Journal of Colloid and Interface Science 409 (2013) 104111

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Journal of Colloid and Interface Science

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Phenol degradation by TiO2 photocatalysts combined with different

pulsed discharge systems
Yi Zhang a,, Jiani Lu a, Xiaoping Wang b, Qing Xin c, Yanqing Cong a, Qi Wang a, Chunjuan Li a
a
School of Environmental Science and Engineering, Zhejiang Gongshang University, Jiaogong Road 198, Hangzhou 310012, Zhejiang, China
b
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemical and Biological Engineering, Zhejiang University, Zheda Road 38,
Hangzhou 310027, China
c
College of Electronic Information, Hangzhou Dianzi University, Xiasha Higher Education Park 2 Street, Hangzhou 310018, Zhejiang, China

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

Article history: Films of TiO2 nanotubes distributed over the inner surface of a discharge reactor cylinder (CTD) or
Received 15 March 2013 adhered to a stainless steel electrode surface (PTD) in a discharge reactor were compared with a sin-
Accepted 31 July 2013 gle-discharge (SD) system to investigate their efciencies in phenol degradation. Morphology studies
Available online 11 August 2013
indicated that the TiO2 lm was destroyed in the PTD system, but that there was no change in the
CTD system after discharge. X-ray diffraction results revealed that the anatase phase of the original sam-
Keywords: ple was preserved in the CTD system, but that an anatase-to-rutile phase transformation occurred in the
Pulsed plasma
PTD system after discharge. The highest efciencies of phenol degradation and total organic carbon (TOC)
TiO2 nanotube lms
Photocatalyst
mineralization were observed in the CTD system, and there was no decrease in phenol degradation ef-
Combined treatment ciency upon reuse of a TiO2 lm, indicating high catalysis activity and stability of the TiO2 photocatalysts
Phenol degradation in the combined treatment. TiO2 photocatalysts favored the formation of hydrogen peroxide and disfa-
vored the formation of ozone. A greater degree of oxidation of intermediates and higher energy efciency
in phenol oxidation were observed with the TiO2-plasma systems, especially in the CTD system, com-
pared to those with the SD system.
2013 Elsevier Inc. All rights reserved.

1. Introduction TiO2 catalysts for 2,4-dinitrophenol degradation with a hydroelec-

Recently, pulsed high-voltage discharge has been widely inves-
tigated for the degradation of pollutants in water, with both chem-
ical and physical effects being initiated by the discharge [13].
Various reactive species, such as OH, O, H, O2 , HO2, H2O2, and
O3 have been invoked as being responsible for the destruction of
organic compounds in pulsed discharge systems [4,5]. Besides
pyrolysis, ultraviolet radiation and ultrasonic degradation are obvi-
ous physical effects during discharge [6,7]. Since the effects of H2O2
and ultraviolet radiation are not utilized efciently in a discharge,
combined technologies such as Fenton [8,9] or TiO2 photocatalysis
[10] systems coupled with pulsed discharge have been developed.
TiO2 photocatalysis is a heterogeneous catalysis system, and the
type of TiO2 photocatalyst in a discharge reactor can be varied. In
early work, TiO2 powder (P-25) was applied in high-voltage dis-
charge systems to investigate its enhancing effect on the degrada-
tion of pollutants [1013]. However, TiO2 powder proved to be
difcult to separate from the treated solution for reuse. Therefore,
several TiO2-loaded catalysts have been utilized in pulsed dis-
charge systems. Qin et al. [14] used TiCl4 as a precursor to prepare
Corresponding author. Fax: +86 571 88071024.
E-mail address: zhangyi@zjgsu.edu.cn (Y. Zhang).
tric plasma. Wang et al. [1518] utilized a traditional solgel meth-
od to support TiO2 on glass beads to form immobilized TiO2
photocatalyst lms and investigated the effect of varying the syn-
thesis conditions on the pulsed discharge system. Zhang et al.
[19,20] prepared TiO2 loaded on activated carbon bers (ACF)
and applied the immobilized catalysts in a pulsed discharge reactor
for methyl orange degradation. It was found that a small quantity
of TiO2 was washed away from the ACF surface, mainly in the rst
cycle, owing to the weak interaction between the small particles
and the surface. In these studies, the TiO2 catalysts were all de-
ployed in liquid discharge reactors and were probably inuenced
by the discharge. However, the usage life and post-discharge con-
dition of the TiO2 were not investigated in detail, despite the fact
that the spark discharges were intense and discharge channels
were formed between high-voltage and ground electrodes.
In this study, TiO2 nanotube lms have been deployed in dis-
charge reactors. Two types of combined TiO2-plasma catalysis sys-
tems have been compared with a single-discharge system to
analyze the synergistic effect between TiO2 and the plasma. The
morphological features and crystal structure of TiO2 have been
analyzed to investigate the characteristics of the TiO2 lms before
and after discharge. In addition, active species such as hydrogen
peroxide and ozone and intermediates of phenol degradation have

