Dyes and Pigments 75 (2007) 443e448

www.elsevier.com/locate/dyepig

TiO2-mediated photocatalytic degradation of a textile dye

derivative, bromothymol blue, in aqueous suspensions
M.M. Haque, M. Muneer*
Department of Chemistry, Aligarh Muslim University, Aligarh 202002, India
Received 6 December 2005; received in revised form 2 March 2006; accepted 19 June 2006
Available online 11 September 2006

Abstract

Photocatalysed degradation of a textile dye derivative, bromothymol blue, has been investigated in aqueous suspensions of titanium dioxide
under a variety of conditions. The degradation was monitored by measuring the change in substrate concentration as a function of irradiation
time employing UV spectroscopic analysis technique. In these studies, a number of byproducts are formed during the photooxidation process,
which can potentially be harmful to the environment, therefore, we have studied the mineralization of the pollutant by measuring the total or-
ganic carbon (TOC) as a function of irradiation time. The degradation kinetics were studied under different conditions such as pH, catalyst con-
centration, substrate concentration, different types of TiO2 and in the presence of electron acceptors such as hydrogen peroxide (H2O2),
potassium bromate (KBrO3) and ammonium persulphate (NH4)2S2O8 besides molecular oxygen. The degradation rates were found to be strongly
influenced by all the above parameters. The photocatalyst, titanium dioxide (TiO2) Degussa P25, was found to be more efficient as compared
with other TiO2 powders. All the electron acceptors markedly enhanced the degradation of the pollutant under investigation.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Photocatalysis; Bromothymol blue; Titanium dioxide; Semiconductor

1. Introduction illumination has been shown to be potentially advantageous

and useful in the treatment of waste water pollutants.
A wide variety of organics are introduced into the environ- There are several studies related to the use of semiconduc-
ment through various sources such as industrial effluents, ag- tors in the photomineralization of photo stable dyes [7e18].
ricultural runoff and chemical spills. Industrial effluents The mechanism constituting heterogeneous photocatalytic ox-
contain several non-biodegradable substrates that can be harm- idation processes has been discussed extensively in the litera-
ful to the environment [1]. One major source of these effluents ture [19,20]. Briefly, when a semiconductor such as TiO2
is the waste arising from the industrial process, which utilizes absorbs a photon of energy equal to or greater than its band
dyes to color paper, plastic and natural and artificial fibers [2]. gap width, an electron may be promoted from the valence
A substantial amount of dyestuff is lost during the dyeing pro- band to the conduction band (e cb) leaving behind an electron
cess in the textile industry [2], which poses a major problem vacancy or ‘‘hole’’ in the valence band (hþ vb). If charge separa-
for the industry as well as a threat to the environment [2e6]. tion is maintained, the electron and hole may migrate to the
Decolourization of dye effluents has therefore acquired increas- catalyst surface where they participate in redox reactions
ing attention. During the past two decades, photocatalytic with sorbed species. Specially, hþ vb may react with surface-
bound H2O or OH to produce the hydroxyl radical (OH )

process involving TiO2 semiconductor particles under UV light
and ecb is picked up by oxygen to generate superoxide radical
anion (O2), as indicated in Eqs. (1)e(3).


* Corresponding author. Tel.: þ91 571 2703515; fax: þ91 571 2702758.
E-mail address: [email protected] (M. Muneer). TiO2 þ hn / e þ
cb þ hvb ð1Þ

0143-7208/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2006.06.043
444 M.M. Haque, M. Muneer / Dyes and Pigments 75 (2007) 443e448

O2 þ e
cb / O2
 
ð2Þ solution for irradiation experiments. The photocatalyst, tita-
nium dioxide Degussa P25, was used in most of the experi-
H2 O þ hþ  þ ments, and other catalyst powders, namely, Hombikat
vb / OH þ H ð3Þ

UV100 (Sachtleben Chemie GmbH), PC500 (Millanium Inor-
It has been suggested that the hydroxyl radicals (OH ) and ganics) and TiO2 obtained from Travancore Titanium Products
superoxide radical anions (O2) are the primary oxidizing spe-

