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Solar Energy 82 (2008) 700705

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A simple route for photocatalytic degradation of phenol in

aqueous zinc oxide suspension using solar energy
S.K. Pardeshi *, A.B. Patil
Department of Chemistry, University of Pune, Ganeshkhind, Pune, Maharashtra 411 007, India

Received 23 May 2007; received in revised form 29 August 2007; accepted 9 February 2008
Available online 5 March 2008

Communicated by: Associate Editor G. Calzaferri

Abstract

In a laboratory study, the eectiveness of zinc oxide-mediated solar photocatalytic degradation of phenol was examined. The eect of
various parameters like concentration of substrate, amount of photocatalyst, pH and irradiation time on the eciency of photocatalytic
degradation was studied. The demineralization of substrate was checked by Chemical Oxygen Demand (COD) reduction method. The
photocatalytic degradation of phenol was found to be more eective under solar light in comparison to articial visible light irradiation.
It was observed that photodegradation of phenol is favorable in weakly acidic or neutral solutions. Zinc oxide can be reused for ve times
as it undergoes photocorrosion only to the negligible extent. This work envisages great potential that sunlight mediated photocatalysis
has in the removal of phenol from waste water.
2008 Elsevier Ltd. All rights reserved.

Keywords: Photocatalysis; Demineralization; Zinc oxide; Phenol; Sunlight

1. Introduction (Lathasree et al., 2004). Therefore, there is a need of an

In most of the industries, phenolic compounds are
widely used and have become common pollutants in waste
water bodies. These are released to the environment, from
euents discharged by industries such as petroleum ren-
ing, coal tar, pharmaceuticals, pesticides, dyestu (Lam
et al., 2005) synthetic resins, paper and pulp mills, tanning
and paint stripping operations and as a byproduct of agri-
cultural chemicals (Parida and Parija, 2006). The phenolic
compounds are quite stable and remain in the environment
for longer period. Due to their toxicity and carcinogenic
character, they are dangerous to the ecosystem in water
bodies and human health. According to environment pro-
tection rules of Central Pollution Control Board (1992)
the discharge limit of phenols in inland water is 1 mg/L
*
Corresponding author. Tel.: +91 020 25601225x514; fax: +91 020
25691728.
E-mail address: skpar@chem.unipune.ernet.in (S.K. Pardeshi).
eective and economic treatment of industrial euents
containing phenolic compounds.
Traditional waste water treatment methods have some
limitations and disadvantages. Chemical oxidation tech-
nique is economically suitable for removal of pollutants of
high concentration but it is unable to mineralize all organics
(Takeda and Teranishi, 1988). Biochemical treatment is slow
and requires control of proper pH and temperature along
with the problem of disposal of activated sludge (Krumme
and Boyd, 1988). Activated carbon adsorption involves
phase transfer of pollutants without decomposition, which
induces another pollution problem. Elimination of toxic
and bio resistant organic pollutants from industrial waste
water by their transformation into non hazardous species
is a demanding area of research. Current trend of waste
water treatment, therefore is intending towards complete
mineralization of cocktail of organic pollutants.
Recently, Advance Oxidation Processes (AOPs) involv-
ing hydrogen peroxide, ozone and Fentons reagent with

