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Chemosphere 46 (2002) 11731181

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Solar light induced and TiO2 assisted degradation


of textile dye reactive blue 4
B. Neppolian a, H.C. Choi
a

a,*

, S. Sakthivel b, B. Arabindoo b, V. Murugesan

Department of Environmental Science and Engineering, Kwangju Institute of Science and Technology (K-JIST),
Kwangju 500 712, South Korea
b
Department of Chemistry, Anna University, Chennai 600 025, India
Received 22 February 2001; received in revised form 10 October 2001; accepted 26 October 2001

Abstract
Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A
solution containing 4  104 M dye was completely degraded in 24 h irradiation time. The intensity of the solar light
was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2 , SO2
4 ,

NO
3 , NH4 and H2 O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate inuenced
the photodegradation eciency. The rapidity of photodegradation of dye intermediates were observed in the presence
of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride
substantially aected the photodegradation eciency. High performance liquid chromatography and chemical oxygen
demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light
induced degradation of textile dye in wastewater is a viable technique for wastewater treatment. 2002 Elsevier
Science Ltd. All rights reserved.
Keywords: Titanium dioxide; Hydrogen peroxide; Potassium persulphate; Photomineralisation

1. Introduction
Textile mills are major consumers of water and consequently one of the largest group of industries causing
intense water pollution. The euent contains wide range
of chemicals of varying kind. Reactive dyes are not
amenable for ready biodegradation. The current treatment of dye waste in textile industries is focussed on the
removal of colour along with aesthetic issues. Several
physico-chemical and biological methods are available
for the treatment of textile wastewater. Unfortunately
these processes have high operating cost and are of
limited applicability. Strong colour is another important component of textile wastewater. If colour is not

Corresponding author. Tel.: +82-62-970-2571/2441; fax:


+82-62-970-2434.
E-mail address: hcchoi@kjist.ac.kr (H.C. Choi).

removed, this may cause disturbance to the ecological


system of the receiving waters (Neppolian et al., 1998;
Chaudhari and Babita, 2000; Wang, 2000). Thus many
processes have been proposed over the years and are
currently employed to destroy toxic chemicals discharged along with textile wastewater. Photocatalytic
detoxication has been focussed as an alternative
method to clean up polluted water (Ray and Beenackers,
1997, 1998; Herrmann et al., 1998). This technique
adopts the possibility of combining the heterogeneous
catalysis with solar light to achieve mineralisation of
toxic pollutants present in textile wastewater. In the past
few years many catalysts like TiO2 , ZnO, WO3 , SnO2 ,
ZrO2 , CeO2 , CdS and ZnS have been attempted for
photocatalytic oxidation of water borne environmental
contaminants (Ollis and Al-Ekabi, 1993; Reutergardh
and Iangphasuk, 1997). However, TiO2 has been proved
to be an excellent catalyst in the photodegradation of
organic pollutants. This technique appears to oer a

0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 2 8 4 - 3

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B. Neppolian et al. / Chemosphere 46 (2002) 11731181

great deal of hope in treating hazardous and toxic


chemical wastes into harmless end-products at ambient
temperature with minimum intermediates. In view of
the advantages of heterogeneous photocatalysis in the
treatment of wastewater, it has been aimed to decolourise and degrade aqueous solution of commonly used
textile dye reactive blue 4 using solar light with TiO2
catalyst.

2. Materials and methods


2.1. Materials
TiO2 used in the experiment was Degussa P-25
(Germany). The titania particles are a mixture of both
anatase and rutile crystalline phase (mostly anatase)
with an average particle size of 30 nm and surface area
of 50 m2 /g. The textile dye reactive blue 4 obtained from
Vanavil (India) limited was used as such. Solutions were
prepared by dissolving requisite quantity of the dye in
double distilled water.
2.2. Photocatalytic reactor
The cylindrical photochemical reactor of 200 ml
capacity was made-up of borosilicate glass having dimensions 8 cm  4:5 cm (height  diameter) with ports
at the top for sampling, gas inlet and gas outlet. Solar
light was used as the energy source for catalyst excitation. Experiments were performed at ambient temperature. The reactor assembly was placed on a magnetic
stirring plate to further enhance the agitation. The
slurry composed of the dye solution and catalyst placed
in the reactor was directly exposed to natural solar
light.
2.3. Analysis
The dye solution with catalyst in the reactor was
withdrawn at periodic intervals and analysed after
centrifugation for decolourisation and degradation.
The decolourisation of reactive blue 4 was measured
with UVVIS spectrophotometer (Model Hitachi
UV-2000, double beam, Japan) at 596 nm. Chemical
oxygen demand (COD) was measured by the closed
reux method (APHA, 1989). Disappearance of aromatic intermediates was observed by high performance
liquid chromatography (HPLC) (Shimadzu LC-10 AT
VP series with RP 18 ODS column). The formation of


