Journal of KerbalaUniversity , Vol. 11 No.2 Scientific .

2013

Study on the photocatalytic degradation of indigo carmine dye

by TiO2 photocatalyst
‫دراسة المعالجة الضوئية لصبغة النيل كامين بوجود ثنائي اوكسيذ التيتانيوم كعامل مساعذ‬
Dr. Ahmed Hassan Ali
Chemical Engineering Department \ Al-MuthannaUniversity \ Al-Muthanna \ Al-Samawa
Email: ahmedbakersham@yahoo.com

ABSTRACT
Dye pollutants produced from the textile industries are becoming a major source of
environmental contaminations. Approximately 150 tonnes every day is estimated to be released
into the aquatic environment all over the world. The release of those dyes in the aquatic
environment is a considerable source of non-aesthetic pollution and these dyes are also resistant
to aerobic degradation, and under anaerobic conditions the dyes can be transformed into
carcinogenic aromatic amines.
This research reports on photocatalytic treatment of a hazardous indigo carmine dye in
wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO2.
The effect of catalyst dose, pH and initial dye concentration on the degradation process has been
assessed. The aqueous dye solution was degraded in a photochemical reactor in presence of UV
light (365nm) along with suspended TiO2 particles. 100 ml of dye solution (25ppm) was
subjected to degradation under UV light. Different concentrations of TiO 2 photocatalyst (0.25,
0.50, 0.75, 1.0 and 1.25g/L), different pH values (4, 7, 9, and 11) and different concentrations of
indigo carmine dye (5, 10, 25, 50, 100 ppm) were employed for the present study. The chemical
oxygen demand (COD) reduction at optimum conditions was examined. The degradation of the
dye was confirmed from the disappearance of peak at 608 nm.
‫الخالصة‬