0038-092X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2008.02.007
 S.K. Pardeshi, A.B. Patil / Solar Energy 82 (2008) 700705
or without ultra violet light have been reported to be useful
for photo oxidation of organic pollutants in waste water
(Krijgsheld and Vander Gen, 1986; Chen et al., 1999). It
reduces substantial amount of Chemical Oxidation
Demand (COD) and Total Organic Carbon (TOC) from
industrial euents. Total oxidation of organics by these
methods is cost and energy consuming.
Among the various AOPs, semiconductor mediated
photo catalysis shows great importance over last few years
due to its ability to destroy a wide range of organic and
inorganic pollutants at ambient temperature and pressure,
without generation of harmful byproducts. The most com-
monly used photo catalysts are TiO2, ZnO, ZrO2, CdS, and
SnO2 (Brezova and Stasko, 1994; Vione et al., 2005).
The use of photo catalysis has been proved to be a good
choice to achieve an eective elimination of phenolic com-
pounds (Brezova and Stasko, 1994). For this purpose inves-
tigations have been carried out mostly with TiO2 under ultra
violet light irradiation (Vione et al., 2005). However, sun-
light contains only a small fraction (4% of solar energy) of
ultra violet light as compared to visible light (43% of solar
energy) therefore technological use of TiO2 is largely
impaired (Sakthivel and Kish, 2003). Use of ultra violet light
in bulk level, for the treatment of huge quantity of industrial
euents is not much feasible and economical.
In the countries where ample amount of sunlight is
available, photo catalysis involving sunlight will be eco-
nomical and preferable. Therefore, there is a need of eec-
tive photo catalyst which undergoes photo catalytic
degradation of organic pollutants under sunlight or visible
light irradiation.
Recent studies have conrmed that zinc oxide exhibits
more eciency than TiO2 in visible light photo catalytic
degradation of some organic compounds in aqueous solu-
tion (Dindar and Icli, 2001). However, most of the work
has been carried out by irradiating zinc oxide suspension
with articial visible light (Peng et al., 2006) or by using
microwave irradiated zinc oxide (Parida and Parija,
2006). The present study focuses ecient use of sunlight
and the ability of ZnO to destroy phenol under solar light
irradiation.
2. Experimental
2.1. Materials
In present work, zinc oxide (assay 99%), phenol (assay
99.5%) and other required chemicals are of reagent grade,
obtained from Merck (Specialities Pvt. Ltd., Mumbai,
India) and were used without further purication. The
desired concentration of phenol solutions was prepared
by using double distilled water.
2.2. Photo catalytic reactor and experimental procedure
Photo catalytic degradation of phenol was performed in
a slurry batch reactor. Sunlight was used as an energy
701
source for photo catalyst. The intensity of Sunlight was
measured with the help of Wind monitor (WM250) and
which is found to be 0.50.7 kW m2. The photo degrada-
tion experiments were performed at ambient temperature
(2538 C). The pH of solutions were adjusted to desired
values from 3 to 11 by using dilute solution of H2SO4
(0.01N) and NaOH (0.01N).
In all the experiments, 100 ml phenol solution of appro-
priate concentration was taken in photo catalytic reactor.
A known quantity of photo catalyst was then added and
resulting reaction mixture was stirred magnetically in order
to obtain uniform suspension in photo catalytic reactor ves-
sel. The whole set up was then placed in sunlight between
8:00 AM and 5:00 PM in the months of DecemberFebru-
ary. Present work is mainly focused on photo catalytic activ-
ity of ZnO under irradiation of sunlight (approximately 4%
UV light and 43% visible light). In order to prove eective-
ness of ZnO in sunlight, its activity is compared with that
of articial visible light from 1000 W xenon lamp, which
mainly emits visible light in the range of 400800 nm. During
these photo catalytic degradation experiments, photo cata-
lytic reaction was conducted in a fabricated photo catalytic
reactor which congures with cylindrical glass vessel
(200 ml capacity), condensation tube, quartz cool trap, mag-
netic stirrer and 1000 W xenon lamp (EX-1000GT) with an
integrated photon ux 3  105 Einsteins cm2 s1. A water
lter is mounted on the lamp housing to eliminate infrared
radiation and thermal eect. In order to cuto wavelength
shorter than 420 nm, a light beam is passed through cut-o
lter (L-42, Kenko) to ensure that photo catalysis is achieved
only by visible light.
The COD determination tests were performed according
to standard dichromate method (Bellaire and Parr-Smith,
1985), using COD digester. The photo degradation e-
ciency was calculated from the following expression
g CODi  CODt =CODi   100;
where g is the Photodegradation eciency, CODi is the
Initial chemical oxygen demand, CODt is the Chemical
oxygen demand at time t.
3. Results and discussion
3.1. Photo degradation of phenol
The solar light assisted photo catalytic degradation of
phenol using ZnO as a photo catalyst was carried out in
a slurry form. The photo catalytic degradation of phenol
was investigated by irradiating the phenol solutions with
sunlight and visible light from 1000 W xenon lamp, in the
absence and presence of ZnO photo catalyst. In the absence
of ZnO the phenol was found to be stable towards irradia-
tion of light and photo catalytic degradation was not
observed. There was maximum 47% degradation when
phenolic solution of 75 ppm mixed with ZnO is irradiated
with visible light from 1000 W xenon lamp. However in
the presence of sunlight and ZnO, phenolic solutions of
702 S.K. Pardeshi, A.B. Patil / Solar Energy 82 (2008) 700705

