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International Journal of Scientific Research in Environmental Sciences, 2(12), pp.

457-469, 2014
Available online at http://www.ijsrpub.com/ijsres
ISSN: 2322-4983; 2014; Author(s) retain the copyright of this article
http://dx.doi.org/10.12983/ijsres-2014-p0457-0469

Full Length Research Paper


Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide
Tapas Kumar Roy, Naba Kumar Mondal*
Environmental Chemistry Laboratory, Department of Environmental Science, The University of Burdwan, Burdwan, 713104,
India
*Corresponding Author: nkmenvbu@gmail.com
Received 12 October 2014; Accepted 28 November 2014

Abstract. Congo Red in aquatic system has been recognized as a serious problem in living organism because of its toxic nature
and therefore, its degradation is highly essential. In the present work, the efficacy of thermally activated ZnO was studied for
photo-catalytic degradation of Congo red (CR) dye. The batch operation was carried out by irradiating the aqueous solution of
dye in the presence of semiconductor. The effect of various parameters such as catalyst loading, pH, oxidant dose, intensity
variations and initial concentration of the dye on degradation was investigated. The maximum degradation capacity of ZnO for
CR was found to be 11.8 mg g-1 at optimized condition [303 K, 60 min, pH (8), dose (0.05g)]. The pseudo-second-order kinetic
model described the CR degradation process with a good fitting. Thermodynamic parameters such as H, S, and G were
calculated, which indicated that the process was spontaneous and exothermic in nature, that was evident by increasing the
randomness of the dye at the solid and liquid interface. The high CR degradation ability and regeneration efficiency of this
photocatalyst suggest its applicability in industrial systems and data generated would help in further upscaling of the
degradation process.
Keywords: Congo Red; Kinetic model; Photo-catalytic degradation; Thermodynamic study; Zinc Oxide

(Akar et al., 2009; Kiran et al., 2009). Also, dyes can


cause allergy, dermatitis, skin irritation and cancer in
humans (Fiorentina et al., 2010). Additionally, colour
in surface water may affect photosynthesis by
preventing light penetration, thereby compromising
aquatic life (Senturk et al., 2010).
Excess use of various dyes in the textile industry
has led to the severe water contamination by releasing
the toxic and coloured effluents, which are usually
disposed by various physical and chemical methods,
such as coagulation or flocculation (Golob et al.,
2005; Allegre et al., 2004), electrocoagulation
(Alinsafi et al., 2005), coagulation/carbon degradation
process (Papic et al., 2004), adsorption, advanced
oxidation process (AOP). However, most of the
methods barely transfer the pollutants from one phase
to another without destruction or have the other
limitations (Wang et al., 2007). But advanced
oxidation process (AOP), a photo-catalytic reaction is
a promising and emerging process for the purification
of water and air (Suzuki et al., 2008). In recent years,
as a promising tool to surrogate the traditional
wastewater treatment, semiconductor-assisted photocatalysis has fascinated the public concern for its
ability to convert the pollutants into the harmless
substances directly in the waste water (Kulkarni et al.,

1. INTRODUCTION
Environmental problems associated with organic
pollutants promote the development of fundamental
and applied research in the area of environment
(Ahmad et al., 2011). Several of these chemicals such
as azo dyes, herbicides and pesticides are actually
present in rivers and lakes, and are in part suspected of
being endocrine-disrupting chemicals (Ohko et al.,
2001; Coleman et al., 2000; Wang and Hong, 2000;
Hong et al., 1998). Synthetic dyes are the major
industrial pollutants and water contaminants
(Modirshahla et al., 2007). These dyes are used
extensively in the textile industry for dying nylon,
cotton, wool, and silk, as well as for colouring oils,
fats, waxes, varnishes, and plastics. The paper, food,
cosmetic, and leather industries are also major
consumers of these dyes (Chen, 2007).
The discharge of dye-coloured wastewaters into
the aquatic ecosystem represents both environmental
and public health risks because of the negative
ecotoxicological effects and bioaccumulation in
wildlife. Most importantly, many dyes contained in
wastewaters can decompose into carcinogenic
aromatic amines under aerobic conditions which can
cause serious health problems to humans and animals

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Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