‫ حيش اٌ يب‬.‫اصجحذ انًهٕصبد انُبرجخ عٍ انصجغبد انًسزخذيخ في انصُبعبد انُسيجيخ يصذسا سئيسيب نهزهٕس انجيئي‬
‫ اٌ طشح ْزِ األصجبغ انى انجيئخ انًبئيخ ثبإلضبفخ نكَٕٓب‬.‫ طٍ يطشح يٕييب يٍ ْزِ انًهٕصبد في جًيع أَحبء انعبنى‬150 ‫يمبسة‬
‫ اٌ ْزِ انصجغبد‬.‫يهٕصخ يعزجش ظبْشح غيش جًبنيخ ٔٔجٕدْب في انجيئخ انًبئيخ غيش الئك يحزبط انى يعبنجخ ٔاصانخ ثصٕسح كبيهخ‬
.‫ركٌٕ يمبٔيخ نهزحهم انٕٓائي رحذ انظشٔف االعزيبديخ كزنك يًكٍ أٌ رزحٕل إنى يشكجبد أييُيخ خطشح ٔيسشطُخ‬
‫ْزا انجحش يزضًٍ عًهيخ يعبنجخ احذ انصجغبد انًسزخذيخ في االَسجخ ٔانزي رطشح يع انًيبِ انصُبعيخ نًعبيم االَسجخ ْٔي‬
‫ حيش رى دساسخ ثعض‬.‫صجغخ انُيم كبسييٍ ٔلذ اسزخذيذ عًهيخ االكسذح انضٕئيخ ثٕجٕد صُبئي أكسيذ انزيزبَيٕو كعبيم يسبعذ‬
‫ نمذ رى‬. ‫ ٔدسجخ انحبيضيخ ٔانزشكيض االثزذائي نهصجغخ‬، ‫انعٕايم انًؤصشح عهى عًهيخ انًعبنجخ يُٓب رأصيش كًيخ انعبيم انًسبعذ‬
‫ رى‬.)‫ َبَٕييزش‬365( ‫دساسخ جًيع انعٕايم انًؤصشح عهى اَحالل صجغخ انُيم كبسييٍ ثٕجٕد االشعخ فٕق انجُفسجيخ ثطٕل يٕجي‬
، 0.25( ‫ رى اسزخذاو رشكيض يخزهفخ نهعبيم انًسبعذ ْٔي‬.)‫نزش‬/‫ يهغى‬25( ‫ يهيهيزش يٍ يحهٕل انصجغخ ثزشكيض‬100 ‫رحضيش‬
‫ رى رحذيذ‬.)11 ، 9 ، 7 ، 4( ‫ كزنك رى اسزخذاو ليى يخزهفخ نذسجخ انحبيضيخ ْٔي‬،‫نزش‬/‫ ) غى‬1.25 ٔ 1.0 ، 0.75 ، 0.50
‫ ٔكبَذ‬4 ‫نزش نهعبيم انًسبعذ ٔدانخ حبيضيخ‬/‫ غى‬0.75 ‫انظشٔف انزي اعطذ الصى دسجخ اَحالل نهصجغخ ٔكبَذ عُذ رشكيض‬
‫ ثعذ رنك رى رضجيذ رهك انظشٔف انميبسيخ نهعبيم انًسبعذ ٔانذانخ انحبيضيخ‬.‫ دليمخ‬35 ‫ في‬%98 ً ‫َسجخ اَحالل انصجغخ رمشيجب‬
‫ رى ليبط اخزضال‬.‫نزش نٓزِ انذساسخ‬/‫) يهغى‬100 ، 50 ، 25 ، 10 ، 5( ‫ٔرغييش انزشكيض االثزذائي نهصجغخ ٔلذ اسزخذيذ انزشاكيض‬
.‫) خالل عًهيخ انًعبنجخ ٔرحذ انظشٔف انًضهى يٍ رشكيض نهعبيم انًسبعذ ٔدانخ حبيضيخ‬COD( ‫يزطهت االٔكسجيٍ انكيًيبئي‬
.‫ َبَٕيزش‬608 ‫اٌ اَحالل انصجغخ رًذ يالحظزّ يٍ خالل اخزفبء لًخ انًُحُي في انطيف انًشئي نهصجغخ عُذ‬

