apsusc
Photocatalytic oxidation of methyl orange in water phase by
immobilized TiO
2
-carbon nanotube nanocomposite photocatalyst
Yinmao Dong
a,b
, Dongyan Tang
a
, Chensha Li
c,
a
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China
b
School of Sciences/Beijing Key Lab of Plant Resource Research and Development, Beijing Technology and Business University, Beijing 100048, China
c
Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China
a r t i c l e i n f o
Article history:
Received 28 July 2013
Received in revised form
21 December 2013
Accepted 21 December 2013
Available online 28 December 2013
Keywords:
TiO
2
Carbon nanotube
Solgel processes
Nanocomposites
Photocatalysis
SEM
a b s t r a c t
We developed an immobilized carbon nanotube (CNT)titanium dioxide (TiO
2
) heterostructure material
for the photocatalytic oxidation of methyl orange in aqueous phase. The catalyst material was prepared
via solgel method using multi-walled CNTs grown on graphite substrate as carriers. The multi-walled
CNTs were synthesized from thermal decomposing of hydrocarbon gas directly on thin graphite plate,
forming immobilized 3-dimensional network of CNTs. The nanophase TiO
2
was synthesized coating on
CNTs to form coral-shaped nanocomposite 3-dimensional network on graphite substrate, thus bringing
effective porous structure and high specic surface area, and possessing the merit of dispersive pow-
der photocatalysts, which is the fully available surface area, while adapting the requirement for clean
and convenient manipulation as an immobilized photocatalyst. Moreover, the CNTTiO
2
heterostructure
reduced the electronhole pair recombination rate and enhanced the photoabsorption and the adsorp-
tion ability, resulting in elevating the photocatalysis efciency. These synergistic effects due to the hybrid
nature of the materials and interphase interaction greatly improved the catalytic activity, and demon-
strated superior photocatalytic performances. Our work can be a signicant inspiration for developing
hybrid nano-phase materials to realize sophisticated functions, and bear tremendous signicance for the
development and applications of semiconductor nano-materials.
2014 Published by Elsevier B.V.
1. Introduction
Titanium dioxide (TiO
2
) is one of the most widely stud-
ied semi-conductors for environmental protection, self-cleaning,
deodorizing and sterilizing applications due to its low cost, abun-
dant resource, photocatalytic activity, harmlessness and resistance
to chemical corrosion and photocorrosion [1]. In order to provide
high photocatalytic activity, it is necessary to synthesize TiO
2
of
high specic surface area, crystallinity and porosity, and extended
life time of the photon-generated electronhole pairs, etc. Many
efforts have been made to inhibit crystal growth and retard the
phase transformation by doping with another inorganic materi-
als, such as SiO
2
[2,3], Al
2
O
3
[4], activated carbon [510], etc.
However, although inorganic materials can work as the support
of nano-sized TiO
2
photocatalysts and concentrate the pollut-
ants and intermediates around TiO
2
, the photodegradation rate is
intrinsically low due to the limited surface area. In recent years
[1120], attention was paid to the fact that carbon nanotubes
(CNTs) are attractive and promising candidates for improving the

Corresponding author. Tel.: +86 10 62797756.