2014; Habib et al., 2013; Khattab et al., 2012). Till


now, many kinds of semiconductors have been studied
as photo-catalysts including TiO2, ZnO, CdS, WO3,
and so on (Baruah et al., 2012; Ram et al., 2012;
Yogendra et al., 2011) among them ZnO is the most
extensively used effective photo-catalyst for its high
efficiency, photochemical stability, nontoxic nature,
and low cost. The wide spread use of ZnO as an
effective photo-catalyst in practical application which
is sensitive to UV light (Rao and Chu, 2009).
Therefore, continued study of ZnO is quite
necessary when illuminated with an appropriate light
source, the photocatalyst generates electron/hole pairs
with free electrons produced in the empty conduction
band leaving positive holes in the valence band. The
photogenerated electron/hole pairs are capable of
initiating a series of chemical reactions at the catalyst
surfaces, which involve adsorbed organic pollutants
and surficial water species that result in the
decomposition of the organic compounds. The
formations of relatively harmless end products
represent another attractive feature of this process
(Rego et al., 2009). It is well known that the highly
reactive OH radicals and holes are generated on the
surface of photocatalyst under the radiation of UV
light. Due to the fact, the photocatalytic property is a
surface reaction (Farbod and Jafarpoor, 2012),
thermally activation process which can improve the
high effective surface area. These nanoparticles have
been reported as efficient photocatalysts against
Congo Red dye at different conditions such as
optimum catalyst dosage and effective pH level. A
ZnO-assisted photocatalytic degradation study of
these Congo Red dyes under UV light (254-nm)
irradiation has been sparse.
In the last few decade, most of the removal
techniques of Congo Red by normal zinc oxide with
uv illumination were studied the optimized condition
of different parameters, adsorption kinetics and
isotherm models. But there have been no report
regarding the thermal activation of ZnO with
optimization of process parameters, adsorption
kinetics and thermodynamic feasibility and
spontaneity of photodegradation of Congo Red.
Kinetic and thermodynamic data can be used to
predict the rate and spontaneity of degradation
respectively. Therefore the aim of the present study
was formulated for degradation efficiency of CR onto
thermally activated ZnO by the illumination of uv
with optimized conditions.

2. MATERIALS AND METHODS


2.1. Thermally activation of ZnO
Thermally activated ZnO powder was obtained by
heating the pure ZnO powder at 500 C in a muffle
chamber by using nickel crucible. The sample was
heated at 500 C for 30 minutes and cooled slowly at
room temperature. After cooling the sample is ready
for dye degradation study.
2.2. Adsorbate and other chemicals
All chemicals were used of analytical grade. Congo
Red (CR), the typical anionic dye was selected as the
adsorbate in the present study. A stock solution of
1000 ppm was prepared by dissolving 1000 mg of CR
in 1L deionized water. The intermediate solution was
prepared by appropriate dilution of the working
solution. The pH of the solution was adjusted by
addition of either 0.1M HCl or 0.1M NaOH solutions
respectively.
2.3. Experimental procedure
In all experiments, the required amount of thermally
heated ZnO was suspended in 100 ml of Congo Red
dye using a magnetic stirrer. pH was measured by
using pH meter (Eutech 700). At predetermined times;
5 ml of reaction mixture was collected and centrifuged
(4,000 rpm, 15 minutes) in a centrifuge. The
absorbance at 497 nm wavelengths of the supernatants
was
determined
using
ultraviolet-visible
spectrophotometer (Systronics- 1203). Photocatalytic
reaction was carried out in a homemade photoreactor
equipped with a Philips120W, high pressure mercury
lamp as a source for near-UV radiation. The reactor
was consisted of graduated 400 cm3 Pyrex glass
beaker and a magnetic stirring setup. The lamp was
positioned perpendicularly above the beaker. The
distance between the lamp and the graduated Pyrex
glass was 10 cm. The whole photocatalytic reactor
was insulated in a wooden box to prevent the escape
of harmful radiation and minimized temperature
fluctuations caused by draughts.
2.4. Degradation experiment
Degradation measurement was determined by batch
experiment of known amount of the adsorbent with
100 ml of aqueous Congo Red solution of known
concentration (4-10 ppm) in a series of 250 ml conical
flasks. Dye concentration in the reaction mixture was
calculated from the calibration curve. Degradation
experiments curve were conducted by varying initial
concentration of the dye, pH, contact time, catalyst

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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

dose under the aspect of degradation kinetics. The


amount of dye adsorbed onto zinc oxide powder at
time t, qt (mg/g) was calculated by the following mass
balance relationship.

(2)
where Co is the initial dye concentration (mg/L), Ct
is the concentration of the dye at any time t, V is the
volume of solution (L) and m is the mass (g) of zinc
oxide powder (ZnO).

(1)
The dye removal efficiency i.e., % of degradation
was calculated as

Table 1: The dye removal capacity at different wave lengths


Sl No.
1
2
3

Parameter
Only UV(Without ZnO)
Only ZnO(without UV)
Both ZnO & UV

Removal (%)
0.00
47.95
96.45

Degradation capacity (mg/g)


0.00
5.70
11.57

Table 2: Summery of parameters for various kinetic models

Kinetic model
Pseudo

first

Equation
)

Constants

qexp (mgg-1)

qcal(mgg-1)

R2 = 0.995

order
KL = 0.0819 min-1

11.50
12.03

R2 = 0.9999
K2 = 0.0586 g.mg1

min-1

Pseudo second
order

11.8 mg.g-1
qt and qe are the amount of dye adsorbed (mg g-1) at time t and at equilibrium and KL (min-1) is the Lagergren rate constant of rst-order degradation and K2 (g
mg-1 min-1) is the second-order degradation rate constant.

