Catalysis Communications 11 (2010) 422–425

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Degradation of paracetamol in self assembly b-cyclodextrin/TiO2 suspension under

visible irradiation
Xu Zhang, Feng Wu, Nansheng Deng *
School of Resources and Environmental Science, Wuhan University, Wuhan 430079, PR China

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

Article history: b-cyclodextrin grafted titanium dioxide (b-CD/TiO2) was synthesized through photo-induced self assem-
Received 27 September 2009 bly methods in this work. After being modified by b-CD, the photocatalytic activities of TiO2 samples
Received in revised form 17 November 2009 increased by 2.3 times the degradation of paracetamol under visible light irradiation. The decrease trend
Accepted 19 November 2009
in final degradation efficiency was 10% after three repetitive experiments. According to present and pub-
Available online 26 November 2009
lished results, b-CD/TiO2 possesses great potential to be an effective and stable catalyst. Mechanism of
photocatalysis with b-CD/TiO2 is also proposed.
Keywords:
Ó 2009 Elsevier B.V. All rights reserved.
Cyclodextrin
TiO2
Paracetamol
Visible irradiation

1. Introduction
Successful improvement of TiO2 performance requires the low-
ering of the band gap to use the visible light and restriction of the
charge-hole recombination to enhance the quantum efficiency.
Common methods include control of particle size, crystallinity,
crystalline phase, doping with ions and surface modification [1].
Some excellent literatures have been published to elucidate the
effect of b-CD on the photochemical properties of TiO2 colloids
[2–6]. Some previous papers have reported the stimulative effect
of cyclodextrin on the photocatalytic degradation of organic pollu-
tants in TiO2 suspension [7–10]. However, it is difficult to recover
cyclodextrin after reaction since b-CD is an expensive reagent. Fur-
thermore, the synthesis of b-CD modified TiO2 colloids was compli-
cated and the colloids would only be stable in acidic conditions and
usually took a long time. Therefore, it would be quite interesting to
synthesize b-CD grafted TiO2 hybrid powder by a new method and
investigate its catalytic performance.
Recently, Toma et al. synthesized the carboxymethyl-b-cyclo-
dextrin modified mesoporous TiO2 films by immersing TiO2 films
in carboxymethyl-b-cyclodextrin solution [11]. Zhou et al. reported
the solar-induced self assembly of TiO2–b-cyclodextrin–MWCNT
composite wires [12]. Our previous work showed b-CD had barely
any degradation in irradiated TiO2 suspension with nitrogen bub-
bling [8]. Therefore, it was reasonable and practical to synthesize
* Corresponding author. Tel./fax: +86 27 68778511.
E-mail address: nsdeng@whu.edu.cn (N. Deng).
b-CD grafted TiO2 hybrid powder using photo-induced self assem-
bly method with the nitrogen protection.
In this work, b-CD/TiO2 was synthesized by photo-induced self
assembly process. Photocatalytic degradation of paracetamol un-
der visible light irradiation was carried out in order to test the cat-
alytic performance of b-CD/TiO2.
2. Experimental sections
2.1. Chemicals and materials
b-CD was purchased from Wako Pure Chemical Inc. (HPLC,
>97%). The photocatalyst nano-TiO2 (particle size 10–20 nm,
crystal structure 100% anatase as determined by X-ray diffraction
analysis) was purchased from High Technology Nano Co. Ltd. (Nan-
jing, PRC). Paracetamol (98%) was purchased from Alfa Aesar (Alfa
Aesar, Britain). Methanol was spectroscopic grade (TEDIA, USA).
Pure water used was treated with an ultrapure water system (Liy-
uan Electric Instrument Co. Beijing, PRC).
2.2. b-CD/TiO2 hybrid nanoparticle preparation and characterization
In a typical synthesis of b-CD/TiO2 hybrid nano-powder, 2.0 g/L
TiO2 and 10.0 g/L b-CD suspended solution was irradiated under a
15 W UV disinfection lamp (Xinghui Lamp Co. Ltd., Hunan, PRC)
emitting 254 nm light with an intensity of 1.04  105 Ein/(Ls)
as established by ferrioxalate actinometry [13] for 24 h with
continuous nitrogen air bubbling. The amount of b-CD used in
the synthesis was about 10 times the maximum adsorption