E-mail addresses: lichnsa@mail.tsinghua.edu.cn, lichnsa@mail.163.com(C. Li).
photocatalytic efciency of TiO
2
due to the contribution of their
high and accessible specic areas, exceptional electronic, adsorp-
tion, mechanical and thermal properties, chemical inertness and
stability [21]. TiO
2
is an n-type semiconductor and the main
process in photocatalysis is activated by photon absorption and
electronhole generation. CNTs have the unique hollow and lay-
ered structure, the electronhole pairs could transport freely along
the cylindrical nanostructure, which thus suppresses the recom-
bination rate of the photo-generated electronhole pairs [22].
Therefore, an enhancement of the photocatalytic properties of
TiO
2
could be achieved in conjunction with CNTs, which promote
electronhole pair separation and migration. It is a process that
leaves an excess of holes in the valence band and the photogenera-
ted electrons move freely fromthe conduction band of the TiO
2
to
the electron-accepting CNT surface. TiO
2
effectively behaves as a
p-type semiconductor in TiO
2
-CNT nanocomposites. Additionally,
the superior adsorption property of nanocomposite catalyst and
the improved suppression of the recombination of the charge car-
riers contribute to the higher photocatalytic activity [13,16]. On
the other hand, the current TiO
2
-CNT nanocomposite photocata-
lysts are generally made in dispersive powder state [1120,2330].
The wide range applications for environmental remediation and
cleanup requires the development of immobilized photocatalytic
0169-4332/$ see front matter 2014 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.apsusc.2013.12.128
2 Y. Dong et al. / Applied Surface Science 296 (2014) 17
systems to guarantee certain advantages [31]: no requirement
for separation or ltration steps, thin lms or plates being easily
adoptedandconguredtocontinuous owsystems, noaggregation
of particles, anda electrical polarizationas far as possible. However,
as the real surface of the semiconductor that is available for the pro-
cess is reduced by comparison to the corresponding exposed area
of a slurry system, due to the immobilization, the photocatalytic
efciencydiminishes [32,33]. Inthis work, inorder toreachthe per-
formance that employ immobilized systems without damnifying
the benets of the semiconduct catalyst phase in powder systems,
we studied to develop an immobilized CNT-TiO
2
nanocompos-
ite photocatalyst which was prepared by coating nanophase TiO
2
on the CNTs immobilized on graphite substrate. The immobilized
CNTs were synthesized from thermal decomposing hydrocarbon
gas directly on thin graphite plate.
Compared to other methods of synthesizing CNTs, such as arc
discharge [34] and laser vaporization [35], the catalytic synthe-
sis of CNTs is simpler, more reproducible, low cost and large
scale production method [36,37]. Decomposition of hydrocarbons,
which an be abundantly supplied in the world, for the growth of
CNTs is an attractive route and many CNTs have been obtained
by the decomposition of CH
4
[38], C
2
H
2
[39], CO [40], benzene
[41], and polyethene [42], etc. In our work, the bulk growth of
CNTs was obtained by the catalytic decomposition of hydrocar-
bon gas over metal nano-catalyst deposited on thin graphite plate.
Some important advantages, which are benet for the production
of downstream products, are demonstrated: the production ef-
ciency is higher and the cost is lower relative to the other methods.
The synthesizedCNTs were stably xedonthe graphite plate witha
highpurity, andthus neednofurther puricationbefore utilization.
More important, the CNTs were grown on the graphite plate with
controllable diameters andformedshrubbery-like 3-dimensional
network, which had effective inter-spaces for mass transport and
accessible surfaces for the deposition of hetero-nanophase, and
thus is suitable for coating other nanophase materials onCNT-walls
by chemistry methods.
We synthesized nanophase TiO
2
coated on this CNTs grown on
thingraphiteplatevia solgel methodtoprepareimmobilizedCNT-
TiO
2
nanocomposites. The immobilized CNT-TiO
2
nanocomposites
formedcoral-liked3-dimensional net-workongraphitesubstrate
which had fully available surface of high specic area, effective
pore-sizes and mutually connected pore spaces, and thus can fully
exert the photocatalytic capability of nanophase semiconducting
catalyst as those in dispersive powder state. The immobilized pho-
tocatalyst composites demonstratedhighphotocatalysis capability,
convenient manipulation, and can be produced with high ef-
ciency, large batch and lowcost.
2. Experimental procedure
2.1. The growth of CNTs on thin graphite plate
Athingraphite plate withthe dimensionof 5cm5cm0.5cm
was rst annealed in air at 500

C for 15min. The NiO nanoparti-


cles were deposited onto the graphite plate by radiofrequency (rf,
14.5MHz) magnetron sputtering using a metal-oxide target of NiO
from Super Conductor Materials Inc. with a purity of 99.99% and
4cmin diameter. The sputtering was carried out at roomtemper-
ature, and the argon deposition pressure was 0.2Pa. The distance
between the substrate and the target was 10cm, and the rf power
was changed between55 and 170W. Catalysts were reduced insitu
during the synthesis of CNTs. The graphite plate depositedwithNiO
nanoparticles, which were the catalyst precursor, was put in the
middle of a horizontal furnace, and heated to 460

C under nitro-
gen. When nitrogen was substituted by hydrogen at ow rate of
250ml/min for 20min, the catalyst precursor was reduced to be
Ni nanoparticles, which were the catalyst for synthesizing CNTs.
After heating the catalyst to 660