CO2 , SO2
2 , NH4 and NO3 as end products were
tested by bubbling through lime water, turbidimeter
procedure and spectrophotometer methods respectively.

3. Results and discussion


Reactive blue 4 dye was degraded in the presence of
TiO2 photocatalyst in the form of suspension by irradiation with solar light. A blank experiment in the absence of solar irradiation illustrated the rapid attainment
of adsorption equilibrium of the dye onto TiO2 . Another
experiment of solar irradiation of the dye solution in the
absence of TiO2 showed no signicant degradation. This
clearly indicates that this phenomenon is photocatalytic
in nature.
3.1. Solar light intensity measurements using Lux meter
The intensity of solar light was measured using Lux
meter at time intervals of 2 h between 8 a.m. and 4 p.m.
The average of the measured intensities are presented in
Table 1.
3.2. Eect of initial concentration of dye
The eect of initial concentration of dye on the rate
of degradation was performed by varying the initial dye
concentration from 1  104 to 5  104 M with constant catalyst loading (2 g/l). It can be seen from Table 2
that both rate constant and percentage degradation decrease as the initial concentration of the dye increases.
The rate of degradation is related to the formation of
OH radicals which is a critical species in the degradation
process. The equilibrium adsorption of reactants on the
catalyst surface and the rate of reaction of OH radicals
Table 1
Average intensity of solar light during dierent months in
Chennai, India
Month (19951999)

Solar light intensity


(Lux = 10)

JanuaryFebruary
MarchApril
MayJune
JulyAugust
SeptemberOctober
NovemberDecember

95 000
101 750
105 000
102 400
92 200
89 710

Table 2
Eect of initial concentration of the dye on the degradation
eciency
Concentration of the
dye (104 M)

k 1 (min1 )

Degradation (%)

1
2
3
4
5

1:36  102
1:04  102
5:22  103
3:96  103
2:90  103

98
98
82
71
32

B. Neppolian et al. / Chemosphere 46 (2002) 11731181

with other chemicals are also signicant in the rate of


degradation. Hence k 1 can be expressed as follows:
k 1 k0 POH Pdye

where k 1 is the overall rate constant, k0 is the reaction


rate constant, POH is the probability of generation of OH
radicals on the catalyst surface and Pdye is the probability
of OH radicals reacting with dye molecules. The reaction
rate k0 is independent of the dye concentration [dye]0
whereas POH and Pdye will be aected by the dye concentration implicitly. This reaction follows pseudorst-order kinetics. Previous workers suggested that
the photocatalytic degradation of aromatic compounds
is through the hydroxylation by hydroxyl radicals
(Matthews, 1984). In addition, Okamoto et al. (1985)
pointed out that the rate-determining step of the reaction could be the formation of OH radicals since they
react very rapidly with aromatic ring compounds. The
hydroxyl radicals are formed through the reaction of
holes with adsorbed OH and water. If we assume that
the positions of adsorbed OH radicals are replaced by
dye ions (dye ) which are generated from the dissociation of sodium salt of dye molecules, then the generation
of OH radical will be reduced since there are only fewer
active sites available for the generation of OH radicals.
Therefore, POH is adversely aected by the catalyst site,
coverage fraction of dye and its oxidation intermediates.
Another important point for this behaviour is that as
the initial concentration of dye increases, the path
length of photons entering the solution decreases, and
in low concentration the reverse eect is observed (Davis
et al., 1994). This proves that the rate of degradation
decreases considerably with increase in the concentration of dye.
3.3. Eect of catalyst loading
A series of experiments were carried out to assess the
optimum catalyst loading by varying the amount of
catalyst from 1 to 4 g/l of the dye solution (4  104 M).
The rate constants of the dye degradation are presented
in Table 3. It is seen that the rate constant increases
linearly with catalyst loading up to 2.5 g/l. Above the
catalyst loading, increase of turbidity of the solution
reduces the light transmission through the solution.