0021-9797/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2013.07.064
 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111
been analyzed. Finally, the energy utilization in phenol degrada-
tion has been compared among the various systems.
2. Materials and methods
2.1. Materials
High-purity titanium plate was supplied by Baoji Deli Titanium
Industry Co., Ltd., Shanxi, China. All chemicals used were of analyt-
ical grade and were purchased from Hz Huipu Chemical & Appara-
tus Co., Ltd., Hangzhou, China. Distilled water was used to prepare
all solutions and to wash the titanium plate.
An electrochemical method was used to prepare TiO2 nanotubes
(NTs), as described previously [21]. A high-purity Ti foil (0.3 mm
thick) was ultrasonically cleaned with acetone and then with dis-
tilled water for 15 min each. A two-electrode anodization process
with the pretreated Ti foil as the anode and a Ni sheet as the cath-
ode was established for reaction at 20 V for 2 h. A mixture solution
of 0.08 mol/L C2H2O42H2O and 0.135 mol/L NH4F was prepared as
the anodization electrolyte. After the 2 h reaction, the anodized
samples were washed with distilled water and dried at room tem-
perature. The as-formed TiO2 NTs were calcined in a mufe furnace
at 400 C for 2 h.
2.2. Experimental apparatus
The discharge experimental apparatus consisted of points-plate
reactors as shown in Fig. 1. In this study, the input voltage was ad-
justed to 12, 14, or 16 kV, with a pulse frequency of 100 Hz and a
storage capacitance Cp of 4 nF. The single-discharge reactor (SD),
as shown in Fig. 1(a), consisted of a Plexiglas cylinder of 50 mm
internal diameter with ve stainless steel needles ( 0.7 mm) as
a high-voltage electrode and a stainless steel ground electrode (
30 mm). The needle points were positioned about 3 mm above
the reactor bottom and the distance between the electrode needles
and the ground electrode was 10 mm. Two types of TiO2 lms were
deployed in the plasma reactors. In the rst case, a circular TiO2
lm was distributed around the inner surface of the discharge
reactor cylinder (CTD), while in the second case, a plate-like TiO2
lm adhered to the stainless steel ground electrode surface in
the discharge reactor (PTD), as shown in Fig. 1(b) and (c), respec-
tively. Oxygen was bubbled from the holes of the needles into
the treated solution at a ow rate of 0.2 m3/h. A cooling water jack-
et was placed around the reactor to keep the temperature of the
treated solution at 25 C. The treated solution contained phenol
- -
Ground
electrode
+ +
Pulsed high
voltage electrodes Oxygen bubbling
(a)
Fig. 1. The schematic diagram of SD (a), CTD (b), and PTD (c) reactors.
105
at an initial concentration of 50 mg/L and the total treated volume
was 50 mL.
2.3. Analytical methods
X-ray diffraction (XRD) analysis and eld-emission scanning
electron microscopy (FE-SEM) were used to identify the morpho-
logical features and crystal structures of the TiO2 nanotube lms.
The ultravioletvisible diffuse reectance spectra (UVvis DRS) of
TiO2 nanotube lms were recorded by a UVvis Spectrometer (Shi-
madzu, UV-3150) with a wavelength range of 220600 nm. The
concentrations of phenol and intermediates derived from there
were analyzed by means of an Agilent HPLC apparatus with a
C18 column and ultraviolet detection at 278 nm. The volume ratio
of the mobile phase between the deionized water and methanol
was 6:4 (V/V) with a ow rate of 1.0 mL/min. The concentration
of hydrogen peroxide was determined by a colorimetric method
based on its reaction with titanyl ions to form the yellow peroxoti-
tanium (IV) complex with maximum absorbance at k = 410 nm
[22]. The concentration of dissolved ozone was determined by
the indigo method [23]. A total organic carbon (TOC) analyzer (Tek-
mar Dohrmann Apollo 9000, USA) was used to analyze the treated