1566-7367/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2009.11.013
 X. Zhang et al. / Catalysis Communications 11 (2010) 422–425 423

amount of b-CD on TiO2. The suspension was centrifuged and the 0.8 1.5
solid phase was collected and carefully washed with ultrapure
water until there was no b-CD detected in the supernatant liquid 1.2
by phenolphthalein colorimetry. Meanwhile, a control experiment 0.6

Intensity
without UV irradiation was also carried out. 0.9
UV–vis diffuse reflectance spectra (DRS) were recorded on a β -CD/TiO2 hybrid powder

Intensity
0.6
Shimadzu 2550 UV–vis Spectrophotometers. Photoluminescence β -CD/TiO2 Adsorption
0.4
(PL) spectra were carried out on a FL-4500 (Hitachi, Japan) fluores- 0.3 Pure TiO 2
cence spectrometer. The XRD patterns of the prepared products
were recorded by using a Dmax-rA powder diffractometer (Rigaku, 0.0
0.2 200 300 400 500 600 700 800
Japan) with Cu Ka as a radiation with a step width of 2h = 0.02. λ/nm

2.3. Photocatalytic experiments

A 250 W metal halide lamp (metal halide indium–thallium–so-
dium lamp, k  365 nm, Chenguang Illumination Instrument, Jinz-
hou, China) was used in the photocatalytic experiments (The
spectrum of the metal halide light is shown in supporting
Fig. S1). A schematic representation of the reactor setup is shown
in supporting Fig. S2. The TiO2 suspended solution containing par-
acetamol was equilibrated in dark for half an hour before irradia-
tion. After this period, 5 mL aliquot was withdrawn to determine
the concentration C0. During all the oxidation reactions, 5 mL ali-
quots was collected at each time interval, filtered and analyzed
for the concentration Ct. Degradation efficiency (E(%)) of paraceta-
mol at different time was defined as Eð%Þ ¼ c0cc
0
t
 100:.
The paracetamol concentrations were analyzed by HPLC [Shi-
madzu LC-6A pump, Kromasil 100-5C18 column (4.6  250 mm,
5 lm)] with a flow rate of 1.0 mL min1 and UV absorbance detec-
tion (Waters 481 detector) at 243 nm. The mobile phase was
CH3OH/H2O mixture (30/70, v/v). The injection volume was 20 ll.
Each experiment was performed in triplicate and all results were
expressed as a mean value of the three experiments. Unless other-
wise specified, all the experiments were carried out at neutral pH
value with the temperature constant at 25 °C.
3. Results and discussion
3.1. Optical properties of different catalyst
It was suggested that the hydroxyl group played an important
role in adsorption on TiO2 surface [14] and it is reasonable that
CDs have higher affinity on TiO2 surface. It was reported that the
adsorption isotherm of b-CD on TiO2 surface was in accordance
with Langmuir adsorption theory [15]. The calculated maximum
adsorption amount of b-CD was 91.0 lM/g in this work. Since the
single surface area occupied by a single b-CD on TiO2 surface was
calculated to be 219 Å2, the estimated distance between two linked
b-CD was 16.7 Å on anatase TiO2 surface.
The UV–vis DRS spectra analysis of particle using bare TiO2 as
reference is presented in Fig. 1. CD modification has a significant
effect on the optical characteristics of anatase TiO2. The increased
visible absorption intensity was due to the ligand to metal charge
transfer (LMCT) between b-CD and TiIV located in octahedral coor-
0.0
350 400 450 500 550
λ/nm
Fig. 1. UV–vis DRS spectra of different catalyst.
It was suggested that holes scavenging ability increases with
the increasing number and spatial distribution of the hydroxyl
groups in alcohols and polyhydroxyl compounds [17]. Therefore,
b-CD could have high reactivity in capturing the photo generated
holes. XRD studies demonstrated that the anatase TiO2 conserved
its anatase crystal features after the modification (XRD patterns
are shown in supporting Fig. S3).
Higher photoluminescence intensity shows a higher recombina-
tion rate of photo generated electron and holes [18,19]. As shown
in Fig. 2, the emission at 400 nm can be attributed to the free exci-
tation of TiO2 and the emission at 470 nm can be assigned to emis-
sion signals originating from the charge-transfer transition of an
oxygen vacancy trapped electron [20,21]. Photoluminescence spec-
tra of bare anatase TiO2 and b-CD/TiO2 was quite similar, however,
b-CD/TiO2 exhibited apparently declined photoluminescence
intensity compared with TiO2, which indicated the electron/hole
recombination has been suppressed after the modification with
cyclodextrin. The catalyst prepared without irradiation showed
less decrease of the photoluminescence intensity.
3.2. Photocatalytic degradation study
3.2.1. Control experiment
As shown in Fig. 3, the concentration of paracetamol had barely
any change after 120 min adsorption on b-CD/TiO2 hybrid powder
surface. The degradation efficiency achieved 35% after 120 min
irradiation using anatase TiO2 mainly because of poor usage of vis-
400
Pure TiO
2
β -CD/TiO Adsorption
2
350 β -CD/TiO hybrid powder
2
Intensity