(TTP), India, were used for comparative studies. Degussa P25
cies in the photocatalytic oxidation processes. These oxidative contains 75% anatase and 25% rutile with a specific BET sur-
reactions would result in the bleaching of the dye. Alterna- face area of 50 m2 g1 and a primary particle size of 20 nm
tively, direct absorption of light by the dye, can lead to charge [22]. Hombikat UV100 consists of 100% pure anatase with
injection from the excited state of the dye to the conduction a specific BET surface area of 250 m2 g1 and a primary par-
band of the semiconductor as summarized in the following ticle size of 5 nm [23]. The photocatalyst PC 500 has a BET
equations: surface area of 287 m2 g1 with 100% anatase and primary
particle size of 5e10 nm [24] and TiO2 obtained from Travan-
Dyeads þ hn / Dyeads  ð4Þ core Titanium Products (TTP), India, has a BET surface area
of 9.82 m2 g1. The other chemicals such as NaOH, HNO3,
Dyeads  þ TiO2 / Dyeþ 
ads þ TiO2 ðe Þ ð5Þ hydrogen peroxide, potassium bromate and ammonium persul-
Earlier studies [7e18] have shown that heterogeneous pho- phate used in the study were obtained from Merck.
tocatalytic oxidation processes can be used for removing color-
ing material from dye effluent in the presence of light. The 2.2. Procedure
model compound bromothymol blue (BTB, 1) is a textile dye
derivative. The photocatalytic degradation of bromothymol For experiments under UV light, stock solutions of the
blue using batch reactor in the presence of TiO2 immobilized compound with desired concentration were prepared in double
on ceramic beads and doped TiO2 has been investigated earlier distilled water. An immersion well photochemical reactor
[21]. No major efforts have been made to study the detailed made of Pyrex glass was used in this study. For irradiation ex-
degradation kinetics, which is essential from the application periment, 250 mL of the desired solution was filled into the re-
point of view. Therefore, we have undertaken a detailed study actor and the required amount of photocatalyst was added and
on the photodegradation of bromothymol blue (1) sensitized the solution was stirred for at least 15 min in the dark to allow
by TiO2 in aqueous solution examining various reaction param- equilibration of the system so that the loss of compound due to
eters, e.g. reaction pH, substrate and catalyst concentrations, adsorption can be taken into account. The pH of the reaction
type of photocatalyst and addition of several electron acceptors. mixture was adjusted by adding dilute aqueous solution of
NaOH or HNO3. The zero time reading was obtained from
blank solution kept in the dark but otherwise treated similarly
to the irradiated solution. The suspensions were continuously
purged with molecular oxygen throughout each experiment.
Irradiations were carried out using a 125 W medium pressure
mercury lamp. IR radiation and short wavelength UV radiation
were eliminated by a water circulating Pyrex glass jacket.
Samples (10 mL) were collected before and at regular inter-
vals during the irradiation for analysis.

2.3. Analysis

The degradation was monitored by measuring the absor-

bance on a Shimadzu UVevis spectrophotometer (Model
1601), whereas the mineralization of the dye was monitored
by measuring the total organic carbon (TOC) content with
a Shimadzu TOC 5000A analyzer by directly injecting the
aqueous solution. The absorbance of the model compound
was followed at 420 nm wavelength.

2. Experimental methods 3. Results and discussion

2.1. Reagents 3.1. Photocatalysis of TiO2 suspensions containing

bromothymol blue
Analytical grade bromothymol blue was obtained from Al-
drich and used as such without any further purification. Dou- Irradiation of an aqueous solution of the BTB (1, 0.25 mM,
ble distilled water was employed in this study to make stock 250 mL) in the presence of TiO2 (Degussa P25, 1 g L1) by
 M.M. Haque, M. Muneer / Dyes and Pigments 75 (2007) 443e448 445