water. The conductivity and pH of the treated solution were mea-
sured by a conductivity meter (DDS-11 A) and pH meter (pHS-25),
respectively.
The values of peak pulse voltage and pulse current were re-
corded by a Tektronix P6015A high-voltage probe and a Tektronix
TCP0150 current probe combined with a Tektronix DPO3012 digi-
tal oscilloscope. The corresponding typical pulsed voltage and cur-
rent waveforms with input voltages of 12, 14, and 16 kV are shown
in Fig. 2. Following the discharge, there were positivenegative
oscillations in the current proles, especially for the strong spark
discharge at 16 kV. On increasing the input voltage, the peak volt-
age increased to 15, 17, and 19 kV, and the peak current increased
to 4.4, 5.2, and 9.3 A, respectively, with a rise time of about 150 ns.
The input energy per discharge Ein (J/discharge) can be obtained
from the following equation [24,25]:
Z C
Ein UIdt 1
0
where U and I are the voltage (V) and current (A) at time t (ns),
respectively, and U is the total time (ns) of one discharge. In this
study, Ein was calculated as 0.008, 0.019, and 0.04 J/pulse at input
voltages of 12, 14, and 16 kV, respectively, based on the data from
Fig. 2.
-
Ground Ground
electrode electrode
TiO2 film
TiO2 film
Pulsed high voltage Pulsed high +
electrodes Oxygen bubbling voltage electrodes Oxygen bubbling
(b) (c)
106 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111
2.0x104
1.5x104
1.0x104
Voltage (V)
5.0x103 U
0.0
-5.0x103
-1.0x104 I to the greatest extent.
-1.5x104
-2.0x104
-6 -6 -6
0.0 1.0x10 2.0x10 3.0x10
Time (min)
Fig. 2. The typical waveforms of voltage and current.
The energy utilization efciency G50 yield (g/kWh) is dened as
the phenol converted per unit input energy, which is calculated by
the following equation [26]:
50%c0 V
G50
Ein ft50
where c0 is the initial phenol concentration (mg/L), V is the treat-
ment volume (L), f is the pulse repetition rate (Hz), and t50 is the
reaction time for 50% phenol degradation (s).
3. Results and discussion
3.1. SEM of TiO2 lm before and after discharge
Fig. 3 shows SEM images of the TiO2 lms of the different dis-
charge systems before and after discharge. Fig. 3(a) shows an
SEM image of the original TiO2 lm before discharge, from which
it is clear that many TiO2 nanotubes were arranged uniformly
and orderly on the surface of the titanium plate. In the CTD system,
the surface morphology of the TiO2 lm (Fig. 3(b)) was almost the
same as that of the original TiO2 lm sample because the TiO2 lm
was spread around the wall of discharge reactor and was not de-
stroyed during the discharge.
Fig. 3(c)(e) show the surface morphologies of titanium plates
at high magnication (35 magnication) in the PTD system after
discharge at 12, 14, and 16 kV, respectively. It is evident that the
surfaces of the titanium plates were extensively destroyed to form
several holes after discharge. Moreover, the surface of the titanium
plate subjected to discharge at 16 kV shows the most and largest
holes. Fig. 3(f) shows the magnied edge of a hole in image (e)
(30000 magnication). It is clear that TiO2 nanotubes around
the hole were destroyed and that no TiO2 nanotubes remained in
the hole. Meanwhile, uniform and undamaged TiO2 nanotubes
similar to those shown in Fig. 3(a) and (b) (SEM not shown) were
observed on the undamaged surface of the titanium plate in the
PTD system.
The formation of holes was likely due to the spark discharge
mode. As in our points-plate reactor, the electrode distance was
about 10 mm, which easily induced simultaneous spark and
streamer formation. The streamers formed at the needle tips
and propagated toward the ground electrode. The spark mode
formed when the streamer came into contact with the ground
electrode [2]. The spark discharge occurred shortly and frequently
following the increase in the voltage pulse from 12 kV to 16 kV.