1. Introduction
Excess use of various dyes in the textile industry has led to the severe surface water and
groundwater contamination by releasing the toxic and colored effluents, which are usually disposed
by various physical and chemical methods, such as coagulation/flocculation [1,2],
electrocoagulation [3], coagulation/carbon adsorption process [4] and so on. However, these
methods barely transfer the pollutants from one phase to another without destruction or have the
other limitations. In recent years, as a promising tool to substitute the traditional wastewater
treatment, semiconductor-assisted photocatalysis among the advanced oxide processes (AOP) has

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attracted the public concern for its ability to convert the pollutants into the harmless substances
directly in the waste water. Till now, many kinds of semiconductors have been studied as
photocatalysts including TiO2, ZnO, CdS,WO3 and so on [5–11]. Among various semiconductor
oxides, TiO2 proves to be the most suitable material because of its many desirable properties, such
as strong oxidizing power, high photo- and thermal-stability, low price, facile synthesis and the low
toxicity of titanium. However, the photocatalytic efficiency of pure TiO 2 needs to be improved to
meet industrial requirements. Several methods have been devoted to enhance the photoactivity,
among which, non-metal doping has attracted much attention recently. It reduces substantial amount
of Chemical Oxidation Demand (COD) and Total Organic Carbon (TOC) from industrial effluents.
Total oxidation of organics by these methods is cost and energy consuming.
The photocatalysed decolorization of a dye in solution is initiated by the photoexcitation of the
semiconductor, followed by the formation of electron-hole pair on the surface of catalyst (Eq. (1)).
The high oxidative potential of the hole (hVB+) in the catalyst permits the direct oxidation of the dye
to reactive intermediates (Eq. (2)).
(MO/MO2) + hv (MO/MO2) ( ) (1)
Metal oxide
hVB + dye dye•+ oxidation of the dye (2)
Another reactive intermediate which is responsible for the degradation is hydroxyl radical (OH•). It
is either formed by the decomposition of water (Eq. (3)) or by reaction of the hole with OH− (Eq.
(4)). The hydroxyl radical is an extremely strong, nonselective oxidant (Eo = + 3.06 V) which leads
to the partial or complete mineralization of several organic chemicals [13]
h+VB + H2O H+ + •OH (3)
+ –
h VB + OH •OH (4)
•OH + dye degradation of the dye (5)
This research aims to study the photocatalytic degradation of indigo carmine. This pigment has
been used for many years in industries, such as textile, paper, and plastics, as colorant. Even in very
small quantity dyes can be easily recognized either in industrial products or in the wastewaters
[12-14]. Stability, important property of dyes, prevents treatment of their aqueous residues, even
when it is present in low concentrations. Commonly used methods are either economically
unfavorable and/or technically complicated [15].
The aim of the present study is to investigate the photocatalytic degradation of indigo carmine dye
over semiconductive, TiO2 as a photocatalyst. The effects of doping of TiO2 as well as the effects of
operational parameters, such as catalyst dose, dye concentration and pH of the solution on the
degradation rate of aqueous dye solutions is examined. Having established optimal operating
conditions.
2. Experimental procedure
2.1 Materials
Indigo Carmine dye was obtained from Loba Chemie (India), The properties, structure and
absorption spectra are given in Table 1. Titanium PC-105 was gifted by Millennium Inorganic
Chemicals and was used as received without further purification .Double distilled water was used
for preparation of various solutions. The pH value of the solutions was adjusted with 1 MHCI or 1
M NaOH.

2.2 Photoreactor
Photocatalytic degradation experiments were carried out in a 1000 ml Pyrex-glass cell in the UV
chamber equipped with eight UV tubes each of 18W (Philips) having a wavelength of 365 nm
(Figure 1). UV light intensity was measured by UVA light meter (Model UVA-365, Lutron) and it
was found to be 0.5 mW/cm2. A magnetic stirrer was used to ensure uniform mixing of solution in
vessel. Prior to irradiation the dispersions were magnetically stirred in dark for 15 min to ensure the
establishment of adsorption/desorption equilibrium. The pH of solutions was measured using WTW
pH-720 digital pH meter. The temperature was maintained constant throughout the reaction time by
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circulating water in the jacketed wall reactor. The spectra were taken with UV–vis
spectrophotometer (Shimadzu UV-1800 PC).
Table 1. Properties and absorption spectra of indigo carmine dye
Name Indigo Carmine
Other name 5,5'-indigodisulfonic acid sodium salt or Indigotine,
Nature Acidic dye
Maximum wave
608 nm
length (λmax)
Empirical formula C16H8N2Na2O8S2
Formula weight 466.36 g mol-1

Molecular
structure

1.4
1.2
1
Absorbance U.A

0.8
0.6
UV–visible spectra
0.4
0.2
0
200 300 400 500 600 700 800
Wave length (nm)n