C in hydrogen, propylene was


introduced with a owrate of 350ml/min and the hydrogen input
was reduced to half. The decomposition reaction proceeded for
30min. Then the product was cooled to room temperature under
nitrogen to obtain CNTs grown on graphite plate (CNT/GP).
2.2. Preparation of the TiO
2
-CNT nanocomposites immobilized on
thin graphite plate (TiO
2
/CNT/GP)
The CNT/GP was annealed in air at 550

C for 15min, then was


heated in concentrated nitric acid at the boiling point tempera-
ture for 40min, then puried by distilled water till pH value being
neutrality and nally dried at 100

C for 24h.
Butyl titanate (kermel), H
2
O, isopropyl alcohol and HNO
3
with
the molar ratio of 1:1.5:20:0.16 [43] were used as starting mate-
rials for preparing immobilized TiO
2
-CNT nanocomposites. Butyl
titanate (15g) was solved in isopropyl alcohol, the CNT/GP was put
inside the solution and stirred in a closed beaker for one hour, the
mixture of H
2
OandHNO
3
was slowly droppedinto it within30min
under stirring. The formed sol was kept at roomtemperature until
it formed gel. Lastly, TiO
2
/CNT/GP was obtained by drying the gel in
an oven at 45

C, annealed at 500

C for one hour in the protection


of Ar gas. For comparison, the TiO
2
particles immobilized on thin
graphite plate (TiO
2
/GP) were prepared under the same conditions
without the synthesized CNTs grown on graphite plate.
2.3. Photocatalytic degradation experiments
A pyrex reactor with the length, width, and depth being 22cm,
8cm and 8cm respective, was utilized. The volume of methyl
orange aqueous solution with the initial concentration of 30mg/L
lledinthereactor was 600mL. Theimmobilizedphotocatalyst was
assembled on the bottom of the reactor. Two 6WUV strip lamps
with the length of 21cm and a wavelength centered at 365nm
(Philips, TUV 6W/G5) were used as the light source above the
solution surface. The distance between the light sources and the
photocatalyst was about 7cm. Constant agitation of the solution
was insured by a magnetic stirrer placed at right angle from the
reactor basis.
The solution was rst stirred in dark for 120min before irra-
diation to reach equilibrated adsorption as deduced from the
steady-state concentrations. Then UV-irradiation started to ini-
tiate the photocatalysis reaction. Microsamplings were drawn
every 5min from the solution, their absorbency were mea-
sured by a 721 UV/vis spectrophotometer at the maximum
absorptive wavemeter of methyl orange (465nm), and used for
determining the time-dependent change of the dye concentra-
tion.
2.4. Materials characteristics
The structure and characteristics were analyzed by trans-
mission electron microscopy (TEM, JEOL-200CX), high resolution
transmission electron microscopy (HRTEM, H-9000NAR), eld
emission scanning electron microscopy (FE-SEM, AMRAY-1910),
X-ray diffraction (XRD, Rigaku D
max
A X-ray diffractometer with
Cu-K radiation, =0.154178nm) and RM2000 ber confocal
Raman spectroscope. The specic area and the pore volume of the
samples were measured by BET method and B.J.H. method [44],
the employedapparatus is SORPTOMATIC1990. ThermoQuest Italia
S.P.A. UVvis absorption spectra were recorded on a Shimadzu
UV-2450double-beamrecordingspectrophotometer. Fluorescence
spectra were obtained on a Shimadzu RF-5301.
Y. Dong et al. / Applied Surface Science 296 (2014) 17 3
Fig. 1. (a) SEMimage of the CNTs grownongraphite substrate, and(b) HRTEMimage
of CNTs showing the multi-walled nanotubes composed of well graphitized layers.
3. Results and discussion
3.1. Characterization of the CNT/GP sample
The graphite plate was rst annealed in air at 500

C for 15min,
its surface was etchedbythe air andbecame more rough, sothat the
catalyst particles can be effectively dispersed on it. The CNTs were
prepared by the decomposition of propylene at 600