the ‘‘Pyrex’’ filtered output of 125 W medium pressure mer- have been written, regarding the mechanistic and kinetic de-
cury lamp, lead to a decrease in the absorption intensity as tails as well as the influence of experimental parameters.
well as depletion in TOC content. Fig. 1 shows the change The degradation and mineralization of bromothymol blue
in absorption intensity and depletion in TOC content as a func- was tested with four different commercially available photoca-
tion of irradiation time for the photocatalytic degradation of talysts, namely Degussa P25, Hombikat UV100, PC500 and
BTB in the absence and presence of the photocatalyst. Both TTP. Fig. 2 shows the degradation rate for the decomposition
the decomposition and mineralization curves can be fitted rea- and mineralization of the compound in the presence of differ-
sonably well by an exponential decay curve suggesting first or- ent photocatalysts. It has been observed that the degradation of
der kinetics. For each experiment, the rate constant was the dye derivative 1 proceeds much more rapidly in the pres-
calculated from the plot of natural logarithm of TOC and ence of Degussa P25 as compared to other employed photoca-
dye concentration as a function of irradiation time. The degra- talyst powders. In all the following experiments, Degussa P25
dation rate for the mineralization (depletion of TOC content vs was used as the photocatalyst since this material exhibited the
irradiation time) and decomposition (decrease in absorption highest overall activity for the degradation of the model com-
intensity vs irradiation time) was calculated using the formula pound under investigation.
given below: The better photocatalytic activity of Degussa P25, could be
attributed to the fact that P25 is composed of small nano-crys-
d½TOC=dt ¼ kcn tallites of rutile dispersed within an anatase matrix. The
smaller band gap of rutile ‘‘catches’’ the photons, generating
d½A=dt ¼ kcn electronehole pairs. The electron transfer, from the rutile con-
duction band to electron traps in anatase phase takes place.
where TOC is the total organic carbon, A, the absorbance, k,
Recombination is thus inhibited allowing the hole to move
the rate constant, c, the concentration of the pollutant, and n,
to the surface of the particle and react [25].
the order of reaction.
Control experiments were carried out in all cases, employ-
ing unirradiated blank solutions. No observable loss of the 3.3. pH effect
compound occurs when the irradiation was carried out in the
absence of TiO2. The zero irradiation time readings were ob- An important parameter in the photocatalytic reactions tak-
tained from blank solutions kept in the dark, but otherwise ing place on the semiconductor particulate surface is the pH of
treated similarly to the irradiated solutions. the solution, since it dictates the surface charge properties of
the catalyst and therefore the adsorption behavior of the pol-
3.2. Comparison of different photocatalysts lutants. Influence of pH on the degradation of BTB (1) in
aqueous suspensions of TiO2 was studied at the pH range be-
Titanium dioxide is known to be the semiconductor with tween 2 and 9 under UV light source. Fig. 3 shows the degra-
the highest photocatalytic activity, is non-toxic, relatively in- dation rate for decomposition and mineralization of
expensive and stable in aqueous solution. Several reviews bromothymol blue as a function of reaction pH. The efficiency
of degradation was found to be more or less similar in the pH

TOC (TiO2 / hν)

1.2 BTB (TiO2 / hν) 0.012
Degradation rate (mole L-1 min-1 * 10-3)

TOC (hν) TOC

BTB (hν)
1.0 0.010 BTB

0.8 0.008
TOC/TOC0
A/A0

0.6 0.006

0.4 0.004

0.2 0.002

0.0 0.000
0 15 30 45 60 75 90 P25 UV100 PC500 TTP
Irradiation time (min) Type of photocatalyst

Fig. 1. Depletion in TOC and change in absorption intensity as a function of Fig. 2. Comparison of degradation rate for the mineralization (TOC depletion
irradiation time for an aqueous solution of bromothymol blue (BTB, 1) in the vs irradiation time) and for the decomposition (change in absorption intensity
presence and absence of the photocatalyst. Experimental conditions: 0.25 mM vs irradiation time) of bromothymol blue (BTB, 1) in the presence of different
BTB, V ¼ 250 mL, photocatalyst TiO2 (Degussa P25, 1 g L1), immersion photocatalysts. Experimental conditions: 0.25 mM BTB, V ¼ 250 mL, photo-
well photoreactor, 125 W medium pressure Hg lamp, absorbance was followed catalysts: TiO2 (Degussa P25 1 g L1), Sachtleben Hombikat UV100
at 420 nm, cont. O2 purging and stirring, and irradiation time ¼ 90 min. (1 g L1), PC500 (1 g L1), TTP (1 g L1), and irradiation time ¼ 90 min.
446 M.M. Haque, M. Muneer / Dyes and Pigments 75 (2007) 443e448

0.0150 0.014
Degradation rate (mole L-1 min-1 * 10-3)

Degradation rate (mole L-1 min-1 * 10-3)

TOC TOC
BTB 0.012
0.0125 BTB

0.010
0.0100
0.008
0.0075
0.006
0.0050
0.004

0.0025 0.002

0.0000 0.000
0 2 4 6 8 10 0.1 0.2 0.3 0.4 0.5
pH Substrate concentration (mM)

Fig. 3. Influence of pH on the degradation rate for the mineralization and de- Fig. 5. Influence of substrate concentration on the degradation rate for the min-
composition of bromothymol blue (BTB, 1). Experimental conditions: eralization and for the decomposition of bromothymol blue (BTB, 1). Exper-
0.25 mM BTB, V ¼ 250 mL, photocatalyst: TiO2 (Degussa P25, 1 g L1), re- imental conditions: BTB concentration (0.15, 0.25, 0.35 and 0.5 mM),
action pH (2.2, 4.6, 7.1 and 9.0), and irradiation time ¼ 90 min. V ¼ 250 mL, photocatalyst TiO2 (Degussa P25, 1 g L1), and irradiation
time ¼ 90 min.