Table 3: Thermodynamic parameters for adsorption of Congo Red onto ZnO particles
Temperature(K)
303
323
343
373

-10.0680
-9.6690
-10.1138
-10.8370

-6.335

11.45

reaction must be favoured. The ultimate goal of the


process is to have a reaction between the activated
electrons with an oxidant to produce a reduced
product and also a reaction between the generated
holes with a reductant to produce an oxidant product.
The photogenerated electrons could reduce the dye or
react with electron acceptors such as O2 adsorbed ZnO
surface or dissolved in water, reducing it to
superoxide radical anion O2- (Konstantinou et al.,
2004). The photongenerated holes can oxidize the
organic molecule to form R*, or react with OH- or
H2O oxidizing them into OH radicals. The resulting
OH radicals, being a strong oxidizing agent (standard

2.5. Photocatalysis
Photocatalysis may be termed as a photoinduced
reaction which is accelerated by the presence of a
catalyst (Mills et al., 1997). These types of reaction
are activated by absorption of a photon with sufficient
energy (equal or higher than the band gap energy of
the catalyst (Carp et al., 2004). The absorption leads
to a charge separation due to promotion of an electron
(e-) from valence band of the semiconductor catalyst
to the conduction band, thus generating a hole (h+) in
the valence band (Gaya et al., 2008).
The
recombination of the electron and the hole must be
prevented as much as possible if a photocatalyst

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Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

reduction potential +2.8V) can oxidise most azo dyes


to the mineral product.

degradation accelerated by magnetic stirring at 400


rpm. Photocatalytic degradation was assessed in the
presence or absence of UV irradiation provided by a
120 w middle lamp producing an intensity of 2.1 mw
/cm2 with the main emission wave length of 254 nm
positioned 10 cm from the surface of the solution. To
saturate the surface degradation capacity of the
nanomaterials, each solution was determined by uvvisible spectro-photometrically.

3. RESULTS AND DISCUSSIONS


3.1. Degradation and photocatalytic degradation
CR degradation experiments were carried out by
photocatalytic agent thermally activated zinc oxide
into 100 ml of solution in the dark at 300C with

100

18

80

Removal(%)

16

B
C

14
70

12

60

50

10

Degradation Capasity(mg/g)

90

40
8
0.02

0.03

0.04

0.05

0.06

Catalyst Dose(g)

Fig. 1: Effect of catalyst dose on photodegradation of CR dye (6 ppm), pH (8.0), Temp. (303K),

(254 nm), Time (60 min)

11.60

96

11.55
11.50

Removal(%)

11.45
11.40
11.35
11.30
94
11.25

Degradation Capasity(mg/g)

B
C

11.20
11.15
4

10

pH

Fig. 2: Effect of pH on photodegradation of CR dye (6ppm), ZnO (0.5mg/L), Temp. (303K),

(254 nm), Time (60 min)

an increase in the value of pH from 5 to 8. However


the dye degradation capacity was decreased from 11.8
to 11.3 when pH increased further from 8.5 to 10. This
behaviour can be explained by the zero point charge
of the photocatalyst. Since the pHzpc of ZnO is
9.3 0.2 (Bahnemann et al.,1987), the surface of the

3.2. Effect of pH
The effect of initial solution pH on the degradation
capacity at equilibrium conditions is shown in Figure
2. The results indicate that the dye degradation
capacity increased from 11.2 mg/g to 11.8 mg/g with

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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

catalyst is positive below pH 9.3. Again the given pKa


for Congo Red is 4.1, therefore Congo Red is
negatively charged above pH 4.1 that might result in
electrostatic attraction between the nanocatalyst and
Congo Red and will increase the degree of
photodegradation. It was further observed that the
degradation efficiency increases with increasing pH
value from 5 to 9 and above decreases. Hence the
maximum degradation range was shown at the pH of 8
- 9. The final pH of photocatalytic treatment were 8.5
that means the photocatalytic removal of colour and
degradation were observed to be faster in slightly
alkaline pH than in acidic or neutral pH range
(Neppolian et al., 2002; Tang et al., 1995; Bahnemann
et al., 1994; Hustert et al., 1992).This is due to two
reason: (a) at very low pH, ZnO particle
agglomeration reduces the dye degradation as well as
photon absorption and (b) in Congo Red, the azo
linkage (-N=N-) is particularly susceptible to
electrophilic attack by hydroxyl radical. However, in
very low pH, the concentration of H+ ions is in excess
and H+ ion interact with azo linkage decreasing the
electron densities at azo group. Consequently the
reactivity of hydroxyl radical by electrophilic
mechanism is also decreased (Gladius et al., 2009).
Hence at acidic pH range, degradation efficiency is
minimum.
Finally the isoelectric point of ZnO (8.7 10.3) is
the pH at which a particular molecule or surface
carries no net electrical charge. In isoelectric point
(IEP), ZnO surface in aqueous suspension are
generally assumed to be covered with hydroxyl
species, Zn-OH. At pH value above the IEP, the
predominate surface species is
which is less
interacted with anionic dye(CR) while at pH values
below the IEP,
species predominate

which is more interacted (Haruta, 2004; Brunelle,


1978).

