Chemical Engineering Journal 112 (2005) 191–196

Decolorization and aromatic ring degradation kinetics of Direct

Red 80 by UV oxidation in the presence of hydrogen peroxide
utilizing TiO2 as a photocatalyst
Niyaz Mohammad Mahmoodi a,∗ , Mokhtar Arami a,b ,
Nargess Yousefi Limaee a , Nooshin Salman Tabrizi a
a Environmental Science and Engineering Department, Iran Color Research Center, Tehran, Iran
b Textile Engineering Department, Tehran Polytechnic University, Tehran, Iran

Received 30 January 2005; received in revised form 19 April 2005; accepted 12 July 2005

Abstract
Textile industry consumes considerable amounts of water during various processes such as dyeing. The existence of color and aromatic rings
in the form of aromatic amines in textile wastewater is a very important problem. In this paper, photocatalytic decolorization and aromatic ring
degradation of Direct Red 80 in a fixed bed photocatalytic reactor, utilizing a very simple analytical method, direct UV–vis spectrophotometric
detection, has been investigated. Photocatalytic decolorization and aromatic ring degradation processes performed using a 5 l solution containing
Direct Red 80. The initial concentration of Direct Red 80 was 50 mg l−1 . The radiation source was two 15 W UV-C lamps. A batch mode immersion
photocatalytic reactor was utilized. The effect of variables such as pH and H2 O2 concentration were studied. Bench scale simulated colored textile
wastewater was completely decolorized in a relatively short time after UV irradiation with a low concentration of hydrogen peroxide. The lack of any
absorbance in the UV–vis spectra was indicative of the complete aromatic ring degradation. Kinetics analysis indicates that the dye photocatalytic
decolorization rates can usually be approximated pseudo-first-order model. UV/TiO2 /H2 O2 process proved capable of the complete degradation
of the Direct Red 80.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Textile wastewater; UV/TiO2 /H2 O2 process; Decolorization; Aromatic ring degradation; Fixed bed photocatalytic reactor; Direct Red 80

1. Introduction of aquatic life [3]. In addition, the stability of their molecular

structures renders them resistant to biological or even chemical
Textile dyes are of environmental interest, because 700 000 t degradation [7,8].
of them are produced in the world annually while, about 50% Over the last two decades semiconductor photocatalysis has
among them are azo dyes [1]. About 15% of the total world been shown to be potentially advantageous and useful for the
production of dyes is lost during textile dyeing which is released treatment of wastewater pollutants [9,10]. This process has sev-
in textile effluents [1–3]. eral advantages over competing processes such as: (1) complete
Azo dyes, which contain one or more azo bonds ( N N ), mineralization, (2) no waste-solids disposal problem, and (3)
are among the most widely used synthetic dyes and usually only mild temperature and pressure conditions are necessary
become major pollutants in textile wastewaters [4]. It has been [11,12].
documented that some azo dyes are toxic and even mutagenic Several studies related to application of photocatalytic degra-
to living organisms in aquatic environment [5,6]. The release dation of various organic compounds exist nowadays [13–27].
of these colored wastewaters in the ecosystem is a dramatic Many catalysts like TiO2 , ZnS, ZnO, ZrO2 , WO3 , SrO2 and
source of aesthetic pollution, eutrophication and perturbation CdS have been utilized for the photocatalytic degradation of a
wide variety of environmental contaminates [28]. Among these
photocatalysts, TiO2 as a durable photocatalyst has been applied
∗ Corresponding author. Tel.: +98 21 77706373; fax: +98 21 22535206. to a variety of environmental cases [10]. The advantages of appli-
E-mail address: nm [email protected] (N.M. Mahmoodi). cation of TiO2 as a photocatalyst are: (1) TiO2 is environmentally

1385-8947/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2005.07.008
192 N.M. Mahmoodi et al. / Chemical Engineering Journal 112 (2005) 191–196

acceptable by being biologically and chemically fairly inert, (2) 2. Experimental