Figure (1) Photocatalytic Chamber

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2.3 Irradiation experiments
The photocatalyst was added to 100 mL of dye solution and the suspension was irradiated under
UV light. At different time intervals the aliquot was taken out with a syringe and then filtered
through Millipore syringe filter of 0.45 µm. Then absorption spectra of the dye solutions were
recorded and rate of decolorization was observed in terms of change in intensity at λmax of the dye.
The decolorization efficiency (%) has been calculated as:
C C
Decolorization efficiency (%)  o  100
Co
Where Co is the initial concentration of dye and C is the concentration of dye after photoirradiation.
3. Results and discussion
3.1 Effect of TiO2 concentration
In slurry photocatalytic processes, catalyst dosage is an important parameter that has been
extensively studied. Before treatment, the UV–vis spectra of indigo carmine exhibit three main
absorption bands – two in the UV region (250 and 285 nm) and one in the visible region (608 nm).
The UV band is characterized by two adjacent rings, and the visible band is associated with a long
conjugated π system that is linked by two azo groups [16,17]. The decolorization of indigo carmine
was simultaneously monitored at 285 and 608 nm in the UV/TiO2 system. The experiments were
carried out using TiO2 catalyst at a fixed dye concentration (25 mg/L), and different catalyst loading
(0.25 to 1.25) g/L at 60 minute of irradiation. Figure 2 displays the percentage decolorization of
indigo carmine for 60 minute using TiO2 photocatalysts. The results indicate that the optimum dose
of TiO2 is 0.75 g/L exhibits higher photocatalytic activity than the others. The rate of photocatalytic
reaction is strongly influenced by concentration of the photocatalyst. Heterogeneous photocatalytic
reactions are known to show proportional increase in photodegradation with catalyst loading [18].
Generally, in any given photocatalytic application, the optimum catalyst concentration must be
determined, in order to avoid excess catalyst and ensure total absorption of efficient photons [19].
This is because an unfavourable light scattering and reduction of light penetration into the solution
is observed with excess photocatalyst loading [20]. The same trend has been observed in earlier
findings with azo reactive dyes [21,22].

100
0.25 g/l
90
0.50 g/l
80
0.75 g/l
70
1.00 g/l
% Dgredation

60
1.25 g/l
50
40
30
20
10
0
0 10 20 30 40 50 60
Time (min)

Figure 2. Influence of catalyst concentration on the degradation rate for the decomposition of
disperse indigo carmine dye in the presence of TiO2 (dye concentration 25 ppm, natural pH)

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3.2 Effect of pH
The efficiencies of photocatalytic processes strongly depend upon the pH of the reaction solution. It
was due to the amphoteric behavior of semi-conductor TiO2. The surface charge-property of TiO2
changes with the change of solution pH.
Figure 3 depicts the color removal efficiency of indigo carmine dye solution as a function of pH in
the range varying from 4 to 11. The maximum decolorization was seen at lower pH (pH ~4).
Natural pH (pH 7.3) was also found to be favorable for the decolorization of dye solutions. The
interpretation of pH effects on the efficiency of the photodegradation is a very difficult task because
three possible reaction mechanisms can contribute to dye decolorization namely hydroxyl radical
attack, direct oxidation by the positive hole and direct reduction by the electron in the conducting
band. The importance of each one depends upon the substrate nature and pH [23]. The point of zero
charge (pzc) for TiO2 is 6.25. The TiO2 surface is positively charged in acidic solutions and
negatively charged in basic solutions. The selected azo dyes had different adsorption behavior to the
surface of TiO2. Indigo carmine was adsorbed on the surface of TiO2 by the sulfuric group [24,25],
which was negatively charged and the acidic solution favored adsorption of the dye onto
photocatalyst surface. Indigo carmine was strongly adsorbed to the TiO− site of the photocatalyst by
a penta-heterocyclic-N group, which was positively charged, and the basic solution favored
adsorption of the dye onto photocatalyst surface [26].
100
90 pH= 4
80 pH = 7
70 pH = 9
% Degradation

60 pH = 11
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50 55 60
Time (mim)v

Figure 3. Influence of pH on the decolorization rate for the decomposition of indigo carmine dye
(catalyst dose 0.75 g/l and 25 ppm)
3.3 Effect of the initial dye concentration
The influence of initial concentration of the dye solution on the photocatalytic degradation is an
important aspect of the study. Initial concentrations of indigo carmine were varied in the range of
5–100 mg l−1 and the photodegradation percent decreased with increasing initial concentration of
the dye solution as shown in Figure 4. An explanation to this behavior is that as initial concentration
increases, more and more organic substances are adsorbed on the surface of TiO2, therefore, the
generation of hydroxyl radicals will be reduced since there are only a fewer active sites for
adsorption of hydroxyl ions and the generation of hydroxyl radicals. Further, as the concentration of
a dye solution increases, the photons get intercepted before they can reach the catalyst surface,
hence the absorption of photons by the catalyst decreases, and consequently the degradation percent
is reduced [27–29]. Similar behavior was observed by Neepolian et al. [30] for reactive red 2 dye
and by Saquib and Muneer [31] for acid green and acid red dye. Concentration of intermediates
formed and absorption of photon by dye and intermediates increases at higher dye concentration
resulting in lesser energy available for hydroxyl generation.