C to 700

C
over the catalyst pre-reduced at about 500

C. The purity of CNTs


was approximate to 98 percent. SEM image (Fig. 1(a)) shows that
the CNTs were grown on graphite substrate to form continuous
3-dimensional network as shrubbery. The shrubbery-liked CNT-
network should be led by the crooked and entangled shapes of
the grown CNTs. HRTEMobservation shows the synthesized multi-
walled CNTs with outer diameters ranging from 20nm to 30nm
had many rope-like structures, as shown in Fig. 1(b).
Fig. 2 shows the Raman shift spectrum of the CNTs, which
was measured at room temperature with a frequency range
4003600cm
1
. Two sharp peaks are present at 1586cm
1
(G
peak) and 1334cm
1
(D peak). These correspond to the character-
istic peak of the graphite structure with a small basal domain size
[45]. Also there is a weaker peak around2644cm
1
whichindicates
2D or D* peak. Those features, including the wavenumbers and
relative integrated intensities, are close to those for multi-walled
carbon nanotubes [46].
The growth of CNTs during above producing process included
the following steps: at rst the feed hydrocarbon molecules were
adsorbed and decomposed on certain surface active sites of the
catalyst metal particles to form carbon species; and then, some
of the surface carbon species dissolved into the bulk and dif-
fuse through the metal particle from the front face (i.e. the
metalCNTs interface), then, some of the surface carbon species
0 500 1000 1500 2000 2500 3000
0
500
1000
1500
2000
Raman shift ( cm
-1
)
I
n
t
e
n
s
i
t
y

(

a
.
u
.

)
1334
1586
2644
Fig. 2. Raman spectrumof the synthesized CNTs.
dissolved into the bulk and diffused through the metal parti-
cle from the front face (i.e. the metalgas interface) to the rear
face (i.e. the metalCNT interface), where carbon was deposited
in the form of the CNTs [47]. Some defect structures with pen-
tagons and heptagons might be formed in CNT-walls during
the deposition of carbon species, resulted in a curly growth of
CNTs. Different from the method of catalytic pyrolysizing met-
allorganics (catalyst precursors) and carbon precursors, which
synthesized densely align-assembled CNTs [48]. This shrubbery-
liked 3-dimensional CNT-network had feasible sized mesh-pores
and enough interspaces for mass transport, and almost fully avail-
able surface areas, thus can become effective carrier for the
coating of hetero-nanophase materials through chemistry pro-
cesses.
3.2. Characterization of the TiO
2
/CNT/GP and TiO
2
/GP samples
The XRD patterns of the solgel prepared TiO
2
/GP sample and
the TiO
2
/CNT/GP sample are given in Fig. 3(a) and (b). The peaks
in all the diffraction patterns of the two correspond to the anatase
TiO
2
(JCPDS no. 21-1272). Fig. 3(b) indicates the two peaks of (002)
and (100) reections of CNTs [49,50]. By the thermogravimetric
analysis (PERKIN-ELMERTGA7), themeasuredratioof CNTs inTiO
2
-
CNT composite was about 13wt%.
The SEM image of TiO
2
/GP sample, as shown in Fig. 4(a), illus-
trates rough, spongelikestructuredTiO
2
coat ongraphitesubstrate.
Though TiO
2
particles are well dispersed to forma network with an
even distribution of mountains and valleys, they stack together to
make large part of particle surfaces being overlapped each other
and very little inter-space of the network being available. The
SEM image of TiO
2
/CNT/GP sample, as shown in Fig. 4(b), demon-
strates that nanophase TiO
2
particles densely coated on the CNTs
grown on the graphite substrate, form coral-liked nanocompos-
ite 3-dimensional network immobilized on graphite substrate. The
pores in this coral-liked nanocomposite 3-dimensional network
aremutuallyconnectedandthepore-spaces arefullyavailable, lead
to the surface area of nanophase TiO
2
coated on CNTs being fully
available. It is indicated in Table 1 that the TiO
2
/CNT/GP sample
Table 1
Specic surface area (Sp) and pore volume (Vp) of the CNT/GP, TiO
2
/GP and
TiO
2
/CNT/GP.
Sample Sp (m
2
/g) Vp (cm
3
/g)
CNT/GP 202.67 0.972
TiO
2
/GP 69.58 0.052
TiO
2
/CNT/GP 173.34 0.758
4 Y. Dong et al. / Applied Surface Science 296 (2014) 17
Fig. 3. XRD patterns of the TiO
2
/GP sample (a), and the TiO
2
/CNT/GP sample (b). (GP substrate was removed. The peaks marked by green bars were led by the glass plate
which carried the TiO
2
/CNT). (For interpretation of the references to color in gure legend, the reader is referred to the web version of the article.)
has higher BET specic surface area and pore volume compared
to TiO
2
/GP sample, this improvement of specic surface area and
pore volume should be owe to the scaffold effect of CNT- network,
as indicated in Table 1.
The TEM micrograph of CNT-TiO
2
nanocomposites (Fig. 4(c))
shows TiO
2
nanoparticles homogeneously and densely spread on
the surfaces of CNTs. A HRTEM micrograph of the heterostructure
betweenCNTs andTiO
2
nanoparticles is presentedinFig. 4(d), quite
well crystallized and organized nanophase TiO
2
is observed on the
CNT surface. Furthermore, the interface between CNTs and TiO
2
is clearly seen, indicating that TiO
2
nanoparticles, whose sizes are
about 10nm, are well attached on the outermost shell of CNTs.
Y. Dong et al. / Applied Surface Science 296 (2014) 17 5
Fig. 4. (a) A SEMimage of the TiO
2
/GP sample, (b) a SEMimage of the TiO
2
/CNT/GP
sample, (c) a TEMimage of the nano TiO
2
coatedCNTs scrapedfromthe TiO
2
/CNT/GP
sample, and (d) a HRTEM image of the nano TiO
2
coated CNTs scraped from the
TiO
2
/CNT/GP sample.
3.3. Effect of photocatalytic degradation
The UVvis absorption spectra of the prepared samples, includ-
ing TiO
2
particles which were removed from the GP substrate,
TiO
2
-GP composite which was the TiO
2
particles together with
the top GP layer removed from the GP substrate, CNTs and TiO
2
-
CNTs composite are shown in Fig. 5. The samples show an intense
absorption in UV region due to electron promotion of TiO
2
from
the valence band to the conduction band. There is a weak differ-
ence of absorption intensity between TiO
2
and TiO
2
-GP. The CNTs
sample exhibits a stronger absorption in the total spectra range,
the reason not only lies in its characteristic as a carbon material,
but also due to its greatly higher specic area compared to the GP.
The TiO
2
-CNTs composite exhibits the strongest absorption in UV
region, indicates that the presence of CNTs with the heterostruc-
ture to nano TiO
2
phase strengthen the absorption capability of UV
light. In order to study the effect of CNTs on the recombination of
e