2575 ppm were completely mineralized to CO2 and H2O to the screening eect of excess ZnO particles in the solu-
within 8 h. tion and scattering of light (Anandan et al., 2006).
The photo catalytic nature of ZnO, eect of substrate
concentration, amount of photo catalyst, irradiation time 3.3. Eect of phenol concentration
and pH on the eciency of phenol degradation was exam-
ined and results are discussed in the following sections. The photocatalytic degradation at dierent initial con-
centrations of phenol in the range 25300 mg/L was stud-
3.2. Eect of amount of photo catalyst ied. The photodegradation eciency of phenol by
sunlight excited ZnO was found to decrease with increase
The minimum amount of photo catalyst required for in concentration of phenol (Table 2). The maximum con-
complete degradation of maximum amount of phenol centration of phenol that could be degraded by 250 mg of
was examined by varying the amount of photo catalyst ZnO is found to be 75 ppm, as shown in Fig. 2. As the ini-
from 50 to 350 mg/100 ml. The phenol solution of tial concentration of phenol is high, more and more phenol
75 ppm concentration, showed 100% degradation when molecules are adsorbed on the surface of ZnO, but the irra-
250 mg/100 ml of ZnO was irradiated with sunlight for diation time, OH and  O 2 radicals formed on the surface
8 h (Table 1). As the amount of photo catalyst increases, of ZnO are constant. Therefore, relative number of OH
the photo degradation eciency increases up to optimum and  O2 radicals attacking the phenol molecules decreases.
loading of ZnO (250 mg/100 ml) as shown in Fig. 1. This Hence photodegradation decreases (Lathasree et al., 2004).
may be due to the fact that as the quantity of ZnO The photocatalytic degradation of phenol was checked by
increased, the number of phenol molecules adsorbed was determining COD at zero irradiation time and also at the
increased owing to an increase in the number of ZnO par- end of each experiment.
ticles. Thus, the photo degradation eciency was
enhanced. Further increase in the amount of photo catalyst 3.4. Eect of pH
showed a negative eect. The decrease in photo degrada-
tion eciency beyond 250 mg of ZnO may be attributed The eect of pH on the eciency of photo catalytic
degradation of phenol was studied in the pH range 311
Table 1 Table 2
Eect of photo catalyst amount on degradation eciency Eect of concentration of phenol on degradation eciency
Amount of photo Final COD Degradation eciency Concentration of Initial COD Final COD Degradation
catalyst (mg/100 ml) (ppm) (g) (%) phenol (ppm) (ppm) (ppm) eciency (g) (%)
50 76.16 58.72 25 62.72 0 100
100 45.69 75.24 50 124.16 0 100
150 30.46 83.49 75 184.51 0 100
200 15.37 91.67 100 265.07 15.52 94.14
250 0 100 150 345.03 31.04 91.00
300 15.52 91.59 200 435.11 107.6 75.27
350 30.40 83.52 250 528.09 217.28 58.85
Concentration of phenol = 75 ppm, initial COD = 184.51 ppm, sunlight 300 652.84 419.07 35.81
irradiation time = 8 h, initial pH 5.61. Amount of photo catalyst = 250 mg/100 ml, sunlight irradiation
time = 8 h, initial pH 56.

100
Photodegradation efficiency (%)

Photodegradation efficiency (%)

100
80

80
60
60
40
40

20
20

0 0
50 100 150 200 250 300 350 25 50 75 100 150 200 250 300
Amount of photocatalyst (mg / 100mL) Concentration of Phenol (mg / L)

Fig. 1. Eect of photo catalyst amount on degradation eciency (concen- Fig. 2. Eect of concentration of phenol on degradation eciency
tration of phenol = 75 ppm, initial COD = 184.51 ppm, sunlight irradia- (amount of photo catalyst = 250 mg/100 ml, sunlight irradiation
tion time = 8 h, initial pH 5.61, sunlight intensity = 0.50.7kW m2). time = 8 h, initial pH 56, sunlight intensity = 0.50.7kW m2).
 S.K. Pardeshi, A.B. Patil / Solar Energy 82 (2008) 700705 703