During the formation of the spark channel from the needle tips
to the ground electrode, intense shock waves were generated
due to the rapidly expanding plasma channel [27]. The resulting
20 shock wave can erode the surface of electrodes resulting in the
16 kV formation of holes during the spark channel formation. As the
16 discharge channels were produced from high-voltage needle elec-
14 kV
12 kV trodes to a plate ground electrode, the TiO2 lm adhered on the
12 ground electrode surface was attacked during the discharge.
Current (A)
Especially in the case of the spark discharge at 16 kV, the energy
8 input was higher and more discharge channels were formed;
hence, the destruction of the surface of the titanium plate was
4
much more extensive and the TiO2 nanotubes were destroyed
0
Fig. 3(g) shows the surface morphology of a titanium plate in
-4 the PTD system following 16 kV discharge after being reused six
times and Fig. 3(h) shows a magnied image of a spot in (g). It
-6
4.0x10 5.0x10-6
is evident that the titanium plate was broken and that the holes
became interconnected after repeated discharge; hence, the de-
stroyed region of the surface of the titanium plate was enlarged
and the TiO2 nanotubes were also extensively destroyed.
3.2. XRD of TiO2 lm before and after discharge
Fig. 4 shows the XRD patterns of TiO2 nanotube lms before (a)
and after use in the CTD (b) and PTD (c) systems at 16 kV. After dis-
2 charge in the CTD system, the TiO2 nanotube lm retained the
same anatase phase diffraction peaks as the original sample, which
also conrmed that the TiO2 lm had not been destroyed during
the discharge. In the PTD system, however, the phase state of the
TiO2 lm had been changed since several peaks representing the
rutile phase were observed in the diffraction pattern, and this
phase has lower catalytic activity compared to the anatase phase.
As high temperatures were reached in the formation of the plasma
channel, an intense shockwave was generated and a pyrolytic reac-
tion was induced [28]. Consequently, the TiO2 lm was calcined
during the high-temperature discharge channel formation and
the crystal of TiO2 was partly transformed into the rutile phase.
It is for this reason that the photocatalytic activity decreased in
the PTD system.
3.3. UVVis DRS analysis of TiO2 lm before and after discharge
Fig. 5 shows the UVvis DRS of fresh and used TiO2 lms. All
samples exhibited a broad band absorption in ultraviolet regions
(400 nm) and no obvious peaks. The absorbance spectra of used
TiO2 nanotubes in the CTD system were similar to that of original
pure TiO2 nanotubes. Compared with original TiO2 nanotubes,
TiO2 nanotubes used in the PTD system exhibited a slight red-shift,
which was probably due to the rutile phase formation [2931]. All
the samples also showed some visible light absorbance (>400 nm),
which may have been caused by the pores or cracks in the nano-
tube arrays [32,33].
3.4. Phenol degradation in different combined systems
Fig. 6 shows the results of phenol degradation experiments per-
formed with the SD, CTD, and PTD systems. It can be seen that
much more phenol was degraded under an input voltage of
16 kV compared to the other input voltages of 12 and 14 kV, both
with the SD and combined systems. Furthermore, more phenol was
degraded in the TiO2-plasma combined systems under different in-
put voltages of 12, 14, and 16 kV. In particular, the removal ef-
ciency of phenol was highest in the CTD system. After 15 min
discharge, the removal efciency reached 98.5% at 16 kV in the
CTD system. Such results show an enhanced effect for phenol deg-
radation of the TiO2 lm photocatalyst induced by the pulsed dis-
charge. This was probably due to the TiO2 photocatalyst induced by
the discharge producing more OH, according to Eqs. (3)(5)
[34,35].
 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111 107

