Materials Science and Engineering B 196 (2015) 53–60

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Photocatalytic degradation of acetaminophen in aqueous solutions by

TiO2 /ZSM-5 zeolite with low energy irradiation
Chang-Tang Chang a , Jia-Jie Wang b , Tong Ouyang b , Qian Zhang c , You-Hai Jing b,∗
a
Department of Environmental Engineering, National I-Lan University, No. 1 Sheen-Long Road, I-Lan City 260, Taiwan
b
College of the Environment and Ecology, Xiamen University, South Road of Xiangan, Xiamen 361102, Fujian, China
c
Graduate Institute of Environmental Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, 10617 Taipei, Taiwan

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

Article history: Photocatalytic degradation of acetaminophen (Ace) in water was studied using Zeolite Socony Mobil-5
Received 8 July 2014 (ZSM-5) supported TiO2 materials, which were synthesized using a sol–gel method. The structural fea-
Received in revised form 5 December 2014 tures of the photocatalysts were investigated by X-ray diffraction (XRD), scanning electron microscopy
Accepted 23 December 2014
(SEM) and surface area (BET) measurements. The best loading content of TiO2 over ZSM-5 was 40 wt%
Available online 6 January 2015
and the initial concentration of Ace was controlled at 15 mg L−1 with low intensity irradiations of
0.97 mW cm−2 , the degradation rate can reach to 96.6% after 180 min irradiation. Hydroxylation and
Keywords:
photolysis were proposed as the initial step for Ace degradation. Main reaction intermediates and prod-
Nanomaterials
PPCPs
ucts were identified by GC–MS analysis. Additionally, the material was regenerated four times, while the
Photocatalyst degradation of Ace remained at a higher level of approximately 90%.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction accumulation of drugs in the aquatic environment, novel and pow-

Pharmaceutical and personal care products (PPCPs) have
received wide attention in recent years. They have been detected
in sewage effluents [1], surface and ground water, and drinking
water [2]. PPCPs mainly include antibiotics, analgesics, disinfec-
tants, hormone cytostatic agents, and immunosuppressive drugs
[3]. As PPCPs are not biodegradable, their treatment using conven-
tional technologies does not result in efficient removal of the target
pollutants. Therefore, PPCPs pose serious threats to public health
and aqueous organism.
Among the variety of PPCPs, acetaminophen (Ace) is a com-
mon analgesic and antipyretic drug and represents one of the
most widely used prescription and over-the-counter drugs [4].
It was found that 58–68% of Ace was excreted from the body
after therapeutic use [5]. Ace has been detected worldwide with
a concentration of up to 6 ␮g L−1 in European sewage treatment
plant effluents [6], up to 10 ␮L−1 in natural waters in the USA
[7], 6.8 ␮g L−1 in wastewater treatment plant influents in Korea
[8], and more than 65 ␮g L−1 within the Tyne River in the UK [9].
The pollutant is hardly biodegradable, more toxic than azo-dyes in
low concentration. When Ace was used excessly or with alcohol,
it could cause liver failure and death [10]. To avoid the undesired
∗ Corresponding author. Tel.: +86 952 2188132.
E-mail address: jingyouhai@xmu.edu.cn (Y.-H. Jing).
erful oxidation techniques are required to remove these pollutants
from wastewater.
Photocatalysis that uses semiconductor catalysts such as TiO2 is
a promising technology for removing PPCPs from wastewater. TiO2
is inexpensive, non-toxic, stable, and potentially reusable in water.
Pei and Hu [11] used TiO2 as the photocatalyst and studied the
ability of high power ultraviolet A light-emitting diode (UVA/LED)
as a light source (365 nm) for the degradation of Ace. They reported
that Ace could be degraded to non-detectable within 20 min. In
their study, the optimal operating catalyst dosage was 0.02 g L−1 .
Zhang et al. [12] investigated the photocatalytic degradation of Ace
in a TiO2 suspended solution under a 250 W metal halide lamp.
After 100 min of irradiation, about 95% of Ace was decomposed in
the 1.0 g L−1 TiO2 aqueous solution with an initial Ace concentration
of 15 mg L−1 .
However, in aqueous systems, separation of TiO2 particles cre-
ates operating costs during treatment, due to the need to undertake
several filtration methods. To overcome these problems, nano-
meter sized TiO2 need to be loaded on supports to facilitate easy
separation as well as to maintain high photocatalytic efficiency [13].
In the study of Fukahori and Fujiwara [14], TiO2 /high-silica zeo-
lite composite was applied for the removal of sulfamethazine (SMT)
antibiotic from water, and simple models including both adsorption
and photocatalytic decomposition were developed. In their study,
80% of the SMT could be removed after 6 h of treatment. Pan et al.
[15] used TiO2 -doped low-silica X zeolite (TiO2 -LSX) to study the