dination environment [2,16]. The same results were obtained in 300

the colloidal system with other modifiers [16]. It was also can be
seen that b-CD could also link to TiO2 surface without any UV irra-
diation. However, it showed less effect on the visible light 250
absorption.
Reaction of b-CD linked to TiO2 surface was probably through
Eq. (1) and Eq. (2) [2,17]
200
350 375 400 425 450 475 500
TiO2 þ hm ! eCB þ hVB
þ
ð1Þ λ/nm

þ Fig. 2. Photoluminescence spectra of different catalyst, kex = 300 nm and kem was
HþVB þ b-CD ! hCD ð2Þ scanned from 350 nm to 550 nm.
424 X. Zhang et al. / Catalysis Communications 11 (2010) 422–425

1.0 a 1.0 Paracetamol Initial Concentration:

5 μM
10 μM
25 μM
0.8 0.8 50 μM

0.6

Ct/C0
Ct/C0

0.6

0.4
0.4 β-CD/TiO2 Hybrid powder Dark Adsorption
β-CD/TiO2 Hybrid powder N2 bubbling
Pure TiO2 0.2
β-CD/TiO2 Adsorption
0.2 β-CD/TiO2 Hybrid powder
0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
t/min
t/min
Fig. 3. Photocatalytic degradation of paracetamol aqueous solutions under various
conditions. Paracetamol = 10 lM. b-CD/TiO2 = 1.0 g/L.
b 0.18

0.16
ible light. The performance of the catalyst prepared without UV

R0 /μM min-1
irradiation was similar to the bare TiO2. As expected, b-CD/TiO2 0.14
was the most efficiency catalyst in paracetamol degradation. 80%
paracetamol was decomposed after 120 min irradiation. However, 0.12
only 13% of paracetamol was decomposed in the nitrogen bubbling
solution, which indicated that oxygen showed its importance in
the photocatalytic degradation of paracetamol. This was mainly
0.10
because hydroxyl radical (OH) was formed not only via hole path-
way but also via the electron pathway which was initiated by the 0.08
reaction of conduction band electron with oxygen [22,23].
10 20 30 40 50
3.2.2. Kinetic study of paracetamol degradation C0 /μM
As shown in Fig. 4, when the initial concentration of paraceta-
mol increased from 5 to 50 lM, the degradation efficiency of par- Fig. 4. The effect of paracetamol initial concentration on the photocatalytic
acetamol decreased from 100 to 42% after 120 min irradiation. degradation (a), and the linear regression fit of the pseudo-first order equation.
b-CD/TiO2 = 1.0 g/L.
This was mainly because that the amount of reactive species like
OH was determined by light flux and the concentration of catalyst
in the solution bulk. Increase in paracetamol concentration would
lead to the apparent decrease of the degradation degree (Ct/C0).
1.0
Langmuir–Hinshelwood kinetics rate model has been applied to
the initial rates of photocatalytic degradation of many organic 0.8 first run
compounds [24,25]. The rate law is shown as Eq. (3), second run
dC 0.6
Ct/C0