TiO2 is inexpensive and reusable, and (3) degradation of major
classes of organic pollutants can be achieved at ambient condi- 2.1. Reagents
tions [4].
Research efforts for understanding the fundamental processes Direct Red 80 (98%≤ purity) was obtained from Ciba Ltd.
and to enhance the photocatalytic efficiency of TiO2 have been and was used without further purification. The chemical struc-
performed by chemists, physicists and chemical engineers [29]. ture of this dye is shown in Fig. 1. Analytical grade H2 O2 (30%
Semiconductor can act as sensitizer for light-reduced (w/w), Merck) was used. Titanium dioxide (Degussa P25) was
redox processes due to their electronic structure, which is utilized as a photocatalyst. Its main physical data are as follows:
characterized by filled valence band and an empty conduction average primary particle size around 30 nm, purity above 97%
band. When a photon with energy of hν matches or exceeds the and with 80:20 anatase to rutile.
band gap energy, Eg , of the semiconductor, an electron, ecb − , is
promoted from the valence band, VB, into the conduction band, 2.2. Fixed bed photocatalytic reactor
CB, leaving a hole, hvb + behind. Excited state conduction band
electrons and valence band holes can recombine and dissipate Experiments were carried out in a batch mode immersion
the input energy as heat, get trapped in metastable surface rectangular fixed bed photocatalytic reactor made of Pyrex glass,
states, or react with electron donors and electron acceptors which is shown in Fig. 2. The radiation source was two UV-C
adsorbed on the semiconductor surface [10]. The hvb + is a lamps (15 W, Philips) which were protected by quartz tubes.
strong oxidant, which can either oxidize a compound directly, The photocatalyst (TiO2 ) powder was immobilized by a UV
or react with electron donors like water or hydroxide ions to resistant polymer in the inner surface of the reactor. Inner sur-
form hydroxyl radicals, which react with pollutants such as faces of reactor walls were cleaned with acetone and distilled
dyes. One efficient electron acceptor is molecular oxygen (O2 ), water to remove any organic or inorganic material attached to or
which forms a superoxide anion radical (O2 •− ) after capturing adsorbed on the surface and was dried in the air. A pre-measured
the electron. In addition, photocatalytic degradation process mass of TiO2 pellets were attached on the inner surfaces of
can be accelerated by hydrogen peroxide (H2 O2 ). During reactor walls using a thin layer of a UV resistant polymer. Imme-
the reaction, H2 O2 can produce hydroxyl radical by reacting diately after preparation, the inner surface reactor wall – polymer
with O2 •− or by direct photolysis. Besides, it can act as a – TiO2 system was placed in the room temperature (25 ◦ C) for
conduction band electron acceptor like O2 and form hydroxyl at least 60 h for complete drying of the polymer.
radicals subsequently [4]. Hydroxyl radicals react with organic A water pump and air pump were utilized for the transferring
pollutants leading to the total mineralization of most of and aeration of dye solutions respectively. The UV irradiation
them [2]. onto the photocatalyst surface causes the photocatalytic oxida-
Photocatalytic degradation is promoted by a photocatalyst, tion of a dye with O2 in the absence of H2 O2 . The existence of
which is dispersed in solution or immobilized on a surface. dissolved O2 is an important factor which increases the photo-
However, the use of a suspension solution requires the sepa- catalytic degradation of a dye. Hence, we used an aquarium air
ration and recycling of the photocatalyst particles. The above pump for the aeration of the dye solutions.
problem can be avoided in a fixed bed photocatalytic reactor. To
our knowledge there is not any paper dealing with the complete 2.3. Methods and analyses
disappearance of UV–vis absorption in photocatalytic decol-
orization and aromatic ring degradation of Direct Red 80 in a The photocatalytic experiments were performed using a 5 l
fixed bed photocatalytic reactor using a very simple analytical solution containing Direct Red 80. The initial concentration of
method, such as direct UV–vis spectrophotometric detection. In Direct Red 80 was 50 mg l−1 . Samples were withdrawn from a
the present study, we investigated the photocatalytic decoloriza- sample point at certain time intervals and analyzed for decol-
tion and aromatic ring degradation of a polyazo dye, Direct Red orization and degradation of Direct Red 80 dye. Decolorization
80, using direct UV–vis spectrophotometric detection. The dye of dye solutions and aromatic ring destruction were checked
is water-soluble and can be used for dying silk, wool, cellulose and controlled by measuring the absorbances of dye solutions
and cotton. The effects of various factors on the photocatalytic at different intervals using a UV–vis CECIL2021 Spectropho-
degradation of the dye were studied and the results were tometer. The maximum absorbances of the dye were at 225,
monitored. 290 and 543 nm. Absorbance measurements of the samples at

Fig. 1. Chemical structure of Direct Red 80.

 N.M. Mahmoodi et al. / Chemical Engineering Journal 112 (2005) 191–196 193

Fig. 2. Scheme of the fixed bed photocatalytic reactor for photocatalytic dye degradation.