http://dx.doi.org/10.1016/j.mseb.2014.12.025
0921-5107/© 2015 Elsevier B.V. All rights reserved.
54 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60
degradation of 17␣-ethinylestradiol (EE2), a higher EE2 removal
efficiency was attained with UV-TiO2 -LSX when compared with
UV-TiO2 or UV alone. In this study, ZSM-5 was selected to support
TiO2 particles. ZSM-5 zeolite, with highly ordered micropores for
diffusion, surface acidity, and ion-exchange capacities, has excel-
lent adsorption properties of various waterborne organic pollutants
including PPCPs, and also play important roles in hole-trapping,
thus increasing the concentration of pollutant near TiO2 particles
and decreasing the possibility of electron–hole recombination.
To make the results in our study more comparable to previous
studies, the Ace concentration range in our study was chosen at
7.5–60 mg L−1 , which was similar with that of Jagannathan et al.
[16], Lin and Yang [17] and Zhang et al. [12]. In their study,
the initial Ace concentrations were 4.8–18 mg L−1 , 50 mg L−1 and
3.75–15 mg L−1 , respectively. Ace presents two absorption charac-
teristics (as shown in Fig. S1), the band at 208 nm is due to a n–␲*
transition and the band at 243 nm is due to the ␲–␲* transition of
the C O group [18].
This study investigated the effects of the loading content of TiO2
over ZSM-5, the initial Ace concentration and oxygen concentra-
tions of the solution on the removal of Ace in wastewater. A kinetic
equation for Ace photocatalytic degradation was evaluated, while
the intermediates and degradation byproducts were also identified.
2. Materials and methods
2.1. Materials
The raw ZSM-5 used as a support in this study was obtained from
Acros (2–3 ␮m particle size, 2.4 nm pore size, 311 m2 g−1 surface
area, Si/Al = 1000). The titanate n-butyl acetate (99%) used was pro-
vided from the same Acros (New Jersey, USA). Ethyl alcohol (99.5%,
v/v) and nitric acid (69.7%, v/v) were supplied by Shiyaku. Ace was
purchased from Acros and used as received by the suppliers with-
out further purification. All of the aqueous solutions were freshly
prepared with deionized (DI) water.
2.2. Methods
2.2.1. Preparation of catalysts
TiO2 /ZSM-5 catalysts were prepared according to a sol–gel pro-
cess (as shown in Fig. S2). The titanate n-butyl acetate, ethanol
and nitric acid were mixed in a 6:24:1 volume ratio, respectively.
After stirring for 30 min at ambient temperature, 2.013 g ZSM-5 was
added into the solution. About 1 mL DI water was slowly added to
the above mixture of solution after stirring for another 1 h. The
solution was kept at 60 rpm of stirring speed and the temperature
was controlled at 343 K to better hydrolyze the butyl titanate to
that it was adsorbed on the surface of the ZSM-5 particles. After its
formation, the gel was dried at 373 K for 12 h to remove the sol-
vent. Then it was washed several times. Finally, the photocatalysts
were generated at the calcination temperature of 673 K for 2 h in a
muffle furnace. The calcination temperature was setting according
to two main reasons. At first, more anatase crystal could formed at
400 ◦ C, which was identified by XRD. Second, the structure of ZSM-5
can be intact in this calcination temperature, which was investi-
gated by TGA and BET. After grinding them into fine powder, the
photocatalysts were stored in an oven and hereafter are referred to
as x wt%GTZ (TiO2 /ZSM-5 compounds which were prepared by gel
method), where x is the loading content of TiO2 in the composite
photocatalyst.
2.2.2. Characterization techniques
The crystalline structures of the photocatalyst were measured