3.3. Effect of Initial Dye Concentration on


photocatalytic degradation of CR dye
The effect of initial dye concentration on the rate of
photocatalytic degradation was studies by keeping all
other experimental conditions constant at light
intensity equal to 254nm , ZnO catalyst dosage was
0.05 g/100ml, pH dye solution was (8) temperature at
303K and changing the initial dye concentration in
range (4-10). The results are plotted in Figure 3. These
results indicate that the rate of photocatalytic
degradation increased with the decreasing of initial
dye concentration. As the initial concentration of a
dye increases, the colour of dye solution becomes
deeper which results in the reduction of penetration of
light to the surface of the catalyst, decreasing the
number of excited dye molecules. Due to increase of
initial concentration of dye more and more organic
substances are adsorbed on the surface of ZnO.
Therefore, the generation of hydroxyl radicals is
reduced, since there are only fewer active sites in the
system causing little adsorption of hydroxyl ions,
which in turn leads to the decrease in the generation of
hydroxyl radicals (Daneshvar et al., 2004). Thus, the
rate of hydroxyl radical generation on the catalyst
surface, accordingly, will decrease. Similar results
have been reported by other researcher for the
photocatalytic oxidation of pollutants (Nikazar et al.,
2007; Mrowetz and Selli, 2006; Mahmoodi and
Arami, 2006; Muruganandham and Swaminathan,
2006; Mahmoodi et al., 2006; Kartal et al., 2001;
Goncalves et al., 1999).
B
C

100

Removal(%)

80

10
70

60
8

Degradation Capasity(mg/g)

12

90

50

10

Concentration(ppm)

Fig. 3: Effect of concentration on photodegradation of CR dye pH (8.0), ZnO (0.5mg/L), Temp. (303K),
min)

461

(254 nm), Time (60

Roy and Mondal


Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

B
C
12

98
96

92
90

Removal(%)

88
86
84

10

82
80
78
76
74

Degradation Capasity(mg/g)

94

72
70
240

8
260

280

300

320

340

360

Wave Length(nm)

Fig. 4: Effect of wave length on photodegradation of CR dye, (6 ppm), pH (8.0), ZnO (0.5mg/L), Temp. (303K), Time (60
min)

increases significantly upon addition of ZnO due to


the production of higher amount of hydroxyl radical
through the interaction of UV with ZnO. But above 50
mg of ZnO, the colour removal efficiency
significantly decreased due to decrease of formation
of hydroxyl radicals. It should be pointed out that, the
catalyst loading aects both the number of active sites
on photocatalysts and the penetration of UV light
through the suspension (Daneshvar et al., 2003). With
increasing catalyst loading the number of active sites
increases, but the penetration of UV light decreases
due to shielding eect (Gouvea et al., 2000). It should
also be noted that the optimum value of catalyst
loading is strongly depended on the type and initial
concentration of the pollutant and the operating
conditions of the photoreactor (Gogate et al., 2004).
The optimum concentration of the catalyst for
efficient UV photodecolorization and degradation is
found to be 0.05 mg/100ml in Figure 1.

3.4. Effect of catalyst loading


The amount of catalyst loading is one of the main
parameters for the degradation studies. The results for
the dye degradation using various amounts of ZnO
(0.02-0.06 g/100ml) are shown in Figure 1. In order to
avoid the use of excess catalyst it is necessary to find
out the optimum loading for efficient removal of dye.
The results showed that when catalyst dosage was
increased from 20-50 mg, the decolourization
increases from 41% to 98.5%. However, on further
increase in dosage of the catalyst beyond 60 mg, there
is a slight decrease in the dye removal rate. Table 1
also demonstrated that the colour removal was
unchanged in the absence of ZnO indicating that CR
dye is difficult to be oxidized by only UV light. The
increase in degradation rate with increase in the
catalyst loading is due to increase in total active
surface area i.e. availability of more active sites on
catalyst surface (Goncalves et al., 1999). However, it

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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

11.60

B
C
96

Removal(%)

11.50

11.45

11.40

Degradation Capasity

11.55

11.35

11.30
94
20

30

40

50

60

70

80

90

100

110

Temperature(C)

Fig. 5: Effect of temperature on photodegradation of CR dye (6ppm), pH (8.0), ZnO (0.5mg/L),


100

(254 nm) , Time (60 min)


12

98

Degradation capasity

96

Removal(%)

94

B
C

92
90
88
86
84
0

20

40

60

80

10
100

Contact Time(min)

Fig. 6: Effect of contact time on photodegradation of CR dye (6 ppm), pH (8.0), ZnO (0.05mg), Temp. (303K),

(254 nm)

conduction band of a semiconductor photo catalyst


and the energy of a photon is related to its wavelength
and the overall energy input to a photocatalytic
process is dependent on light intensity. The rate of
degradation increases when more radiation falls on the
catalyst surface and hence more hydroxyl radicals are
produced. The degradation efficiency is found to be
maximum (i.e. 25 W/m2) in the middle area of the
photoreactor. Also similar results were reported by
Habib et al. (2012); Karimi et al. (2011); Karimi et al.
(2010); Akpon et al. (2009).