254 nm were taken as an indication of the aromatic compound rate of hydroxyl radicals in two ways. Firstly, the reduction of
content [30]. A pH-meter (Hach) was utilized for the adjustion H2 O2 at the conduction band would produce hydroxyl radicals.
and investigation of pH variation during the process. The pH of Secondly, the self-decomposition by illumination would also
the dye solutions was adjusted prior to irradiation by NaOH or produce hydroxyl radicals [32]. As seen in Fig. 5, the decoloriza-
H2 SO4 . tion rate increased when H2 O2 concentration changed from 0 to
300 mg l−1 . No changes were observed at decolorization time
3. Results and discussion when the concentration further increased to 1200 mg l−1 . A con-
centration of 300 mg l−1 appears to be optimal. However, when
3.1. Decolorization and aromatic ring destruction present at high concentration, H2 O2 can also become a scav-
enger of valence bond holes and hydroxyl radicals [4,20,35].
Direct Red 80 is a tetrakis azo dye, which has a strong
absorbance in the UV–vis region. The chromophore part con- 3.3. pH effect
taining azo linkage has an absorption in the visible region while
benzene and naphthalene rings in the UV region; naphthalene The wastewater from textile industries usually has a wide
ring absorption wavelength is higher than that of benzene ring range of pH values. Generally, pH plays an important role both
[31,32]. The absorbance peaks at 225, 290 and 543 nm are, in the characteristics of textile wastewater and generation of
respectively, attributed to benzene, naphthalene rings [31,32]
and azo linkage. Moreover, changes in the absorption spectra
of Direct Red 80 (50 mg l−1 ) with H2 O2 (300 mg l−1 )/TiO2 /UV
at different time intervals of irradiation and pH 6 are shown in
Fig. 3.
With a time elapse of 15 min, the spectral height at 543 nm
decreased rapidly. This wavelength indicates the N N bond
of the dye which is the most active site for oxidation attack
[33,34]. The absorbance at 290 and 225 nm decreased from 0.78
to 0 and from 0.5 to 0, respectively, after 35 min of experiment.
The destruction of the aromatic rings becomes evident in Fig. 4.
All initial absorbance disappeared after 40 min.

3.2. H2 O2 effect

Hydrogen peroxide has different effects on dye decompo-

sition depending on its concentration and nature of reductants Fig. 3. Changes in the absorption spectrums of Direct Red 80 (50 mg l−1 ) with
[4,32]. At optimal concentration, H2 O2 increases the formation H2 O2 (300 mg l−1 )/TiO2 /UV at different time intervals of irradiation.
194 N.M. Mahmoodi et al. / Chemical Engineering Journal 112 (2005) 191–196

Fig. 4. Photocatalytic aromatic ring destruction of Direct Red 80 at different

Fig. 7. The pseudo-first-order decay rate constants of Direct Red 80 decoloriza-
concentrations of hydrogen peroxide at 254 nm and pH 6.
tion at different H2 O2 concentrations.

Table 1
Parameters for the effect of different H2 O2 concentrations on the decolorization
rate of Direct Red 80 after 15 min of irradiation
H2 O2 (mg l−1 ) k (min−1 ) R2

50 0.0676 0.9993
150 0.1337 1.0000
300 0.2976 0.9435
600 0.2096 0.9983
1200 0.2046 0.9952

because the different reaction mechanisms such as hydroxyl rad-

ical attack, direct oxidation by positive hole and direct reduction
Fig. 5. Photocatalytic disappearance of Direct Red 80 with different concentra- by the electron in the conducting band can contribute to dye
tions of hydrogen peroxide at 543 nm and pH 6. degradation. The importance of each one depends on the sub-
strate nature and pH [37,28]. In this study pH 6 was found to
hydroxyl radicals [36]. Hence, the photocatalytic degradation be the optimal pH under the given experimental conditions. All
of the dye was studied in a pH range between 2 and 10. The pH dye solutions become slightly acidic after photocatalytic degra-
of dye solutions was adjusted by NaOH or H2 SO4 before irra- dation process as it has also been observed elsewhere [30].
diation. Fig. 6 shows the effect of pH on the decolorization rate
of Direct Red 80. It can be seen that percentage decolorization 3.4. Kinetics of dye disappearance
decreases with decreasing initial pH of the dye solutions. The
possible explanation for this behavior is that as the initial pH of The kinetics of disappearance of Direct Red 80 is represented
dye solution decreases, TiO2 presents a positive charge in surface in Fig. 7. First-order kinetic model was utilized as follows:
which may highly promote the adsorption of dye since it con-
tains negative sulfonate groups. This phenomenon hinders the ln C0 /C = kt (1)
photon absorption by the photocatalyst. Consequently, the decol-
where C0 , C, t and k are the initial dye concentration, dye con-
orization rate of dye was decreased. Different optimal pHs (6–7)
centration in t, decolorization time (min) and the global reaction
have also been observed for other sulfonated azo dyes [37,38].
apparent rate constant (min−1 ), respectively.
However, the interpretation of pH effects on the efficiency of
The linear fit between the ln C0 /C and irradiation time under
the photocatalytic degradation process is a very difficult task,
pH 6 and different concentrations of H2 O2 can be approximated
as pseudo-first-order kinetics. The parameters k (rate constant,
min−1 ) and R2 (correlation coefficient) of decolorization process
are shown in Table 1. The order of rate constants was pH 6