by X-ray diffraction using Cu Ka radiation ( = 1.54 Å) operating
at 40 kV and 40 mA and scanning rate of 28 min−1 (XRD, Rigaku,
Ultima IV). The surface morphologies of the raw ZSM-5 and TiO2
supported catalysts were also determined by using Scanning Elec-
tion Microscope (SEM, Mac Science, MXP18) operating at 20 kV
using catalyst powders supported on a carbon tape. The surface area
was calculated based on the N2 adsorption–desorption isotherms
according to the Brunnauer–Emmett–Teller (BET, Micromeritics,
ASAP 2020N) equation and the pores sizes were measured by the
BJH method of adsorption. UV–vis absorption spectra of the Ace
solution were determined using a UV-visible spectrophotometer
(Hitachi, U-3900). The total organic carbon (TOC) was measured
with a Tekmar Dohrmann carbon analyzer model Phoenix 8000 and
GC-MS (Hewlett packard, HP 6890) which use the Mass Selective
Detector (Hewlett packard, 5973) was used to detect the pho-
todegradation byproducts.
2.2.3. Photocatalytic reaction
Photocatalytic activities were evaluated in a photocatalytic
reactor with the diameter of 7 cm and height of 40 cm. The volume
of the solution was controlled at 500 mL. A 14 W UV lamp (254 nm,
0.97 mW/cm2 the spectrogram of the lamp is shown in Fig. S3) was
used as the source of the light. All the experiments were performed
at the temperature of 313 K by means of a continuous circulation
of water in the reactor and at the initial pH of the Ace solution (pH
6.8). The dosage of the catalyst was controlled at 1.0 g L−1 .
Before turning on the light, the solution was magnetically stirred
for 30 min in the dark to ensure adsorption–desorption equilib-
rium. The UV–vis absorption of 15 mg L−1 Ace solution before
and after adsorption–desorption equilibrium was measured (Fig.
S4), there was no change of the maximum absorption wave-
length. Then, the light source was turned on. The photodegradation
ran for 180 min, samples were withdrawn from the suspension
under the UV irradiation using syringe and a Millipore filter
(pore size 0.45 ␮m) to remove the photocatalysts before chemi-
cal analyzing. The absorbance of the solution was measured by a
UV-vis spectrophotometer at the maximum absorption wavelength
( = 243 nm) of the Ace. The removal efficiency (, %) of Ace has been
calculated by applying the following equation:
C0 − C
= × 100 (1)
C0
where C0 is the initial Ace content and C was the remaining Ace
concentration in solution after treatment.
3. Results and discussion
3.1. Character of photocatalysts
3.1.1. XRD
The XRD patterns of 5 wt%GTZ, 10 wt%GTZ, 20 wt%GTZ,
40 wt%GTZ and TiO2 which was also prepared by the sol–gel
method, are presented in Fig. 1. 40 wt%MTZ (TiO2 and ZSM-5 were
mechanically blended) was also synthetized to make a comparison.
The patterns of TiO2 loaded catalysts demonstrate relatively wide
and low diffraction of peak intensities. The XRD pattern demon-
strated TiO2 diffractions with signals at d101, d004, d200, and d211
planes of anatase at 25.4◦ , 37.9◦ , 48.0◦ and 54.4◦ , respectively. This
result is consisted with the finding of Neren Ökte and Yılmaz [19].
The rutile phase of TiO2 was not detected due to the stabilizing
effects of silica present in the ZSM-5 framework, as previously
reported in the literature [20]. With the increasing loading content
of the TiO2 on ZSM-5, the diffraction peaks of TiO2 became more
intense and sharper. The crystal structures of the ZSM-5 did not
change even after TiO2 loading, as there was no significant shift of
zeolite in the TiO2 /ZSM-5 peaks by comparison with those of pure
zeolite.
 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60 55