3.5. Effect of wave length of uv light


The influence of UV light intensity on the degradation
efficiency has been examined on dye solution (6 ppm)
at a pH 8.5 and ZnO loading of 0.05 g/100ml. It is
evident from the results that the experiment was
conducted by three different wave length (254, 312,
365 nm) and percentage degradation increases with
decrease in wave length of uv light in Figure 4. The
UV irradiation generates the photons required for the
electron transfer from the valence band to the

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Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

Fig. 7: Pseudo-first-order kinetics for degradation of Congo Red by photocatalytic agent ZnO

Fig. 8: Pseudo-second-order kinetics for degradation of Congo Red by photocatalytic agent ZnO

this work (Habib et al., 2012; Karimi et al., 2011;


Karimi et al., 2010).

3.6. Effect of uv irradiation


The effect of UV irradiation on the decolorization of
CR was also investigated. There was no observable
loss of color when the dye is irradiated with only UV
which suggests that the dye is resistant to direct UVphotolysis. The combined action of UV and ZnO
however produced an increase from 47.95% to 98.5%
in decolorization compared to that of ZnO alone due
to the reaction of hydroxyl radicals generated upon
photolysis. A higher percentage of removal by
ZnO/UV showed that Zn- catalyzed decolorization
with UV was more efficient than that of UV-catalyzed
in producing the hydroxyl radical responsible for the
oxidation of the dye. For ZnO/UV system, a complete
color removal was observed after 60 min of
irradiation. The high efficiency of this process is due
to the formation of more hydroxyl radical which is
attributed to zinc/UV-catalyzed (homogeneous and
heterogeneous). Table 1 summarized the results for
the color removal of CR by all system investigated in

3.7. Effect of Irradiation Time


The contact time necessary to reach equilibrium
depends on the initial dye concentration. The effects
of contact time on the decolouration of Congo Red at
60 min are illustrated in Figure 6. Figure 6 clearly
indicates that dye decolouration increase with contact
time. Hence it appears that a rapid initial degradation
occurs with equilibrium reached in 60 minutes. The
first degradation of dye molecule is due to effective
interaction of semiconducting materials and dye
molecule is faster than the solute solute interaction
(Dogan et al., 2006). However, Movahedi et al.,
(2009) pointed out that (CR) is strongly adsorbed on
thermally heated ZnO particles surfaces through the
two oxygen atoms, of the sulphonate group of the dye
molecules.

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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

Fig. 9: plot of lnK versus 1/T for the degradation of CR on ZnO

3.8. Kinetics of Photocatalytic Degradation of


Congo Red

(CR) by zinc oxide in aqueous phase is well fitted


with the second order kinetic model.

3.8.1. Pseudo first order kinetic model

3.9. Thermodynamic study

In this study degradation data are applied to the


pseudo first order kinetic models to find the rate
constants of dye degradation according to Eq. 3
)
(3)

Thermodynamic parameters can be determined from


the thermodynamic equilibrium constant K0, where K0
is the ratio of degradation capacity (mg.g-1) and
concentration
at
equilibrium
state.
The
thermodynamic parameters (G, H and S) of the
degradation of CR on ZnO were calculated using
equations and G = RT ln K0, where R is the ideal
gas constant, T is the temperature (K) and K0 is the
distribution coefficient calculated from the
experiment. The values of H and S were calculated
from the slope and intercept of the Vant hoff plots in
Figure 9 and listed in Table 3. The thermodynamics of
Congo Red degradation has been investigated
extensively. The negative value of free energy
(Table 3) indicates the feasibility of the process and its
spontaneous nature in Table 3. The experimental
values of
at different temperatures are negative.
The negative values of
for all the systems confirm
the exothermic nature of process. The positive values
of S observed for the removal of CR molecule
suggested increased the randomness during the
process. The thermodynamic values of parameters for
the CR reported in the present study and in good
agreement with literature (Vijayakumar et al., 2012).