range studied within the experimental error limits, except that

slight lower mineralization rates were observed when the reac- shows the degradation rate for the decomposition and mineral-
tion was carried out at pH 2.2. ization of the dye as a function of substrate concentration em-
It has been found that when the reaction of the dye derivative ploying Degussa P25 as photocatalyst (1 g L1). It was
1 was carried out at pH 9.0, there was appearance of new ab- observed that the degradation rate was found to increase
sorption peak at 645 nm besides its lmax of 420 nm as shown with the increase in substrate concentration from 0.12 mM
in Fig. 4. The absorption intensities of the peaks that appeared to 0.35 mM. A further increase in substrate concentration
at these wavelengths were found to decrease as a function of ir- leads to decrease in the degradation rate of the dye. This
radiation time. We have followed the decrease in absorption in- may be due to the fact that as the initial concentrations of
tensity at 420 nm for determining the degradation rate. the dye increase, the color of the irradiating mixture becomes
more and more intense which prevents the penetration of light
to the surface of the catalyst. Hence, the generation of relative
3.4. Effect of substrate concentration
amounts of OH and O2 on the surface of the catalyst does not


increase, as the intensity of light and the irradiation time are

It is important both from mechanistic and application points
constant. Conversely, their concentrations will decrease with
of view to study the dependence of photocatalytic reaction rate
increase in concentration of the dye as the light photons are
on the substrate concentration. Hence, the influence of sub-
largely absorbed and prevented from reaching the catalyst sur-
strate concentration on the degradation rate was studied at dif-
face by the dye molecules. Consequently, the degradation ef-
ferent concentrations varying from 0.15 to 0.5 mM. Fig. 5
ficiency of the dye decreases as the dye concentration
increases.
BTB (pH 9.0)
1.6 BTB (pH 7.2)
BTB (pH 4.6)
3.5. Effect of catalyst concentration

1.2 The influence of the photocatalyst concentration on the

Absorbance

degradation kinetics of bromothymol blue was investigated us-

ing different concentrations of Degussa P25 varying from 0.5
0.8 to 3 g L1. Fig. 6 shows the degradation rate for the decompo-
sition and mineralization of the pollutant as a function of cat-
alyst concentration. It could be seen from the figure that the
0.4
addition of photocatalyst improves the degradation rate of
the pollutant under investigation, which is the characteristic
0.0 of heterogeneous photocatalysis and results are in agreement
360 400 440 480 520 560 600 640 680 with a number of studies reported earlier [26e28].
Wavelength (nm) The adsorption of the dye derivatives on the surface of the
Fig. 4. Absorption spectra of the dye derivative bromothymol blue (BTB, 1) at photocatalyst was investigated by stirring the aqueous solution
pH values 4.6, 7.1 and 9.0, showing the appearance of a new peak at wave- in the dark for 24 h in a round-bottomed flask containing vary-
length 645 nm at pH 9.0. ing amounts, 0, 0.5, 1, 2 and 3 g L1, of photocatalyst.
 M.M. Haque, M. Muneer / Dyes and Pigments 75 (2007) 443e448 447

0.020 4. Conclusion
Degradation rate (mole L-1 min-1 * 10-3)

TOC
BTB
TiO2 can efficiently catalyze the photodegradation of the
0.015
dye derivative bromothymol blue in the presence of light
and oxygen. The results of this study clearly demonstrate the
0.010
importance of choosing the optimum degradation parameters
to obtain high degradation rates of the model compound,
which is essential for any practical application of photocata-
0.005 lytic oxidation processes. Degussa P25 was found to be
a more efficient catalyst as compared to other TiO2 powders.
The electron acceptors have been found to enhance the degra-
0.000 dation rate of the pollutant.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Catalyst concentration (gL-1) Acknowledgements
Fig. 6. Influence of catalyst concentration on the degradation rate for the min-
eralization and for the decomposition of bromothymol blue (BTB, 1). Exper- Total Organic Carbon (TOC) Analyzer used for the analy-
imental conditions: 0.25 mM BTB, V ¼ 250 mL, photocatalyst: TiO2 (Degussa ses of the samples was a gift equipment from the Alexander
P25 0.5, 1, 2 and 3 g L1), and irradiation time ¼ 90 min. von Humboldt Foundation, Bonn, Germany. Financial support
by the Department of Chemistry, Aligarh Muslim University,
Aligarh, India and The Muslim Association for the Ad-
Analysis of the samples after centrifugation indicates no ob- vancement of Science (MAAS), India, for providing Post Doc-
servable loss of the dye. toral Research Fellowship to Dr. M. M. Haque is gratefully
acknowledged.
3.6. Effect of electron acceptors
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