Fig. 3. SEM image of TiO2 lm (a) before discharge, (b) discharge in CTD system, (c) corona discharge in PTD system, (d) streamer discharge in PTD system, (e) spark discharge
in PTD system, (f) a magnication of edge of a hole in image (e), (g) spark discharge in PTD system after sixth used, (h) a magnication of a spot in image (g).

A: anatase
A
R: rutile Original
T Ti: titanium
A CTD
T A
Intensity (A.U.)

PTD
Intensity (A.U.)

A T A (a)
T

(b)

R R
(c)

20 30 40 50 60 70 80 250 300 350 400 450 500 550 600

2Theta (Degree) Wavelength (nm)

Fig. 4. The XRD patterns of TiO2 nanotubes lm original (a) and after used in CTD Fig. 5. UVVis DRS of TiO2 nanotubes lm original and after used in CTD and PTD
(b) and PTD (c) systems. systems.
108 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111

100 stances, such as H3O+ ions, hydrogen peroxide, ozone, and organic
acids, were produced during the discharge [36,37], the treated
solution became more acidic and more conductive with increasing
80
Removal efficiency (%)

residence time. Therefore, in the CTD system, the degraded phenol

could produce more organic acids than in the other two systems,
60 which indicated that cooperation between the TiO2 lm and dis-
charge in the CTD system could enhance phenol degradation
markedly.
40

3.5. Comparison of original TiO2 lm and used TiO2 lm for phenol

20 removal

0
Phenol removal efciencies of an original TiO2 lm are com-
0 5 10 15 20 25 30 pared with those of a lm used six times in the SD, CTD, and PTD
Time (min) systems at 16 kV in Fig. 7. In the CTD system with a six times used
16 kV+SD 16 kV+CTD 16 kV+PTD TiO2 lm, the phenol removal efciency was similar to that with an
14 kV+SD 14 kV+CTD 14 kV+PTD original TiO2 lm. In the PTD system with a six times used TiO2
12 kV+SD 12 kV+CTD 12 kV+PTD lm, however, the phenol removal efciency decreased compared
to that with an original TiO2 lm, but was still higher than that
Fig. 6. Phenol degradation in SD, CTD, and PTD system at 12, 14, and 16 kV. in the SD system. The results indicate that a TiO2 lm deployed
H2 O ! H  OH 3 in the CTD system retained high photocatalytic activity over a
longer period of usage, whereas its activity was lost in the PTD sys-

tem. This can probably be attributed to the destruction of the TiO2
TiO2 hv ! h e 4 lm during discharge channel formation in the PTD system but not
in the CTD system.

h H2 O ! H  OH 5
3.6. Active species formation in different combined systems
However, the location of the TiO2 lm in the discharge reactor also
affected the phenol removal efciency. This was probably due to the Fig. 8 indicates the extent of H2O2 formation in distilled water
destruction of the TiO2 lm in the PTD system, which affected the in the SD, CTD, and PTD systems. The concentration of H2O2 in
TiO2 photocatalytic activity, whereas there was no change in the the distilled water attained levels of 126, 173, and 154 mg/L after
TiO2 lm after discharge in the CTD system, which enhanced the 30 min discharge at 16 kV in the SD, CTD, and PTD systems, respec-
synergistic effect between the TiO2 photocatalyst and the plasma. tively, which were all higher than those at 12 and 14 kV. In
This provides an explanation for the enhancing effect on phenol
degradation in the PTD system being smaller than that in the CTD 100
system, especially at a high energy input of 16 kV. This has been dis-
cussed in detail in Sections 3.1 and 3.2.
Table 1 lists the variations in TOC, pH, and conductivity (r) values 80
Removal efficiency (%)

before and after treatment with the different discharge systems.

With increasing input voltage, the mineralization of TOC increased 60
in each of the SD, CTD, and PTD systems. Moreover, the mineraliza-
tion of TOC in the CTD system was higher than that in the SD and
PTD systems at the same voltage input. The highest mineralization 40
CTD
of TOC after 30 min degradation was about 65%, decreasing from
CTD for TiO2 sixth times used
40.04 to 14.01 mg/L in the CTD system at 16 kV input. 20 PTD
The changes in pH and liquid conductivity listed in Table 1 PTD for TiO2 sixth times used
show that the pH decreased and liquid conductivity increased after
SD
30 min discharge. For example, in the CTD system with 16 kV in- 0
0 5 10 15 20 25 30
put, the pH decreased to 3.4, which was lower than that in the
Time (min)
PTD system (3.6) or the SD system (3.9). The liquid conductivity
of the phenol solution increased to the highest value (809 lS/cm) Fig. 7. Comparison of original and sixth used TiO2 lm for phenol removal in SD,
in the CTD system compared to those in the PTD system (683 lS/ CTD, and PTD system at 16 kV.
cm) and SD system (545 lS/cm). As several acid-causing sub-
Table 1
Variations of TOC, pH, and conductivity (r) values during the treatment.