R0 ¼  ¼ kre K s C 0 =ð1 þ K s C 0 Þ ð3Þ third run

dt
where R0 is the initial rate of disappearance of substrate and C0 is 0.4
the initial concentration of paracetamol. kre is the reaction rate con-
stant and Ks is taken to be the Langmuir adsorption constant. The 0.2
magnitudes of Ks and C0 are on the order of 103 and 106 respec-
tively, the value of KsC0 << 1. Therefore, as shown in Eq. (4), the
0.0
apparent rate constant kapp (1/min) in this equation is a constant 0 100 200 300 400 500
with the initial concentration of paracetamol when the other t/min
parameters remain unchanged.
Fig. 5. Cyclic photocatalytic degradation of paracetamol aqueous solution: Para-
dC cetamol 10 lM and b-CD/TiO2 = 1.0 g/L each run.
R0 ¼  ¼ kre K s C 0 ¼ kapp C 0 ð4Þ
dt
Therefore, the photodegradation of paracetamol could be ex-
pressed as a pseudo-first order reaction. The calculated result for CD and OH is 4.2  109 L/(mols) [26]. However, the lifetime of
kapp was 0.00208 1/min from the linear fit of Eq. (4) shown in OH is quite short (about 20 ns) [27], and therefore, only those rad-
Fig. 4b. icals generated in the close proximity could react with b-CD. An-
other important radical in illumination b-CD/TiO2 is superoxide
3.2.3. Sequential study of paracetamol photocatalytic degradation anion radical (O2 ). Actually, cyclodextrin derivates were used to
As shown in Fig. 5, the decrease trend in final degradation effi- improve the efficiency for O 2 trapping using various nitrone as
ciency was 10% after three repetitive experiments. Photogenerated scavengers [28]. Furthermore, b-CD was aforehand linked to the
radicals would have great effect on the stability of b-cyclodextrin surface of TiO2, so that the reaction between b-CD and diffusion
linked on the surface of TiO2. The reaction constant between b- mediated O 2 could be neglected.
 X. Zhang et al. / Catalysis Communications 11 (2010) 422–425
b-CD/TiO2 exhibited apparently declined photoluminescence
intensity compared with TiO2, which indicated the electron/hole
recombination has been suppressed in the CD grafted TiO2. There-
fore, the quantum efficiency of TiO2 was enhanced since the
þ
recombination of eCB =hVB was decreased, which resulted in higher
OH generation amount. Hence, the degradation of paracetamol
could be accelerated.
4. Conclusion
b-CD/TiO2 hybrid powder was synthesized through photo-in-
duced self assembly methods. After modified by b-CD, the catalytic
degradation of paracetamol can be significantly enhanced under
visible light irradiation in b-CD/TiO2 suspension. Sequential photo-
catalytic degradation of paracetamol under visible light revealed
that b-CD/TiO2 possessed great potential to be an effective and sta-
ble catalyst. b-CD/TiO2 could show significant photocatalytic activ-
ity mainly because b-CD could trap the photo generated holes
þ
resulting in the lower e CB =hVB recombination. Furthermore, b-CD
could play a role as ‘‘channel” or ‘‘bridge” between organic com-
pounds and TiO2 powders, which facilitated the interaction be-
tween them.
Acknowledgements
The author Xu Zhang thanks Dr. Yan Li for her valuable sugges-
tion on this paper. Other reviewers are also gratefully acknowl-
edged. This work was financed by the Natural Science
Foundation of PR China (No. 20777057).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.catcom.2009.11.013. Figures
425
showing spectrum of the metal halide light used in this work,
and the schematic representation of the reactor setup.
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