(Table 3). It was observed that, phenol degradation is

Photodegradation efficiency (%)

120
favorable at weakly acidic or neutral solutions as shown
100
in Fig. 3. In weakly acidic condition, most of the phenol
molecules remain undissociated, hence maximum number 80
of phenol molecules are adsorbed on the surface of zinc
oxide. Due to which more photo degradation was 60

observed. In alkaline medium surface of ZnO is negatively 40

charged and phenolate intermediates may be repelled away
from ZnO surface which opposes adsorption of substrate 20
molecules on the surface of photo catalyst (Ku et al.,
0
1996). As a result of this photo degradation of phenol in 1 2 3 4 5 6 7 8 9
alkaline medium decreases. Irradiation time (h)
Irradiation of sunlight
Irradiation of visible light(400-800nm) from 1000W Xenon lamp.
3.5. Eect of irradiation time
Fig. 4. Eect of irradiation time on degradation eciency (concentration of
The eect of irradiation time on photo degradation e- phenol = 75 ppm, initial COD = 184.51 ppm, amount of photo catalyst =
ciency of phenol was studied by keeping other parameters 250 mg/100 ml, initial pH 5.61, sunlight intensity = 0.50.7kW m2, inte-
constant. During these photo degradation experiments, grated photon ux for 1000 W xenon lamp = 3  105 Einsteins cm2 s1).
samples were irradiated with visible light from sun and
1000 W xenon lamp separately, in order to prove eective-
Table 4
ness of sunlight over articial visible light. The photo deg-
Eect of irradiation time on degradation eciency
radation of phenol in sunlight was found to increase with
Irradiation time (t) (h) Irradiation by Irradiation by 1000 W
increase in irradiation time and within 8 h there was
sunlight xenon lamp
100% degradation as shown in Fig. 4. However, when sun-
CODta (ppm) g(%) CODta (ppm) g (%)
0 (dark) 170.29 7.7 170.29 7.7
Table 3 1 150.74 18.3 167.1 9.44
Eect of pH on photo degradation eciency 2 121.85 33.96 154.38 16.33
pH Final COD (ppm) Degradation eciency (g) (%) 3 60.93 66.97 146.95 20.36
4 60.93 66.97 139.33 24.49
3 46.12 75
5 45.67 75.25 127.91 30.67
4 15.37 91.67
6 15.37 91.67 107.21 41.89
5 0 100
7 6.97 96.22 104.18 43.54
5.61* 0 100
8 0 100 99.5 46.07
6 0 100
9 0 100 97.61 47.09
7 7.61 95.87
8 30.46 83.49 Concentration of phenol = 75 ppm, initial COD = 184.51 ppm, amount of
9 33.91 81.62 photocatalyst = 250 mg/100 ml, initial pH 5.61.
a
10 46.69 74.69 Chemical Oxygen Demand (COD) at time t.
11 63.84 65.40
Concentration of phenol = 75 ppm, initial COD = 184.51 ppm, amount of
photo catalyst = 250 mg/100 ml, sunlight Irradiation time = 8 h.
*
pH of 75 ppm phenol solution (without adjustment).
light was replaced by visible light from 1000 W xenon
lamp, there was maximum 47% photo degradation within
nine hours and 100% degradation was never observed.
Photodegradation efficiency (%)

100
When phenol solution (75 ppm) along with ZnO is magnet-
ically stirred for 8 h in the absence of light (dark), negligible
80
(7.7%) photo degradation was observed (Table 4). For ref-
60
erence it is considered as zero hour irradiation. Thus zinc
oxide is an eective photo catalyst in sunlight as compare
40 to articial visible light.

20 4. Identication of intermediates and mechanism

0 During the initial period of irradiation, it was found that

3 4 5 5.61* 6 7 8 9 10 11
pH milky white suspension gradually changed to light brown.
The intensity of brown color was increased up to 4 h. After
Fig. 3. Eect of pH on photo degradation eciency (concentration of
phenol = 75 ppm, initial COD = 184.51 ppm, amount of photo catalyst = this, as time passed and irradiation is continued, intensity
250 mg/100 ml, sunlight irradiation time = 8 h, sunlight intensity = 0.5 of brown color was decreased and nally milky white sus-
0.7kW m2) *pH of 75 ppm phenol solution (without adjustment). pension reappeared. It was observed that, for the phenol
704 S.K. Pardeshi, A.B. Patil / Solar Energy 82 (2008) 700705