100

80

60

C/Co (%)
40 5 wt% GTZ
10 wt% GTZ
20 wt%GTZ
40 wt%GTZ
20 P25
ZSM-5
TiO2

0
0 50 100 150 200

Time (min)

Fig. 3. Influence of TiO2 loading content on ZSM-5 to Ace removal.

much larger than the pore size of ZSM-5, these particles might not
Fig. 1. XRD pattern of (a) ZSM-5, (b) 5 wt%GTZ, (c) 10 wt%GTZ, (d) 20 wt%GTZ, (e) be located within the pores or inner surfaces of the support, instead
40 wt%GTZ, (f) 40 wt%MTZ, (g) TiO2 . they can be adsorbed on the outer surfaces of ZSM-5.

Table 1
3.1.3. SEM
Surface area and pore size of all supported catalysts and raw zeolite.
The morphology of the raw ZSM-5 and 5, 10, 20, and 40 wt%GTZ
Catalysts Surface area (m2 g−1 ) Pore size (nm) was investigated using SEM, as illustrated in Fig. 2. The SEM results
ZSM-5 311 2.40 were also in agreement with the finding of XRD as there was no
5 wt%GTZ 318 3.28 major change in the structure of the ZSM-5. The particle size of the
10 wt%GTZ 343 3.74 ZSM-5 was about 2–3 ␮m while their diameters ranging from 50
20 wt%GTZ 284 3.84
to 500 nm. The TiO2 particles were aggregated on the surface of
40 wt%GTZ 235 4.20
the ZSM-5, that was the reason why the TiO2 particles observed
by SEM were bigger than that observed by XRD. These findings are
3.1.2. BET surface area consistent with the work of Zhao et al. [21].
The surface area (SBET ) and the pore size of ZSM-5 and 5, 10,
20, and 40 wt%GTZ were determined based on the N2 adsorption– 3.2. Performance of catalysts
desorption isotherms using the Barrett–Joyner–Halenda (BJH)
method. The results are listed in Table 1. The surface area and pore 3.2.1. Effects of TiO2 content
size of the ZSM-5 is 311 m2 g−1 and 2.40 nm, respectively. With the To find the best TiO2 loading content for degradation of Ace in
increasing TiO2 load content from 5 wt% to 40 wt%, the surface area aqueous solutions, the effects of different TiO2 loading contents
of the materials decreased from 311 to 235 m2 g−1 and the pore size (5, 10, 20 and 40 wt%) on ZSM-5 were investigated at an initial Ace
increased from 2.40 to 4.20 nm. The results indicate that the sol–gel concentration of 15 mg L−1 (as shown in Fig. 3). The photocatalyst
process employed in this study could expand the pores of the mate- dosage was controlled at 1.0 g L−1 and the pH was kept at the
rials. Since TiO2 particle sizes (50–500 nm, observed in SEM) are initial value of 6.8. The results indicated that the best TiO2 loading

Fig. 2. SEM photographs of ZSM-5 and 40%GTZ.

56 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60

content on the ZSM-5 for attaining the maximum the degradation 12000
of Ace was 40 wt%, where the removal reached 96.58% after
180 min of UV irradiation. The removal rate was enhanced with the 10000 1/k =214.59C -2485.0
app o
2
increasing TiO2 loading from 5 wt% to 40 wt%. This was attributed r =0.9757
to the increase in the amount of TiO2 particles, which generated 8000
additional active sites.