The first order rate constant KL can be obtained from


the slope of plot between
) versus time t
is shown in Figure 7.
3.8.2. Pseudo second order kinetic model
A pseudo second order model can be used to explain
the dye degradation kinetics. The pseudo second order
model can be expressed as
(4)
Where t is the contact time (min), qe and qt are the
amount of dye adsorbed (mg/g) at equilibrium and at
any time t. A plot between t/qt versus t gives the value
of the constant K2 is shown in Figure 8 and also qe can
be calculated.
As it can be seen from Table 2, the degradation did
not comply well with the pseudo first order model
because of the absence of linearity between
) Vs t. In this study pseudo second order model
fitted better when compare with the first order kinetic
model in Table 2. From this study we can described
that the experimental value of qe of first order model
are not well matched with the calculated value
whereas in case of second order model, the
experimental value of qe are very close to the
calculated value. So the photocatalytic degradation of

4. CONCLUSION
The active species generated in the degradation of CR
under uv light irradiation were studied using thermally
heated ZnO as model systems. The present
investigation shows that zinc oxide can be utilized for
the removal of hazardous dye from aqueous solution.
The removal process is a function of shaking time,

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Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

pH, temperature and catalyst dose. It was observed


that the removal process followed the pseudo second
order kinetic model. The values of qe calculated from
pseudo second order plot are in good agreement with
the experimental value. The thermodynamic study
showed that the process is spontaneous and
exothermic in nature. Therefore, it can be concluded
that the hazardous dye such as CR can be comfortable
degraded by using thermally heated ZnO under uv
light irradiation.

feedback dye laser. Appl. Phys. Lett., 91:


051109.
Coleman HM, Eggins BR, Bryne JA, Palmer FL, King
E (2000). Photocatalytic degradation of 17-oestradiol on immobilized TiO2. Appl.
Catal. B:Environ., 24: L1 - L5.
Daneshvar N, Salari D, Khataee AR (2003). J.
Photochem, Photobiol. A. Chem., 157: 111.
Daneshvar N, Salari D, Khataee AR (2004).
Photocatalytic Degradation of Azo Dye Acid
Red 14 in Water on ZnO as an Alternative
Catalyst to TiO2. J. Photochem. Photobiol. A:
Chem., 162: 317-322.
Dogan M, Alkan M, Demirbas O, Ozdemir Y,
Ozmetin C (2006). Degradation kinetics I of
maxilon blue GRL onto sepiolite from aqueous
solutions. Chem. Eng., 124: 89-101.
Farbod M, Jafarpoor E (2012). Fabrication of
Different ZnO Nanostructures and Investigation
of Morphology Dependence of Their
Photocatalytic Properties. Mater. Lett., 85(15):
47-49.
Fiorentina LD, Triguerosa DEG, Mdenesb AN,
Espinoza-Quinonesb FR, Pereiraa NC, Barrosa
STD, Santosa OAA (2010). Biosorption of
reactive blue 5G dye onto drying orange
bagasse in batch system: kinetic and
equilibrium modeling. Chem. Eng. J., 163: 6877.
Gaya UI, Abdullah AH (2008). Heterogeneous
photocatalytic
degradation
of
organic
contaminants over TiO2: A review of
fundamentals, progresss and problems. J.
Photochem. Photobiol.C: Photochem. Rev., 9: 1
12.
Gladius LR, Shanthi M (2009). Photocatalytic
degradation of ortho-cresol by Zinc-oxide-UV
process. Nature Env. Pol. Tech., 8(3): 447
450.
Gogate PR, Pandit AB (2004). A review of imperative
technologies for wastewater treatment II: hybrid
methods. Adv. Environ. Res., 8: 553597.
Golob V, Vinder A, Simonie M (2005). Efficiency of
the coagulation/flocculation method for the
treatment of dye bath effluents. Dyes Pigments,
9397.
Goncalves MST, Oliveira-Campose AMF, Pinto
EMMS, Plasencia PMS, Queiroz MJRP (1999).
Photochemical Treatment of Solutions of Azo
Dyes Containing TiO2. Chemosphere, 39: 781786.
Gouva CAK, Wypych F, Moraes SG, Durn N,
Peralta- Zamora P (2000). Semiconductorassisted photocatalytic degradation of reactive
dyes in aqueous solution. Chemosphere, 40:
433440.