/h
+
produced by TiO
2
, the photoluminescence spectra (PL) are
detected, as shown in the inset of Fig. 5. TiO
2
shows a strong PL
emission band. Compared with the spectrum of TiO
2
, it is found
that the PL peak of the TiO
2
-CNTs composite in the same wave-
length range is much lower than that of TiO
2
. The reduction of PL
intensity in the TiO
2
-CNTs composite indicates the decrease of the
radiative recombination process. Thus, with the assistance of CNTs,
the recombination of e

/h
+
excited by TiO
2
under UV light can be
decreased and the photon efciency can be increased.
The adsorption abilities of TiO
2
/CNT/GP and TiO
2
/GP to the
methyl orange in solution were rst measured. The adsorption
ratios of methyl orange by TiO
2
/CNT/GP and TiO
2
/GP are shown
in Fig. 6. It is indicated that the TiO
2
/GP has lower capabil-
ity of adsorbing methyl orange in aqueous solution whereas the
TiO
2
/CNT/GP has evident effect of adsorbing methyl orange. This
can be attributed to the superior adsorption property of CNTs
[16,19,51] and the large effective surface area of the TiO
2
/CNT/GP,
which correlates to a strong adsorption ability.
Fig. 7(a) demonstrates the concentration change of methyl
orange during the photocatalytic degradation by the TiO
2
/CNT/GP
and TiO
2
/GP respectively at different temperature. The experimen-
tal data indicated that the photocatalytic degradation of methyl
orange is consistent with the rst-order reaction: lnC/C
0
=kt,
where C
0
is the initial methyl orange concentration, C is the con-
centration at a certain time, and t is time. k is the apparent reaction
rate constant, it is not only determined by Arrhenius formula, but
also is inuenced by some other properties of the reaction system
[12,14,18], such as the specic area and porosities of the photo-
catalyst, the photon absorption and scattering properties, etc. The
measured apparent reaction rate constants of the photodegrada-
tion of methyl orange by the TiO
2
/CNT/GP and TiO
2
/GP respective
at different temperature are shown in Fig. 7(b). Fig. 7 indicates that
the photodegradation rate increases as the temperature rising. The
reason lies in that the subsequential oxidationreduction reactions
led by the photocatalysis can be obviously inuenced by tempera-
ture. Moreover, higher temperature can accelerate the exchange of
reactants, and enhance the conductivity of photo-induced carriers
in solid phase, results in the efciency of migration and transport of
the photo-inducedcarriers inTiO
2
andCNTs being increased, hence
promoted the redox reactions. But the photocatalysis capabilities
for methyl orange degradationof TiO
2
/CNT/GP are evidently higher
than that of TiO
2
/GP. The reason should be as follows:
First, CNTs enhance the disassociation efciency of photogen-
eratedholes andelectrons inTiO
2
semiconductor. CNTs are capable
of forming a Schottky barrier at the CNTTiO
2
interface, where
there is a space charge region. TiO
2
is an n-type semiconductor, in
the presence of CNTs, photogenerated electrons may move freely
toward the CNT surface, which may have a lower Fermi level. Thus
the CNT acts as an electron sink. This leaves an excess of holes
6 Y. Dong et al. / Applied Surface Science 296 (2014) 17
340 360 380 400
TiO
2
-CNTs
Wavenumber ( nm )
I
n
t
e
n
s
i
t
y