1/kapp (min)
The photodegradation abilities of raw ZSM-5 and TiO2 were 6000
also studied. The removal mechanism of Ace by ZSM-5 including
adsorption and photodegradation. It was obviously that there was 4000
an adsorption–desorption equilibrium when in the later 15 min
dark experiment. However, when the light was tuning on, the con- 2000
centration of Ace kept decreasing. According to this phenomenon,
we supposed that ZSM-5 also has photodegradation ability, more 0
details will be studied in our later research. The combining of the
degradation of the two materials was 71.08%, which was lower than
-2000
that of 40 wt%GTZ. The results indicated that the coupling of the 0 10 20 30 40 50 60 70
TiO2 and ZSM-5 has synergistic effects to promote photocatalysis.
Initial concentration of Ace (ppm)
In this study, commercial P25 was also used for comparison, after
180 min UV irradiation, only 32% of Ace was degraded with an initial Fig. 4. The relationship between 1/k1 and [Ace0 ].
concentration of 15 mg L−1 .
The degradation of Ace with an initial concentration of 15 mg L−1
under three different conditions is shown in Fig. S5. The results The results presented in Fig. 4 indicated a satisfactory linear
showed that UV (254 nm) radiation alone degraded a negligible relationship (r2 = 0.9757) between 1/kapp and C0 , which suggests
amount of Ace, while 17.7% of Ace in the solution can be removed that the surface reaction of Ace, such as oxidation by sur-
by adsorption with 40 wt%GTZ alone (without UV). face • OH, remain important [24]. kini and KAce were obtained
as 4.66 × 10−3 mg L−1 min−1 and 0.086 L mg−1 , respectively. The
results of this study fit better with the L–H equation than that of
3.2.2. Effect of initial Ace concentration other studies [4,11] (which reported r2 = 0.93 and 0.9707, respec-
The effect of Ace on the photocatalyst degradation rate was stud- tively). This is due to the much higher photocatalyst degradation
ied by varying its concentration from 7.5 to 60 mg L−1 . As there is efficiency of TiO2 /ZSM-5 than that of pure TiO2 . The degradation
interference due to ions in the natural water, which would reduce rate in our study is higher than that of Jagannathan et al. [16], who
the degradation ability of our photocatalysts, initial concentrations used similar range concentration of Ace.
of Ace in this study was higher than the detected levels in the envi-
ronment [22]. The results are shown in Fig. S6. The finding revealed
3.2.3. Effect of oxygen concentration
that the degradation reaction rate decreased with increasing ini-
Minimizing the electron–hole pair recombination would accel-
tial concentration of Ace. When the initial concentration of Ace
erate the photodegradation of the Ace in aqueous solution. Using
increased from 7.5 to 60 mg L−1 , the degradation efficiency of Ace
oxygen as an economical electron acceptor, photocatalytic degra-
decreased from 96% to 3%, after 180 min of UV irradiation. When
dation efficiencies can be enhanced [25]. In this study, N2 gas was
the initial concentration of Ace increased from 7.5 to 15 mg L−1 ,
added in the solution to reduce O2 concentration. Using a dissolved
degradation rate was maintained at a high level. This is attributed
oxygen (DO) meter, the DO at air ventilation rates of 0, 2.5, 5.0, and
to the fact that the production of radicals and holes remained con-
10.0 L min−1 and a N2 ventilation rate of 5.0 L min−1 were 4.3, 5.6,
stant for a given dosage of photocatalyst. Under the same optimum
7.8, 7.9 and 1.7 mg L−1 , respectively. The degradation efficiency is
conditions, the amount of radicals and holes produced by the GTZ
presented in Fig. S7. The adsorption of Ace in the ventilated solu-
is sufficient for the degradation of Ace until the concentration of
tions all increased. The addition of oxygen into the solution also
Ace reaches 15 mg L−1 . Based on this, 15 mg L−1 was chosen as the
increased the photocatalytic degradation rate. The removal effi-
initial concentration of Ace for the subsequent studies. The effect
ciency of Ace after 90 min irradiation using 40 wt%GTZ with oxygen
of low Ace concentration on reaction rate will be the key point of
our further studies. At a higher initial concentration, Ace molecules
absorbed additional photons. Consequently, this decreased avail- 800
able photons to activate TiO2 .
The photocatalytic oxidation kinetics of Ace can be success- 1/kapp=1066.3× 1/[O2]+27.078
fully modeled using the Langmuir–Hinshelwood (L–H) equation r2=0.9774
600
to describe a correlation between degradation rate constants and
initial Ace concentrations [23]. The rate law is listed in Eq. (2),
1/kapp (min)