Table 2
Parameters for the effect of different pH values on the decolorization rate of
Direct Red 80 after 15 min of irradiation (H2 O2 300 mg l−1 )
pH k (min−1 ) R2

2 0.066 0.9912
6 0.2976 0.9435
Fig. 6. Effect of pH on the photocatalytic decolorization of Direct Red 80 10 0.1587 0.9998
(543 nm and H2 O2 (300 mg l−1 )).
 N.M. Mahmoodi et al. / Chemical Engineering Journal 112 (2005) 191–196 195

(0.2976 min−1 ) > pH 10 (0.1587 min−1 ) > pH 2 (0.066 min−1 )

(Table 2).
It is apparent that the photocatalytic degradation is more
favored in neutral solutions.
Fig. 11. Chemical structure of Direct Orange 108.
4. Conclusions

In this research, a very simple analytical method, direct References

UV–vis spectrophotometric detection, has been investigated for
the examination of decolorization and aromatic ring destruction [1] C. Bauer, P. Jecque, A. Kalt, J. Photochem. Photobiol. A: Chem. 140
(2001) 87–92.
of Direct Red 80. Direct Red 80 could be successfully decol- [2] A. Houas, H. Lachheb, M. Ksibi, E. Elaloui, C. Guillard, J.M. Herrmann,
orized and degraded by UV/TiO2 /H2 O2 process in a novel fixed Appl. Catal. B: Environ. 31 (2001) 145–157.
bed photocatalytic reactor. The effect of different variables such [3] T. Sauer, G. Cesconeto Neto, H.J. Jose, R.F.P.M. Moreira, J. Photochem.
as H2 O2 concentration and pH was studied. The decoloriza- Photobiol. A: Chem. 149 (2002) 147–154.
tion rate goes through a maximum when the concentration of [4] C.M. So, M.Y. Cheng, J.C. Yu, P.K. Wong, Chemosphere 46 (2002)
905–912.
hydrogen peroxide increases from 0 to 300 mg l−1 . The pho- [5] H.M. Pinheiro, E. Touraud, O. Thomas, Dyes Piments 61 (2004)
tocatalytic decolorization kinetics follows a pseudo-first-order 121–139.
model. In this study pH 6 was found to be the optimal pH under [6] K.T. Chung, G.E. Fulk, A.W. Andres, Appl. Environ. Microbiol. 42
the given experimental conditions. The observations of these (1981) 641–648.
investigations clearly demonstrate the importance of choosing [7] S. Dai, W. Song, T. Li, Y. Zhuang, Adv. Environ. Sci. 4 (1996) 1–9.
[8] S. Dai, Y. Zhuang, Y. Chen, L. Chen, Environ. Chem. 14 (1995)
the optimum degradation parameters to obtain a high degra- 354–367.
dation rate, which is essential for any practical application of [9] M. Saquib, M. Muneer, Dyes Pigments 56 (2003) 37–49.
UV/TiO2 /H2 O2 process. Thin-film coating of photocatalyst may [10] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev.
resolve the problem of decolorization. Hence, this technique 95 (1995) 69–96.
may be a viable one for the treatment of large volumes of textile [11] A. Mills, R.H. Davies, D. Worsley, Chem. Soc. Rev. 22 (1993) 417–
425.
wastewater. The experimental results confirmed that photocatal- [12] D.S. Bhatkande, V.G. Pangarkar, A.A.C.M. Beenacker, J. Chem. Tech-
ysis appears as a subdivision of heterogeneous catalysis, which nol. Biotechnol. 77 (2001) 102–116.