Experimental conditions TOC (mg/L) Mineralization of TOC (%) pH r (lS/cm)

Initial Final Initial Final Initial Final
SD 39.25 1.97 4.6 145
12 kV CTD 38.87 2.92 4.1 174
PTD 39.05 2.47 4.3 144
SD 36.50 8.84 4.1 468
14 kV CTD 40.04 34.77 13.16 6.56.8 3.6 1.54.5 530
PTD 35.39 11.61 3.8 510
SD 25.55 36.19 3.9 545
16 kV CTD 14.01 65.01 3.4 809
PTD 18.76 53.15 3.6 683
 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111 109

200 HO3 !  OH O2 10
16 kV+TiO2 around
14 kV+TiO2 around
160
12 kV+TiO2 around 3.7. Primary intermediate formation in the different discharge systems
16 kV+TiO2 plate
H2O2 (mg/L)

120 14 kV+TiO2 plate Hydroquinone (HQ), catechol (CC), and benzoquinone (BQ) are
12 kV+TiO2 plate the main by-products formed by pulsed high-voltage discharge
16 kV during phenol degradation [40]. To investigate the catalytic effect
80
14 kV of TiO2 on phenol degradation, changes in the concentrations of
12 kV these primary intermediate products against treatment time in
40
4
(a) HQ
BQ
0
CC

Concentration (mg/L)
0 5 10 15 20 25 30 3
Time (min)

Fig. 8. H2O2 formation in SD, CTD, and PTD systems at 12, 14, and 16 kV.
2

addition, the obtained results showed that the photocatalysis of

the TiO2 lms was more distinct in the TiO2-plasma combined
1
systems compared with the SD system, especially in the case of
the CTD system. As reported in the literature [34], H2O2 might be
produced by electron attack on water molecules and OH combina-
0
tion, as shown in Eqs. (6) and (7). TiO2 photocatalysis induced by 0 5 10 15 20 25 30
discharge can produce more OH (Eqs. (4) and (5)), which is Time (min)
considered to enhance H2O2 formation.
11
2H2 O ! H2 O2 H2 6
10 (b) HQ

OH  OH ! H2 O2 7 9
BQ
Concentration (mg/L)

8 CC
In TiO2-plasma combined systems, the concentration of H2O2 gener-
7
ated in the CTD system was higher than that generated in the PTD
6
system. This was consistent with the fact that the TiO2 lm was not
destroyed in the CTD system, so that the synergistic effect between 5
the TiO2 photocatalyst and the plasma was enhanced compared to 4
that in the PTD system. 3
Ozone is one of the most important active species produced in 2
the discharge process when oxygen is present [38]. Table 2 lists 1
the dissolved ozone concentrations in distilled water after reaction 0
in each discharge system. With increasing input voltage, the ozone 0 5 10 15 20 25 30
concentration in solution increased in both the single-discharge Time (min)
and TiO2-plasma combined systems. Compared with that in the
pulsed discharge SD system, the dissolved ozone concentrations
were lower in both combined systems and that in the CTD system
8
(c)
was the lowest of all. The highest ozone concentration produced in 7 HQ
the SD system was about 0.050 mg/L, followed by about 0.041 mg/ BQ
Concentration (mg/L)

6 CC
L in the PTD system and about 0.024 mg/L in the CTD system. It
was shown that the concentration of dissolved ozone relates to 5
the photocatalytic reaction. In the TiO2-plasma combined system, 4
ozone accepts electrons to produce O 3 radicals when the photoca-
talysis process is induced. Subsequently, OH radicals are generated 3
by radical chain reactions to inhibit the recombination of electrons 2
and positive holes, thereby enhancing the photocatalytic activity of
1
TiO2 in the combined systems. The radical reactions are shown in
Eqs. (8)(10) [20,39]: 0
 0 5 10 15 20 25 30
e O3 ! O
3 8
Time (min)

O 
3 H ! HO3 9 Fig. 9. Changes of HQ, BQ, and CC against treatment time at 16 kV in SD (a), CTD (b),
and PTD (c) systems.