REFFERENCES
Ahmad M, Alrozi R (2011). Removal of malachite
green dye from aqueous solution using
rambutan peel based activated carbon:
Equilibrium, kinetic and thermodynamic
studies. Chem. Eng. J., 510 516.
Akar ST, zcan AS, Akar T, zcan A, Kaynak Z
(2009). Biosorption of a reactive textile dye
from aqueous solutions utilizing an agro-waste.
Desalination, 249:757761.
Akpan UG, Hameed BH (2009). Parameters affecting
the photocatalytic degradation of dyes using
TiO2-based photocatalysts. A review, J. Hazard.
Mater., 170: 520 529.
Alinsafi A, Khemis M, Pons MN, Leclerc JP,
Yaacoubi A, Benhammou A, Nejmeddine A
(2005). Electro-coagulation of reactive textile
dyes and textile wastewater. Chem. Eng.
Process, 44: 461-470.
Allegre C, Maisseub M, Charbita F, Moulin P (2004).
Coagulation-flocculation decantation of dye
house effluents: concentrated effluents. J.
Hazard. Mater., Bll6: 57-64.
Bahnemann DW, Kormann C, Hoffmann MR (1987).
Preparation and characterization of quantum
size zinc oxide: a detailed spectroscopic study.
J. Phys. Chem., 91: 3789-3798.
Bahnemann DW, Cunningham J, Fox MA, Pelizzetti
E, Pichat P, Serpone N, Zeep RG, Heltz GR,
Crosby DG (1994). Aquatic
surface
Photochemistry. Lewis Publishers, Boca Raton,
261.
Baruah S, Pal SK, Dutta J (2012). Nanostructured
Zinc Oxide for Water Treatment. J. Nanosci. &
Nanotechnol., 2: 90-102.
Brunelle JP (1978). Preparation of Catalysts by
Metallic Complex Adsorption on Mineral
Oxides. Pure Appl. Chem., 50: 1211-1229.
Carp O, Huisman CL, Reller A (2004). Photoinduced
reactivity of titanium oxide. Solid state chem.,
32: 33-177.
Chen Y, Li Z, Zhang Z, Psaltis D, Scherer A (2007).
Nanoimprinted circular grating distributed

466

International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

Habib MA, Muslim M, Shahadat MT, Islam MN,


Ismail
IMI
(2013).
Photocatalytic
decolorization of crystal violet in aqueous nanoZnO suspension under visible light irradiation.
J. Nanostructure chem., 3:70.
Habib MA, Ismail IMI, Mahmood AJ, Ullah MR
(2012).
Photocatalytic decolorization of
Brilliant Golden Yellow in TiO2 and ZnO
suspensions. J. Saudi. Chem. Soc., 16:
423429.
Haruta M (2004). Nanoparticulate Gold Catalysts for
Low-Temperature CO Oxidation. J. New Mat.
Elect. Syst., 7: 163172.
Hong CS, Wang Y, Bush B (1998). Kinetics and
products of the TiO2, Photocatalytic
degradation of 2-chlorobiphenyl in water.
Chemosphere, 36: 1653-1667.
Hustert K, Zepp RG (1992). Photocatalytic
degradation of selected azo dyes. Chemosphere,
24: 335-342.
Kartal OE, Erol M, Ouz H (2001). Photocatalytic
destruction of phenol by TiO2
powders.
Chem. Eng. Technol., 24: 645649.
Karimi L, Mirjalili M, Yazdanshenas ME, Nazari A
(2010). Effect of nano TiO2 on self-cleaning
property of cross-linking cotton fabric with
succinic acid under UV irradiation. Photochem.
Photobiol., 86: 10301037.
Karimi L, Zohoori S, Yazdanshenas ME (2011).
Photocatalytic degradation of azo dyes in
aqueous solutions under UV irradiation using
nano-strontium
titanate
as
the
nanophotocatalyst. J. Saudi. Chem. Soc., in
press.
Khattab IA, Ghaly MY, Osterlund L, Ali MEM, Farah
JY, Zaher FM, Badawy MI (2012).
Photocatalytic degradation of azo dye Reactive
Red 15 over synthesized titanium and
zinc
oxides photocatalysts: a comparative study.
Desalin. and Water Treat., 48: 120-129.
Kiran I, Ilhan S, Caner N, Iscen CF, Yildiz Z (2009).
Biosorption properties of dried Neurospora
crassa for the removal of Burazol Blue ED dye.
Desalination, 249: 273278.
Konstantinou IK, Albanis TA (2004). TiO2 Assisted
photocatalytic degradation of azo dyes in
aqueous solution : Kinetic and Mechanistic
investigation- A review. Appl. Catal.
B:Environ., 49: 1-14.
Kulkarni M, Thakur P (2014). Photocatalytic
Degradation and mineralisation of reactive azo
dye using semiconductor metal oxide nano
particles. Int. J. Eng. Res. and Gen. Sci., 2: 245254.
Mahmoodi NM, Arami M (2006). Carbon-supported
iridium catalysts in the catalytic wet air