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100
90 5 ppm
80 10 ppm
70 25 ppm
Degradation %
60 50 ppm
50
100 ppm
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min)m

Figure 5. Influence of substrate concentration on the degradation rate for the decomposition of
indigo carmine dye (catalyst dose 0.75 g/l and pH=4)
3.4 Mineralization studies
As the reduction of chemical oxygen demand (COD) reflects the extent of degradation or
mineralization of an organic species, the percentage reduction in COD was studied for dye samples
(initial concentration 25 mg/L) under optimized conditions (catalysts dose 0.75 g/L, pH 4) as a
function of irradiation time.
Figure 5 shows the percentage decolorization and percentage COD reduction as a function of
irradiation time. It can be seen that the COD reduction is lesser than percentage decolorization
which may be due to the formation of smaller uncolored products. Therefore, it seems that to
achieve complete mineralization of dyes, longer irradiation time is required [32,33]
It was observed that the percentage COD reduction lies between 100 % after 40 min. The COD
reduction is lesser than percentage decolorization which may be due to the formation of smaller
uncolored products. Therefore, it seems that to achieve complete mineralization of dyes, longer
irradiation time is required.

100
90
80
% Declorization
70
% COD Reduction
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40
Time (min)

Figure 6. Comparison of %decolorization and %COD reduction for indigo carmine dye

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3.5 Kinetics study
In practical research, kinetic experiments were performed to study the photodegradation of the
indigo carmine dye. The dependence of the degradation rate on the influencing factors (e.g., catalyst
dose, pH and initial dye concentration) were investigated and gotten from the corresponding kinetic
data. The kinetic models of the photodegradation process are essential to the optimization of
experimental conditions and subsequently, to the design of large-scale photocatalytic reactors.
Several kinetic models have been developed and most of them can not completely account for all
possible factors affecting the degradation rate. The Langmuir–Hinshelwood model has been widely
used to formulate the rate equations for the photocatalytic reaction. For a surface-catalyzed reaction,
chemisorption is the interest. Langmuir developed the adsorption isotherm that leads to a uni-
molecular layer of adsorbed molecules. [34,35].
Figure 6 shows the kinetics of disappearance of indigo carmine dye for an initial concentration of
25 mg L–1 under optimized conditions. The results show that the photocatalytic decolorization of
this dye in aqueous ZnO can be described by the first order kinetic model, ln (C 0/C) = kt, where C0
is the initial concentration and C is the concentration at any time, t. The semi logarithmic plots of
the concentration data gave a straight line. The correlation constant for the fitted line was calculated
to be R2 = 0.9431. The rate constants were calculated to be 0.1456 min–1.

4
y = 0.1456x - 0.5762
R² = 0.9431
3
ln(Co/C)n

0
0 5 10 15 20 25 30 35 40
Time (min)

Figure 7. Kinetic analysis for the decolorization of indigo carmine dye using TiO2

4. Conclusion
In the present study, the efficiency of photocatalytic decolorization of indigo carmine dye solution
using TiO2 by suspending in aqueous media in presence of UV light has been studied. The effect of
catalyst loading, initial concentrations of the dyes, pH, and metal doping on TiO 2 have been
investigated. The experimental results demonstrated that the optimal catalyst load was 0.75 g/l with
indigo carmine dye concentration of 25 ppm. The optimal operational pH was 4, which was
adjusted by diluted HCl solution. Average of 98% color removal has been achieved in a relatively
short UV irradiation time of 40 min at pH 4.
The COD was reduced from 25 ppm indigo dye solution more than 98% in 35 minutes. The
Langmuir–Hinshelwood (L–H) model based on the hydroxyl radicals attack and direct hole attack
rate was developed and could explain the experimental data.

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