kini KAce
kapp = (2) 400
C0 KAce + 1

with a linearized expression of

200
1 1 1
= C0 + (3)
kapp kini kini KAce

where C0 is the initial concentration of Ace (mg L−1 ), kapp is 0

the apparent reaction rate constant (min−1 ), kini is the intrinsic 0.0 .2 .4 .6 .8
reaction rate constant (mg L−1 min−1 ) and KAce is the L–H adsorp- 1/[O2] (mg L)
-1

tion constant of Ace over 40 wt%GTZ surface (L mg−1 ) in aqueous

environments. Fig. 5. The relationship between 1/kapp and 1/[O2 ].
 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60 57

1.0 100
-1
[O2]=4.3 mg L [Ace]0=7.5 ppm
-1
[O2]=4.3 mg L [Ace]0=15 ppm
-1 TOC removal

Relative concentration C/Co(%)

.8 [O2]=5.6 mg L [Ace]0=15 ppm
80
-1 Degradation
[O2]=7.9 mg L [Ace]0=15 ppm
calulated-
-1
[O2]=4.3 mg L [Ace]0=7.5 ppm
.6 60
caculated-
C/Co

-1
[O2]=4.3 mg L [Ace]0=15.0 ppm
caculated-
-1
.4 [O2]=5.6 mg L [Ace]0=15.0 ppm
caculated- 40
-1
[O2]=7.9 mg L [Ace]0=15.0 ppm

.2
20

0.0
0 20 40 60 80 100 120 140 160 180 0
0 20 40 60 80 100 120 140 160 180
Radiation time (min)
Radiation time (min)
Fig. 6. Experimental and calculated normalized Ace concentration versus radiation
time under different initial Ace concentration and oxygen concentration. Fig. 8. TOC removal and degradation efficiency of Ace by 40 wt%GTZ.

concentrations of 1.7, 4.3, 5.6, 7.8 and 7.9 mg L−1 were 31%, 78%,
82%, 85% and 88%, respectively.
The DO value of the solution was not significantly enhanced where kapp is the degradation rate constant (min−1 ), kO2 is
when the ventilation rate increased from 5.0 to 10.0 L min−1 , while the intrinsic rate constant (mg L−1 min−1 ) of the Ace reaction,
the degradation rate constant increased significantly. This was and KO2 is the Langmuir adsorption constant of oxygen over a
attributed to the vigorous agitation of the solution, which increased 40 wt%GTZ surface (mg L−1 ) [24]. A plot of the 1/kapp against 1/[O2 ]
the probability of collision between Ace molecules and 40 wt%GTZ. result in a satisfactory linear correlation (r2 = 0.9774), as shown
Effects of oxygen concentration on the degradation rate could be in Fig. 5. This indicates that introducing oxygen into the reac-
described using the following equation: tion system, effectively inhibited electron–hole recombination,
as oxygen consumed conduction band electrons, thus increas-
kO2 KO2 [O2 ] ing the photocatalytic degradation rate. Based on the slope and
kapp = (4)
[O2 ]KO2 + 1 intercept of the fitted curve, kO2 and KO2 values were obtained
with a linearized expression of as 0.0369 mg L−1 min−1 and 0.025 mg−1 L, respectively. Oxygen
reacted with conduction band electrons of TiO2 , thus forming
1 1 1 1 superoxide radical anions (O2 −• ), which can also directly degrade
= · + (5)
kapp kO2 KO2 [O2 ] kO2 Ace.