solutions of higher concentration, even after 8 h irradia- Table 5

tion, brown color to the photoreaction mixture persists Reuse of photo catalyst
and for such samples of phenol complete mineralization Photo degradation Photo Final COD Degradation eciency
was not observed. batch catalyst (ppm) (g) (%)
The brown color to the photoreaction mixture may be 1 Z 0 100
due to mixture of various reaction intermediates viz. 2 Z1 0 100
3 Z2 0 100
benzoquinone, hydroquinone and catechol. The existence 4 Z3 7.1 96.15
of various intermediates was conrmed by HPLC and 5 Z4 14.95 91.89
GC/MS. Concentration of phenol = 75 ppm, initial COD = 184.51 ppm, amount of
The excitation of ZnO by solar energy leads to the for- recovered photo catalyst used = 250 mg/100 ml, initial pH 5.61, sunlight
mation of an electronhole pair. The hole combines with irradiation time = 8 h.
water to form OH radicals while electron converts oxygen Z is original ZnO (Merck). Z1, Z2, Z3 and Z4 are recovered ZnO photo
to super oxide radical  O
2 , a strong oxidizing species. It is
catalysts obtained after rst, second, third and fourth photo catalytic
degradation experiments, respectively.
shown as follows:
sunlight
ZnO ! h e ; 1
VB CB
and also DHBs. The direct combination of two phenoxy
H2 O h !  OH H ; 2 radicals can lead to intermediates with two aromatic rings
O 2 e !  O 
2; 3 attached to each other by a single bond (Peiro et al., 2001).
 O 
2 H ! HO2 : 4
5. Reuse of photo catalyst
When phenol molecules are adsorbed on the surface of ex-
cited ZnO particle, there is activation of phenol molecules
At the time of study of eect of various parameters, for
by reaction with OH radical (2). The hydroxyl radical
every photo catalytic degradation experiment fresh ZnO
shows electrophilic character and prefer to attack electron
(Merck) was used. Reuse of ZnO was separately studied,
rich ortho or para carbon atoms of phenol. It forms
by keeping all other parameters constant. During this
dihydroxycyclohexadienyl (DCHD) radicals that undergo
study, after sunlight irradiation for 8 h, every photoreac-
further reaction with dissolved oxygen to yield dihydroxy
tion mixture was centrifuged and ltered through a
benzenes (DHBs) with simultaneous generation of HO2
0.45 lm Polytetrauro ethylene (PTFE) lters. Filtrate
radical. DCHD radicals are also converted to phenoxy
was used for COD determination and ZnO residue was
radical, as shown in the following equation:
OH
washed several times with double distilled water in ultra-
OH
OH
sonic bath followed by ltration and drying at 110 C in
OH
O2
.
an electric oven. Recovered ZnO was then reused for new
+ HO2
.
H photo degradation batch, without any further treatment
H
such as heating in any kind of furnace. All photo catalytic
degradation experiments are carried out in duplicate, under
.
OH OH
.O OH sunlight. Activity of recycled ZnO was found to retain even
after fth photo degradation experiment (Table 5). The
.
OH + H2O CO2 + H2O
reusability of ZnO is due to its stability and negligible
. OH
photo corrosion (Lathasree et al., 2004).
OH .
OH OH

6. Conclusion
O2 .
. + HO2
The zinc oxide photo catalyst was found to be inactive in
HO H
H dark as compared to articial visible light. In articial vis-
OH ible light maximum photo degradation of phenol was
Phenoxy radical exists in three mesomeric forms, as found to be 47%. Phenol solutions of lower concentration
shown below were completely mineralized by photo catalytic degrada-
.
O O O tion on the surface of ZnO under solar light irradiation.
The photo catalytic degradation of phenol was favorable
. in weakly acidic or neutral solutions. ZnO can be reused
for ve times as it undergoes photo corrosion only to the
. negligible extent. Higher concentration solutions of phenol
These phenoxy radicals can react with OH to form benzo- may be completely mineralized by modied ZnO, which is
quinone, hydroquinone, which are colored intermediates our current interest of research.
 S.K. Pardeshi, A.B. Patil / Solar Energy 82 (2008) 700705
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