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While below this level, it is assumed that the catalyst


surface and absorption of light by the catalyst are limiting. Particleparticle interaction becomes signicant
as the number of particles in solution increases. This
reduces the site density for surface holes and electrons
(Lea and Adesina, 2001). Many authors have investigated the reaction rate as a function of catalyst loading under dierent experimental conditions (Matthews,
1990; Mengyue et al., 1995). Our results are in good
agreement with reported values in the literature. Chen
et al. (1990) has described the possible explanation for
this behaviour. The increased loading of catalyst increases the quantity of photons adsorbed and consequently the degradation rates. Hence an optimum
amount of catalyst has to be added in order to avoid
unnecessary excess and also ensure total absorption
of light photons for ecient photomineralisation
(Herrmann, 1995).
3.4. Eect of pH
The wastewater from textile industries usually has a
wide range of pH values. Generally, pH plays an important role both in the characteristics of textile wastes
and generation of hydroxyl radicals. Hence attempt has
been made to study the inuence of pH in the degradation of dye at pH values in the range of 313. The
eect of pH on the percentage degradation of dye is
shown in Fig. 1. At 4  104 M concentration of dye (2.5
g TiO2 /l), acidic pH has not shown much inuence on
the percentage degradation of dye whereas the inhibitory eect seems to be more pronounced in the alkaline
range (pH 1113). In acidic solutions (pH < 5), the
photodegradation of the dye is retarded by the high
concentration of proton, resulting in lower degradation
eciency. But in alkaline medium (pH > 10), the presence of hydroxyl ions (OH ) neutralises the acidic endproducts that are produced in the photodegradation
reaction. A sudden drop of degradation was observed

Table 3
Eect of TiO2 loading on the degradation of the dye
Amount of TiO2 (g/l)

k 1 min1  103

Degradation (%)

1.0
2.0
2.5
3.0
4.0

2.89
3.96
5.22
5.41
5.70

60
71
82
82
82

Fig. 1. Inuence of pH on the degradation of the dye.

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B. Neppolian et al. / Chemosphere 46 (2002) 11731181

Table 4
Chemical structure and absorption maxima of reactive blue 4
dye
Dye
(commercial
name)

Chemical structure

Reactive
blue 4

kmax
(nm)
596, 253

were carried out during JanuaryApril and JuneSeptember. In tropical countries like India intense sunlight
is available almost through out the year and hence solar
light could be eectively used for photocatalytic degradation of pollutants in wastewater. In case of large
surface demanding photocatalytic degradation, sunlight
would be the ultimate source.
3.6. Mineralisation product of the dye

when the initial pH of the reaction mixture was kept at


11. From the chemical structure of the reactive blue dye
in Table 4, substituents of an electron-donating group
such as NH2 in the a-positions of the carbonyl group
are capable of forming intramolecular hydrogen bonds
at high pH values (Rys and Zollinger, 1992). Therefore,
the dye structure becomes chemically stable at high pH
ranges. The chromophores of the dye remain intact after
light irradiation and hence, reduce the degradation rate
of the dye (Tusi and Chu, 2001). Hence the changes in
the behaviour of the dye molecule may be responsible
for the change in the percentage degradation of dye at
higher pH.
3.5. Inuence of solar irradiation

When aqueous suspension of reactive blue 4 dye


(4  104 M) is irradiated with 2.5 g of TiO2 /l, the OH
radicals formed on the surface of the semiconductor are
strong non-selective oxidising agents with an oxidation
potential of 2.8 eV. They can attack the dye molecules
located close to the surface of the catalyst, thus leading
to complete mineralisation (Eq. (2)). The photocatalytic
degradation of reactive blue 4 dye may involve several
chemical and photocatalytic stages and a number of
intermediates. The nal species identied in the photo
degradation of reactive blue 4 are CO2 , SO2
4 , NO3 and

NH4 (Ray and Beenackers, 1998). Fig. 3 shows the


chromatograms obtained from HPLC analysis at various irradiation time. As irradiation time increases, the
dye degrades to compounds of lower molecular weight,
and the intermediates gradually disappear during the
remaining period of irradiation. Complete mineralisation of the dye is accomplished at an irradiation time
of 24 h.
C23 H11 O8 N6 S2 Na2 Cl2 34O2 ! Intermediates

The inuence of solar light on the degradation of the


dye was investigated at various time intervals as shown
in Fig. 2. The maximum degradation (96%) of the dye
was observed (concentration of dye 4  104 M and 2.5
g TiO2 catalyst/l) during AprilJune, peak summer period of the year in Chennai, India. Most of the reactions

3.7. Inuence of hydrogen peroxide

Fig. 2. Inuence of solar light on the degradation of dye in


dierent months (19951999): initial concentration of the
dye 4  104 M, initial COD 108 mg/l and irradiation
time 8 h.