(

a
.

u
.

)
TiO
2
Wavenumber ( nm )
A
b
s
o
r
p
t
i
o
n
a b
c
d
200 280 360 480 240 320 400 440 520 560
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
Fig. 5. UVvis spectra of the samples: (a) TiO
2
, (b) TiO
2
-GP composite, (c) CNTs, and (d) TiO
2
-CNTs composite. Inset: a comparison of photoluminescence (240nmexcitation)
spectra of TiO
2
and TiO
2
-CNTs in homogeneous water solutions at roomtemperature.
0 20 40 60 80 100 120 140 160 180 200
25
26
27
28
29
30
TiO2/CNT/GP
C
o
n
c
e
n
t
r
a
t
i
o
n

(

m
g
/
L
)
Time (min)
TiO2/GP
Fig. 6. Absorption of methyl orange by the immobilized photocatalyst of TiO
2
/GP
and TiO
2
/CNT/GP respectively. Temperature: 24

C.
in the valence band of the TiO
2
, which can migrate to the sur-
face and react. The TiO
2
therefore effectively behaving as a p-type
semiconductor [52]. A continuous CNT network ensures higher
electrical conductivity and electron storage capacity, thus may act
as extremely effective electron sinks. The CNT-network grown on
the graphite substrate formed a continuous conducting network
of cylindrical nanostructure, let the electronhole pairs to trans-
port freely along these network paths, and effectively suppresses
the recombinationrate of the photo-generatedelectronhole pairs.
Moreover, the nanoscale TiO
2
phase coated on CNT surfaces (as
indicated in Fig. 4) with high aspect ratio may also play a role in
retardation of electronhole recombination [53], and this effect is
promoted by the continuous network of CNT-scaffolds. In addi-
tion, the high aspect ratio and nanoscale geometry allows electron
accumulation at the ends of CNTs [54], providing highly effec-
tive reduction sites; secondly, CNTs can effectively adsorb methyl
orange in the aqueous solution, as shown in Fig. 6, to result in the
methyl orange being concentrated around the CNTs carried TiO
2
phases, and the photocatalysis reaction being promoted; thirdly,
20 30 40 50 60 70
0.000
0.004
0.008
TiO2/GP
(b)
R
e
a
c
t
io
n

r
a
t
e

c
o
n
s
t
a
n
t

(

/

m
in

)
TiO2/CNT/GP
Temperature ( )
0 100 200
0.0
0.4
0.8
Time ( min )
( a )
C
/
C
0
f
e
d
c
b
a
Fig. 7. (a) Photocatalyzed degradation of methyl orange by TiO
2
/GP (a: 24