Fig. 7. The relationship between calculated degradation rate constant, initial Ace concentration and oxygen concentration.
58 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60

Fig. 9. Proposed pathway for photocatalytic degradation of Ace solution with 40 wt%GTZ.

3.2.4. Degradation kinetics of Ace temperature controlled at 313 K. Therefore, Eq. (6) was simplified
Since an expression of degradation kinetics is useful to design as follows:
a large-scale photoreactor, a series of experiments under vari-
ous conditions were carried out as mentioned earlier in Sections [O2 ] C
rs = K × × (7)
3.2.1–3.2.3. If the effects of light intensity, initial concentration of 1 + KO2 · [O2 ] 1 + KAce C0
Ace, dissolved oxygen, and temperature are considered, the photo-
catalytic degradation rate could be expressed completely with the where K is a constant with the range of [O2 ] between 4.3 and
following expression [24]: 7.9 mg L−1 . In contrast, C0 varied between 7.5 and 15 mg L−1 . Apply-
ing the experimentally obtained kinetic constant (KAce and KO2
 E  were obtained in Eqs. (3) and (5), the values were 0.025 mg L−1
KO2 [O2 ] KAce CS
rs = k0 × exp −
a
× Iˇ × × (6) and 0.086 mg−1 L, respectively) and knowing experimental param-
RT 1 + KO2 · [O2 ] 1 + KAce CS0 eters such as oxygen concentration and initial Ace concentration,
a kinetic equation for Ace photocatalytic degradation in this study
where rs is the photocatalytic degradation rate, I is the light inten- could be expressed as follows:
sity, and ˇ is the kinetic constant relative to light intensity. In
this study, the experiments were conducted at initial pH value of [O2 ] C
rs = −0.075 × × (8)
6.8, a constant light intensity of 0.97 mW cm−2 , and experimental 1 + 0.025 · [O2 ] 1 + 0.086 · C0
 C.-T. Chang et al. / Materials Science and Engineering B 196 (2015) 53–60 59

The comparison between the calculation based on the empir- 100

ical equation and the experimentally obtained degradation rate 1st run 2st run 3st run 4st run
constants are shown in Fig. 6. The agreement between theoretically
calculated and experimentally obtained suggests that this graph 80
can be used to simulate Ace concentrations along the reaction time
[11]. Matrix laboratory (MATLAB) was applied in this study to sim-
ulate the relationship between degradation rate constants, initial 60

C/Co (%)
Ace concentrations, and oxygen concentrations (Fig. 7). The results
indicate that the degradation rate constant of Ace was faster with
higher oxygen concentrations. 40

3.2.5. TOC removal

The TOC removal and degradation of Ace (15 mg L−1 ) solution by 20
40 wt%GTZ was determined. The results (presented in Fig. 8) indi-
cated that the Ace was nearly completely removed, while only 58%
of TOC was eliminated after 180 min of UV irradiation. This indi- 0
cates that some of the intermediate by-products remained in the 100 210 310 420 520 630 730 840
solution after treatment. As reflected in Fig. 8, it is obvious that Time (min)
Ace was degraded much faster than its mineralization. Moctezuma
et al. [18] used TiO2 powders to oxidize the Ace solution; hydro- Fig. 10. Effects of regeneration on degradation rate of Ace (15 ppm) with a
quinone, benzoquinone, p-aminophenol, and p-nitrophenol were 40 wt%GTZ loading of 1.0 g L−1 .