The photoassisted degradation of organic substrates


is signicantly improved either in the presence of hydrogen peroxide or potassium persulphate. Since reactive hydroxyl radicals are easily generated by the
breakdown of hydrogen peroxide, the presence of hydrogen peroxide in the reaction mixture will play key
role in the photocatalytic process (Kiwi et al., 1993).
In order to understand this eect, hydrogen peroxide
was added in the dye solution in the concentration
range of 4:4  103 2:6  102 M and the photocatalytic studies were performed after each addition of
hydrogen peroxide. The results are shown in Fig. 4.
Complete degradation has been achieved within 8 h
irradiation in the presence of hydrogen peroxide concentration of 8:8  103 M. The 100% degradation has
been found to be possible in the presence of hydrogen
peroxide in comparison to the results in the absence of
hydrogen peroxide. It has been widely reported that

2

Intermediates ! 23CO2 6NO


3 2SO4 3H

2Na 2Cl 4H2 O

B. Neppolian et al. / Chemosphere 46 (2002) 11731181

1177

Fig. 3. HPLC chromatograms (RB4) as a function of irradiation time: (a) 4 h, (b) 8 h, (c) 16 h and (d) 24 h.

Fig. 4. Inuence of hydrogen peroxide: initial concentration of


the dye 4  104 M, initial COD 108 mg/l and irradiation
time 8 h.

the addition of small amount of hydrogen peroxide


greatly enhances the oxidation of organic pollutants
mediated by TiO2 catalyst (Kiwi et al., 1993). The enhanced photodegradation eciency in the presence of
hydrogen peroxide may be either directly via conduction
band electrons or indirectly via superoxide radical
anion which produces hydroxyl radicals (Pichat et al.,
1995). The following Eqs. (3)(6) implies that the addition of hydrogen peroxide during photocatalytic degradation increases the rate of degradation. In the
absence of TiO2 , 2025% degradation of the dye was
observed when H2 O2 (4:4  103 2:6  102 M) was
added in the dye solution. This is due to the photolytic
cleavage of H2 O2 by solar irradiation (Eq. (5)). In
addition to the heterogeneous reaction, the homogeneous reaction is also taking place simultaneously which
further enhances the rate of degradation of the dye.

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B. Neppolian et al. / Chemosphere 46 (2002) 11731181

H2 O2 e ! OH OH

3.8. Inuence of potassium persulphate



H2 O2 O
2 ! OH OH O2

H2 O2 ! 2 OH

H2 O2 ! O2
2 2H

The eect of persulphate ion (electron scavenger) on


the photocatalytic degradation of the dye was investigated by varying its amount from 0.25 to 2 g/l dye
solution and the data are presented in Fig. 6. The percentage degradation of the dye increases with increasing
amount of persulphate and attained cent percent degradation within 8 h irradiation time. The enhanced degradation in the presence of persulphate ion may be
attributed to the following facts. It is a benecial oxidising agent in photocatalytic detoxication because
SO
4 is formed from the oxidant by reactions (Eqs. (7)
and (8)) with the semiconductor generated electrons (e
cb ).

The oxidising power of these radicals is strong enough to break azo groups of dyes adsorbed on the surface of TiO2 leading to the formation of ammonium and
nitrate ions. This shows that reactions involving ring
nitrogen compounds are more complex and there are
many signicant reaction paths leading to nitrate ions
in addition to ammonium ions (Pelizzetti and Minero,
1994). The HPLC chromatograms of reactive blue 4 dye
is presented in Fig. 5. The chromatograms indicate the
existence of small amount of parent dye without their
fragments even after longer irradiation, which suggests
that the mineralisation of the fragments is tremendously
faster in the presence of hydrogen peroxide.