C; b:
46

C; c: 67

C) and TiO
2
/CNT/GP (d: 24

C; e: 46

C; f: 67

C). (b) Apparent reaction


rate constants of TiO
2
/GP catalyst and TiO
2
/CNT/GP catalyst at various temperature.
the higher surface area of our prepared nanocomposite photocata-
lyst (as indicated in Table 1) can enhance its apparent photoactivity
due to the higher interface for the redox reaction and the higher
rate of photon absorption, which is shown in Fig. 5. In addition,
the unique structure of the prepared immobilized photocatalyst
TiO
2
/CNT/GP is also propitious to enhancing photocatalysis capa-
bility. Different from those immobilized CNT-TiO
2
photocatalysts
which were fabricated by sticking CNT-TiO
2
powder on a sub-
strate to form a compacted lm of CNT-TiO
2
composites, also
different from those aligned CNTs densely grown on substrates,
whose heterojunctions with other nanophase materials may only
be formed on the tops of CNTs [55], our prepared CNTs grown
on graphite substrate formed shrubbery-like 3-dimensional net-
work, the synthesized nanophase TiO
2
were uniformly and densely
coated on the CNT-walls to formcoral-liked nanocomposite net-
work immobilized on graphite substrate, as shown in Fig. 4(b). This
coral-liked nanocomposite network of photocatalyst exhibited
high and accessible specic surface area, pore volume (as indicated
Y. Dong et al. / Applied Surface Science 296 (2014) 17 7
in Table 1), and available inter-spaces. The mutual connected pores
with enough available volume formed a channel network to let
the solution freely ow through to promote the exchange of reac-
tants. Without the CNTs as scaffolds, the synthesized TiO
2
particles
tightly stacked together, result in low specic area, pore volume
and unavailable pore spaces, as indicated in Fig. 4(a) and Table 1.
In the future work, some methods will be developed to
further enhancing photocatalysis capability of the immobilized
TiO
2
/CNT/GP photocatalyst. Firstly, the novel surfactant wrapping
solgel method will be adopted in order for coating a uni-
form and well-dened nanoscale TiO
2
layer on CNTs [12,14,18].
Nanophase of TiO
2
coating CNT-walls with a higher coverage
rate and controlled thickness should contribute to a closer con-
tact of heterophase, diminish the losses of photons by absorption
and scattering by the bare CNT phase, enhance the efciencies
of disassociation and migration of the photogenerated carri-
ers, and increase the available specic area of the TiO
2
-CNTs
nanocomposites, thus should effectively improve the photocata-
lysis performance. Secondly, controlling the composition ratio in
TiO
2
-CNTs is crucial to obtainanoptimal synergistic effect between
CNTs and TiO
2
, for reason that it can inuence the photo absorp-
tion and scattering, the size and the uniformdistribution degree of
the nanophase TiO
2
, etc. [12,14,15,18]. Therefore, the effect of the
CNTs/TiO
2
ratio on the photocatalysis performance will be studied.
Thirdly, theimmobilizedTiO
2
/CNT/GPphotocatalyst canbedirectly
used as the electrode for photo-electro-catalytic process [12,18]
due to the semiconducting scaffolds (CNTs) and substrate (graphite
plate), the efciency of photocatalysis will be further enhanced by
combining a photo-electro-catalytic system.
4. Conclusion
Nanocarbon-TiO
2
systems have been widely investigated and
are promising materials for future high activity photocatalysts
[16,56,57]. In order to adapt the requirements for effective
photocatalysis capability and immobilization of photocatalyst sys-
tem based on nanocarbon-TiO
2
, we developed an immobilized
TiO
2
-CNTs nanocomposite. The CNTs synthesized from thermal
decomposing hydrocarbon gas grew on thin graphite plate to
formshrubbery-like3-dimensional network. ThenanophaseTiO
2
was synthesized by solgel method to be coated on CNT-walls
and formed coral-liked nanocomposite network immobilized
on graphite substrate, which had high and accessible specic
area, effective pore-sizes and available inter-spaces, thus can
greatly enhance and fully exert the photocatalytic capability
as a nano-photocatalyst. The prepared immobilized TiO
2
-CNTs
nanocomposite demonstrated superior photocatalysis perfor-
mance while adapt the application need of clean and convenient
manipulation, and the batch production process with low cost. In
the future, it is promising to greatly improve the performance of
our immobilized TiO
2
-CNTs photocatalyst by combining the newly
novel techniques of preparing TiO
2
-CNTs nanocomposites.
Acknowledgements
This work was supported by the Major State Basic Research
Development Programof China, Grant No. 10332020.
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