Table 2
Dissolved ozone concentrations after reaction under different discharge systems.

Experimental conditions 12 kV 14 kV 16 kV
SD CTD PTD SD CTD PTD SD CTD PTD
Dissolved ozone concentration (mg/L) 0.0056 0.0020 0.0047 0.0079 0.0047 0.0061 0.0495 0.0236 0.0411
110 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111

the SD (a), CTD (b), and PTD (c) systems at 16 kV were measured,
and the results are shown in Fig. 9. It was found that the concen-
trations of HQ, CC, and BQ were higher in the presence of TiO2, Ground electrode
especially in the CTD system, than those in the SD system. This
was probably due to the higher catalytic effect of the TiO2 lm in
the CTD system in promoting the conversion of phenol into HQ,
CC, and BQ. These results indicated that the synergistic CTD system
OH H2O2 OH
had a higher oxidation capability. TiO2 film Discharge zone TiO2 film
hv O3 hv
3.8. Comparison of the degradation of organic pollutants in various
systems

Table 3 lists the rate constants and energy utilization efcien-

cies (G50) of phenol degradation at 16 kV in the SD, CTD, and PTD
systems. The CTD and PTD TiO2-plasma systems exhibited higher
rate constants and G50 values than those in the SD system. More-
over, the highest rate constants and G50 values were obtained in
the CTD system since the TiO2 lm was not destroyed and the pho-
tocatalysis was greatly enhanced. Also included in Table 3 are G50
values for different organic compounds reported in previous liter-
ature [12,16,19]. The G50 value for phenol removal in the CTD sys-
tem (2.15 g/kWh) is nearly three times that in the SD system
(0.95 g/kWh). Compared with other studies, the enhancing effect
of TiO2 in the CTD system was the highest. The results also indicate
that the TiO2 lm was not destroyed in the CTD system and so
could be utilized more efciently compared to when TiO2 powder
was deployed in the discharge reactor.
TiO2 photocatalysis combined with a pulsed discharge system
has been studied by several researchers to achieve the degradation
of different organic pollutants [1114,19,20]. All the studies indi-
cated that the combined system could enhance dyes and phenolic
derivatives efciently. In our study system, we also investigated
the applicability of this method to dyes, such as Methyl orange
(MO), and hepatotoxic monocyclic heptapeptides, such as Microcy-
stin-LR (MC-LR), which has rarely been studied in this combined
method. The kinetic constant and G50 for MO and MC-LR degrada-
tion are also shown in Table 3. It was found that our results for the
kinetic constants for MO and MC-LR degradation were higher in
the TiO2-plasma combined systems compared with the SD system,
especially in the case of the CTD system, which was similar to the
phenol removal. The enhanced effect of TiO2 for non-color com-
pounds, i.e., phenol and MC-LR, is greater than that of colored com-
pound MO, which was probably due to the colored pollutant
hindering the ultraviolet light emitted from plasma channels
reaching the TiO2 surface [12]. In conclusion, in our TiO2 photocat-
alyst combined discharge system, this hybrid method potentiality
Pulsed high voltage
electrodes
Fig. 10. Reaction mechanism of discharge combined with TiO2 nanotubes lm.
performs higher when applied to other dyes and other organic
pollutants.
In addition, the TiO2 nanotube photocatalysis for phenol degra-
dation was compared with the TiO2-plasma combined system. The
spectral distribution induced by spark discharge is similar to that
of the sunlight and the light intensity of UV light is  hundreds
lW/cm2 [2,41]. In the photocatalyst system, a xenon lamp is used
as an articial sunlight source, in which the UV light intensity was
similar with that induced by spark discharge, and this was selected
for phenol removal. The photocatalysis degradation of phenol was
only about 17.7% after 30 min. While for the 16 kV discharge, the
maximal phenol degradation levels were 55.9% in the CTD system
and 34.0% in the PTD system, which was a little higher than that for
the photocatalysis reaction. The enhanced effect in TiO2-plasma
combined system is probably due to the excess of H2O2 combined
with the ultrasonic effect that occurred during discharge and as-
sisted in the TiO2 photocatalysis of phenol [42,43].
3.9. Reaction mechanism in plasma-TiO2 combined process
Fig. 10 shows the probable reaction mechanism in the plasma-
TiO2 photocatalysis process of the CTD system. When the plasma
was present between the high-voltage electrodes and ground elec-
trode, lots of UV light and ozone were produced in the discharge
zone. So, TiO2 photocatalysis induced by UV light can produce
more OH and enhance other active species, such as H2O2 genera-
tion. In addition, ozone accepts electrons to produce O
3 radicals