oxidation of carboxylic acids:kinetics and


mechanistic
interpretation.
Photochem.
Photobiol. A: Chem., 182: 6066.
Mahmoodi NM, Arami M, Limaee NY (2006).
Photocatalytic degradation of triazinic ring
containing azo dye (Reactive Red 198) by using
immobilized TiO2
photoreactor: Bench
scale study. J. Hazard. Matter., 133(1-3):113-8.
Mills A, Hunte L (1997). An overview of
semiconductor photocatalysis. J. Photochem.
Photobiol, A: chem., 108: 1-35.
Modirshahla N, Behnajady MA, Ghanbary F (2007).
Decolorization and mineralization of C.I. Acid
Yellow 23 by Fenton and photo-Fenton
processes. Dyes Pigm., 73: 305-310.
Movahedi M,
Mahjoub AR,
Janitabar-Darzi S
(2009). Photodegradation of congored in
aqueous solution on ZnO as an alternative
catalyst to TiO2. J. Iran. chem. Soc., 6(3):
570-577.
Mrowetz M, Selli E (2006). Photocatalytic
degradation of formic and benzoic acids and
hydrogen peroxide evolution in TiO2 and ZnO
water suspensions.
Photochem.
Photobiol. A: Chem., 180: 1522.
Muruganandham M, Swaminathan M (2006).
Photocatalytic decolourisation and degradation
of Reactive Orange 4 by TiO2-UV process.
Dyes Pigm., 68: 133142.
Neppolian B, Choi HC, Sakthivel S, Arabindoo B,
Murugesan V (2002). Solar light induced and
TiO2 assisted degradation of textile dye reactive
blue 4. Chemosphere, 46: 1173-1181.
Nikazar M, Golivand K, Mohanpoor K (2007). Using
TiO2 supported on Clinoptilolite as a catalyst
for
photocatalytic degradation of azo
dye Disperse yellow 23 in water. Kinet. Catal.,
+ 48 (2): 214220.
Ohko Y, Ando I, Niwa C, Tatsuma T, Yamamura
T, Nakashima T, Kubota Y, Fujishima A
(2001). Degradation of bisphenol A in water
by TiO2 photocatalyst. Environ. Sci. Technol.,
35: 2365-2368.
Papic S, Koprivanac N, Bozic AI (2004). Metes, A
removal of some reactive dyes from synthetic
wastewater
by
combined
Al(III)
coagulation/carbon degradation process. Dyes
Pigm., 293300.
Ram C, Pareek RK, Singh V (2012). Photocatalytic
Degradation of Textile Dye by Using Titanium
Dioxide Nanocatalyst. Int. J. Theor. and Appl.
Sci., 4(2): 82-88.
Rao YF, Chu W (2009). A new approach to quantify
the degradation kinetics of
linuron with
UV, ozonation and UV/O3 processes.
Chemosphere, 74: 1444-1449.

467

Roy and Mondal


Photocatalytic Degradation of Congo Red Dye on Thermally Activated Zinc Oxide

Rego E, Marto J, So Marcos P, Labrincha JA


(2009). Decolouration of Orange II solutions by
TiO2 and ZnO active layers screen-printed on
ceramic tiles under sunlight irradiation. Appl.
Catal., A 355(s 12):109114.
Senturk HB, Ozdes D, Duran C (2010). Biosorption of
Rhodamine 6G from aqueous solutions onto
almond shell (Prunus dulcis) as a low cost
biosorbent. Desalination, 252: 8187.
Suzuki N, Naranmandura H, Hirano S, Suzuki LT
(2008). Theoretical calculations and reaction
analysis on the interaction of pentavelent
thioarsenicals
with
biorelevant
thiol
compounds. Chem. Res. Toxicol., 21: 5503.
Tang WZ, An H (1995). Photocatalytic degradation
kinetics and mechanism of acid blue
40 by
TiO2/UV in aqueous solution. Chemosphere,
31: 41714183.

Vijayakumar G, Tamilarasan R, Dharmendirakumar


M (2012). Adsorption, Kinetic, Equilibrium and
Thermodynamic studies on the removal of basic
dye Rhodamine-B from aqueous solution by the
use of natural adsorbent perlite. J. Mater.
Environ. Sci., 3(1): 157-170.
Wang Y, Hong C (2000). TiO2-mediated
photomineralization of 2-chlorobiphenyl: the
role of O2. Water Resour., 34: 2791-2797.
Wang H, Xie C, Zhang W, Cai S, Yang Z and Gui
Y (2007). Comparison of dye degradation
efficiency using ZnO powders with various size
scales. J. Hazard. Mater.,141:64552.
Yogendra K, Naik S, Mahadevan KM, Madhusudhana
N (2011). A comparative study of
photocatalytic activities of two different
synthesized ZnO composites against Coralene
Red F3BS dye in presence of natural solar light.
Int. J. Environ. Sci. and Res., 1(1): 11-15.

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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014

Mr T. K. Roy received his M.Sc. degree in Chemistry (Organic Chemistry) from the faculty
of Science, Visva-Bharati Unviersity, Santiniketan.

Dr Naba Kumar Mondal presently holding the position as Assistant professor in the
department of Environmental Science, The University of Burdwan, India. Dr Mondal has
experience more than 16 years of teaching and research in both Education and
Environmental Science (masters degree). His research interest includes: Pure
Science:Adsorption Chemistry, Nutrient dynamics, indoor pollution, soil Chemistry, Plant
Physiology, Social Science: corporal punishment, development of teaching methodology,
noise and its impact on school children etc. Dr Mondal also published more than 130
research papers in reputed International and National Journals and four (04) Ph.D. scholars
(upto May 2014) and has been serving as an guest Editor and reviewer in many prestigious
International Journals.

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