Professional Documents
Culture Documents
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 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 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
/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