is able to convert Direct Red 80 to minerals such as CO2 , H2 O [13] D.M. Blake, Bibliography of Work on the Photocatalytic Removal of
and etc. without using high pressure of oxygen or heating. This Hazardous Compounds from Water and Air, National Renewal Energy
manuscript has discussed the photocatalytic decolorization and Laboratory, USA, 1999.
[14] H. Goto, Y. Hanada, T. Ohno, M. Matsumura, J. Catal. 225 (2004)
aromatic ring destruction experiments of only one dye (Direct 223–229.
Red 80) but this method could be use for the degradation of other [15] I. Arsalan, I.A. Balcioglu, D.W. Babnemann, Dyes Pigments 47 (2000)
dyes such as Direct Red 23, Direct Red 31, Direct Red 81 and 207–218.
Direct Orange 108 that have very similar chemical structures [16] M. Vautier, C. Guillard, J.M. Hermann, J. Catal. 201 (2001) 46–
with Direct Red 80 (Figs. 8–11, respectively). 59.
[17] A. Mills, A. Belghazi, R.H. Davies, D. Worsley, S. Morris, J. Photochem.
Photobiol. A: Chem. 79 (1994) 131–139.
[18] Y. Xu, C.H. Langford, Langmuir 17 (2001) 897–902.
[19] K. Vinodgopal, I. Bedja, S. Hotechandani, P.V. Kamat, Langmuir 10
(1994) 1767–1771.
[20] O. Legrini, E. Oliveros, A.M. Braun, Chem. Rev. 93 (1993) 671–
698.
Fig. 8. Chemical structure of Direct Red 23. [21] J.C. Crittenden, J. Liu, D.W. Hand, D.L. Perram, Water Res. 31 (1997)
429–438.
[22] K. Tanaka, K. Padarmpole, T. Hisanaga, Water Res. 34 (2000) 327–
333.
[23] Y. Ku, C.B. Hsieh, Water Res. 26 (1992) 1451–1456.
[24] J. Chen, D.F. Ollis, W.H. Rulkens, H. Bruning, Water Res. 33 (1999)
1173–1180.
[25] W. Choi, M.R. Hoffmann, Environ. Sci. Technol. 37 (1997) 89–95.
[26] H. Gupta, S. Tanaka, Water Sci. Technol. 31 (1995) 47–54.
[27] J. Zhao, T. Wu, K. Wu, K. Oikawa, H. Hidaka, N. Serpone, Environ.
Fig. 9. Chemical structure of Direct Red 31. Sci. Technol. 32 (1998) 2394–2400.
[28] B. Neppolian, H.C. Choi, S. Sakthivel, B. Arabindoo, V. Murugesan, J.
Hazard. Mater. B89 (2002) 303–317.
[29] A.L. Linsebigle, G. Lu, J.T. Yates, Chem. Rev. 95 (1995) 735–758.
[30] D. Georgiou, P. Melidis, A. Aivasidis, K. Gimouhopoulos, Dyes Pig-
ments 52 (2002) 69–78.
[31] W. Feng, D. Nansheng, H. Helin, Chemosphere 41 (2000) 1233–1238.
[32] J.M. Lee, M.S. Kim, B. Hwang, W. Bae, B.W. Kim, Dyes Pigments 56
Fig. 10. Chemical structure of Direct Red 81. (2003) 59–67.
196 N.M. Mahmoodi et al. / Chemical Engineering Journal 112 (2005) 191–196

[33] Z. Sun, Y. Chen, Q. Ke, Y. Yang, J. Yuan, J. Photochem. Photobiol. A: [36] B. Neppolian, H.C. Choi, S. Sakthivel, B. Arabindoo, V. Murugesan,
Chem. 149 (2002) 169–174. Chemosphere 46 (2002) 1173–1181.
[34] J. Li, C. Chen, J. Zhao, H. Zhu, J. Orthman, Appl. Catal. B: Environ. [37] W.Z. Tang, Z. Zhang, H. An, M.O. Quintana, D.F. Torres, Environ.
37 (2002) 331–338. Technol. 18 (1997) 1–12.
[35] S. Malato, J. Blanco, C. Richter, B. Braun, M.I. Maldonado, Appl. Catal. [38] I. Poulios, I. Aetopoulou, Environ. Technol. 20 (1999) 479–487.
B: Environ. 17 (1998) 347–356.