detected as the main intermediate species in their study. The pho-

tocatalytic degradation pathways and intermediates of this study
were discussed in Section 3.2.6.
3.2.6. Preliminary reaction mechanism
The reaction mechanisms of the photocatalytic degradation of
Ace (as shown in Fig. 9) was proposed based on the data taken by GC
results (mass spectra data was shown in Fig. S8). The detected prod-
ucts in the Ace samples were presented in Table S1. On one hand,
hydroxylation and photolysis represent the staring step of Ace
degradation. For hydroxylation reaction, ipso-substitution was pro-
posed to be the main pathway for reaction with • OH. Hydroquinone
and 1,4-benzoquinone were the main intermediates in this reaction
pathway. On the other hand, photolysis was also considered as an
initial step for Ace degradation. The photolysis of Ace at  = 254 nm
led to the formation of 1-(2-amino-5-hydroxyphenyl)ethanone and
1-(2-hydroxyphenyl-5-amino)ethanone.
Similar reactions were reported for the TiO2 photocatalytic
degradation of Ace by Pozdnyakov et al. [26]. In their study,
1-(2-amino-5-hydroxyphenyl)ethanone was the main primary
photo-Fries product. Zhang et al. [12] found that the direct oxi-
dation by hole (h+ ) was proposed. Phenoxy and quinoneimine
were the main intermediates, which could not be detected in this
study. Subsequently, the intermediates were further oxidized and
resulted in the breakdown of their aromatic structures, leading to
the formation of carboxylate acid and carbon dioxide. The pH value
of the Ace solution after photocatalysis was measured. It was found
that after 180 min irradiation, the pH value was down to 4.3, which
was consistent with the GC result that some acid intermediates
were formed.
3.2.7. Regeneration of the photocatalyst
The photocatalyst was recycled and reused to study the stabil-
ity. At the end of the first catalytic cycle, the catalyst was filtered,
washed, dried at 373 K, and then calcified at 673 K for 2 h, in order
to remove the Ace and intermediates absorbed on the catalyst. The
same procedure was employed after the second and third cycles
of usage. The degradation efficiency is shown in Fig. 10. At the end
of three cycles, there was a slight decrease in the degradation rate
of Ace from 96.58% to 89.79%. It was likely due to the accumu-
lation of organic intermediates on the surface of the catalyst and
slight leaching of TiO2 particles. In order to study the effect of the
regeneration of the materials, the surface areas and pore sizes of
the recycled catalysts were tested by a N2 adsorption and desorp-
tion analyzer and the surface characterization was studied by XRD.
The results suggested that after the forth regeneration, the sur-
face area and the pore size of the photocatalysts do not change
obviously, the data was shown in the supplementary materials. The
XRD spectra also indicated that the crystal structure did not change.
Generally speaking, it proves that the catalyst could be regenerated
for multiple cycles.
4. Conclusions
Photocatalytic degradation of Ace in water was studied using
TiO2 /ZSM-5 materials, which were synthesized by a sol–gel
method. The anatase phase was mainly observed. The optimum
loading content of TiO2 on ZSM-5 for photocatalytic degradation
of Ace was 40 wt%. The degradation rate can reach to 96.6% after
180 min UV irradiation (0.97 mW cm−2 ) at the optimum operat-
ing condition of 15 mg L−1 Ace concentration, pH 6.8 and 1.0 g L−1
40 wt% GTZ dosage. The degradation rate increasing with the
increasing of oxygen concentration and the decreasing of Ace con-
centration. Based on the experimental data, the kinetic equation
was achieved. The GC–MS analysis indicated hydroxylation and
photolysis were the initial step for Ace degradation. Hydroquinone,
1,4-benzoquinone, 1-(2-hydroxyphenyl-5-amino)ethanone and
1-(2-amino-5-hydroxyphenyl)ethanone were the main interme-
diates of Ace degradation by TiO2 /ZSM-5. The photocatalyst was
regenerated four times, with its degradation rate remained at a
higher level of about 90%. The finding of this study could benefit
future applications in water and wastewater treatment.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.mseb.
2014.12.025.
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