2

S2 O2
8 eaq ! SO4 SO4


2

S2 O2
8 ecb ! SO4 SO4

The sulphate radical anion (SO


4 ) is a strong oxidant
(E0 2:6 eV) and engages in the following three possible

Fig. 5. HPLC chromatograms (RB4) as a function of hydrogen peroxide (8:80  103 M): (a) 4 h, (b) 6 h, (c) 8 h and (d) 12 h.

B. Neppolian et al. / Chemosphere 46 (2002) 11731181

Fig. 6. Inuence of potassium persulphate: initial concentration of the dye 4  104 M, initial COD 108 mg/l and irradiation time 8 h.

modes of reactions with organic compounds: (i) by abstracting a hydrogen atom from saturated carbon, (ii) by
adding hydrogen to unsaturated or aromatic carbon
and (iii) by removing one electron from the carboxylate
anion and from certain neutral molecules (Nasr et al.,
1997). In addition, it can trap the photogenerated electrons and/or generate hydroxyl radical (Nasr et al., 1997;
Pelizzetti et al., 1991; Minero et al., 1993).
SO
4
SO
4

e
cb

SO2
4

H2 O ! OH

9
SO2
4

10

The sulphate radical anion and hydroxyl radical


formed (Eqs. (7), (8) and (10)) are powerful oxidants
that can degrade the dye molecules at faster rate. The
SO
4 has the unique nature of attacking the dye molecule at various positions and hence the fragmentation
of the dye molecules is rapid.

2
SO
intermediates
4 dye ! SO4 dye

11


intermediates
SO
4 dye

SO2
4

CO2 HNO3 other inorganics

1179

Fig. 7. Inuence of sodium carbonate: initial concentration of


the dye 4  104 M, initial COD 108 mg/l and irradiation
time 8 h.

decreases with increasing carbonate ion concentration as


shown in Fig. 7 (Buxton et al., 1988). The decrease in the
degradation of dye in the presence of carbonate ions is
due to the hydroxyl scavenging property of carbonate
ions which can be accounted from the following reactions (Eqs. (13) and (14)).



OH CO2
3 ! OH CO3

OH

HCO
3

! H2 O

CO
3

13
14

This type of trend was also observed in the photocatalytic degradation of reactive dyes (Nansheng et al.,
1996). Behar et al. (1970) reported the possibility of
generating carbonate radical anions (CO
3 ) with the
help of hydroxyl radicals. Thus the free hydroxyl radical
which is a primary source (oxidant) for the photocatalytic degradation decreases gradually with increase in
carbonate ions and ultimately signicant decrease in the
percent degradation of reactive blue 4.
3.10. Inuence of sodium chloride

12

3.9. Inuence of sodium carbonate


Sodium carbonate is the common auxiliary chemical
employed in textile processing operations. Sodium carbonate is mainly used in the dyeing bath in order to
adjust the pH of the bath as it plays an important role
in xing the dye on the fabrics and in the fastness of
colour. Therefore the wastewater from the dyeing operation contains considerable amount of carbonate ion.
Hence it is important to study the inuence of carbonate
ion in the photomineralisation eciency. Experiments
were performed in the presence of dierent quantities
of sodium carbonate. The percent degradation gradually

In the present investigation the eect of another


common interfering inorganic ion, chloride (sodium
chloride) on the photocatalytic degradation has also
been studied. Sodium chloride usually comes out in the
euent along with sectional wastes of textile mills. Irradiation studies have been carried out with sodium
chloride in the range 0.252 g/l of the dye solution
(Fig. 8).
The percentage degradation of reactive blue 4 decreases with increase in the amount of chloride ion. The
results shown in Fig. 8 are in good agreement with those
published by Abdullah et al. (1990) who reported a
strong inhibiting eect of chloride and phosphate ions
when they studied the photocatalytic degradation of
salicylic acid, aniline and ethanol. The decrease in the

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B. Neppolian et al. / Chemosphere 46 (2002) 11731181

tion and washing the catalyst. Hence the photodegradation of textile dyes employing solar energy may
emerge as a viable method because of its eco-friendliness
and cost eective.

Acknowledgements
This work was supported partially by Brain Korea 21
project 2000. The authors are grateful to the research
grant from the Ministry of Education, South Korea.

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Fig. 8. Inuence of sodium chloride: initial concentration of
the dye 4  104 M, initial COD 108 mg/l and irradiation
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Cl h
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It is evident that TiO2 catalysed photodegradation
using solar irradiation is a suitable technique for removal of dyes in wastewater from textile industries. The
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