Table 3
Kinetic constant and G50 in our study and other literatures.

Experimental conditions k (min1) R2 Ein (J/pulse) G50 (g/kwh) Enhanced effect References
16 kV Phenol 50 mg/L SD 0.04 0.98 1.1 1
CTD 0.12 0.93 3.1 2.8
PTD 0.07 0.97 1.95 1.8
16 kV MO 50 mg/L SD 0.32 0.99 0.04 8.5 1 In this study
CTD 0.43 0.99 11.7 1.4
PTD 0.34 0.99 9.1 1.1
16 kV MC-LR 1.0 mg/L SD 0.64 0.96 0.34 1
CTD 1.10 0.97 0.59 1.7
PTD 0.81 0.97 0.43 1.3
14 kV Phenol 100 mg/L Without TiO2 0.89 1 Ref. [12]
With TiO2 (50 mg/L) 1.97 2.2
21 kV Phenol 100 mg/L Plasma alone 0.03 0.99 0.538 4.1 1 Ref. [16]
Plasma-photocatalysis 0.05 0.99 6.5 1.6
6 kV MO 80 mg/L Without ACF/TiO2 5.6 1 Ref. [19]
With ACF/TiO2 (1250 mg/L) 8.86 1.6
 Y. Zhang et al. / Journal of Colloid and Interface Science 409 (2013) 104111
and then OH radicals are generated by radical chain reactions. In
fact, the TiO2 lm was not destroyed in the CTD system with the
TiO2 lm distributed around the inner surface of the discharge
reactor cylinder, so the synergistic effect between the TiO2 photo-
catalyst and the plasma was highest in this system.
4. Conclusions
Phenol degradation efciencies in SD, CTD, and PTD systems
have been compared. In the CTD system, the surface morphology
of the TiO2 nanotube lm did not change after discharge and an
anatase phase was detected by XRD analysis of both the original
and reused TiO2 lms. In the PTD system, however, the TiO2 lm
was destroyed and a rutile phase was also detected after discharge.
The phenol degradation efciency and TOC mineralization ef-
ciency were found to be higher in the CTD system compared with
those in the PTD and SD systems. The removal efciency of phenol
was improved to 100% and the TOC mineralization efciency was
enhanced to 65% after 30 min reaction at 16 kV discharge. More-
over, the phenol degradation efciency was not changed after re-
use of the TiO2 nanotube lm, indicating high stability of its
photocatalytic activity in the CTD system.
The highest hydrogen peroxide concentration and lowest ozone
concentration were detected in the CTD system, which indicated
that ozone accepted electrons to produce O 3 radicals in the photo-
catalysis process. More OH radicals were generated by radical
chain reactions, thereby improving the hydrogen peroxide forma-
tion. In addition, higher concentrations of HQ, CC, and BQ were de-
tected and higher energy utilization efciency was observed for
phenol oxidation in the combined systems compared with the SD
system. In conclusion, the novel CTD system combining a TiO2 pho-
tocatalyst and discharge is promising for phenol removal.
Acknowledgments
This work is nancially supported by the National Natural Sci-
ence Foundation of China (Nos. 20906079, 21006017, 20976162),
Zhejiang Provincial Natural Science Foundation of China (Grant
No. Y5100356), and the Science and Technology Project of Zhejiang
Province (2012C23062).
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