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Digital Object Identifier: http://dx.doi.org/10.4172/2157-7048.1000106

Chemical Engineering & Elaziouti et al. J Chem Eng Process Technol 2011, 2:2
http://dx.doi.org/4172/2157-7048.1000106
Process Technology
Research Article
Research Article Open
OpenAccess
Access
ZnO-Assisted Photocatalytic Degradation of Congo Red and Benzopurpurine

4B in Aqueous Solution
Elaziouti1*, N. Laouedj2 and Bekka Ahmed1
1
LCPCE Laboratory, Faculty of sciences, Department of industrial Chemistry, University of the Science and the technology of Oran (USTO M.B). BP 1505 El M’naouar
31000 Oran, Algeria
2
Dr. Moulay Tahar University, Saida, Algeria
Abstract
The photocatalytic degradation of two commercial azo dyes Congo red (CR) and Benzopurpurine 4B (BP4B) in
aqueous solution was investigated under UV-A light at different operating conditions, including irradiation time, pH
solution, initial dye concentration, amount of catalyst, light intensity as well as band gap of other semiconductor groups
by UV-spectrophotometric monitoring. The highest decomposition were obtained at pH 8 as a result of 95.02 and 97.24
% degradation efficiencies of CR and BP4B for 60 and 80min of irradiation time respectively. Photodecomposition
reactions of both dyes were correlated with pseudo-first-order kinetic model. For BP4B, the degradation data were
satisfactory described by Langmuir–Hinshelwood (L-H) mechanism, whereas those of CR were not sufficient to
conclude that the L-H mechanism is the most suitable one to describe the photocatalytic process of CR. These
findings can support the design of remediation processes and also assist in predict their fate in the environment.
Keywords: Photocatalysis; Zinc oxide; Congo red; Benzopurpurine (HO.ads). The stepwise photocatalytic mechanism is illustrated below:
4B; Langmuir–Hinshelwood (L-H)
ZnO + hν → ZnO (e− (CB) + h+ (VB)) (1)
Introduction
O2ads + e− → O•− 2ads (2)
Heterogeneous photocatalysis oxidations performed with
light irradiated semiconductors dispersions has been extensively O•− 2ads + H+→ HO2 ads
(3)
investigated owing to their highly efficiency to completely mineralize O•−2ads + 2H+ + e− → H2O2ads (4)
the harmful organic and inorganic ions species to CO2 and water [1].
Most researches has been focalized on the heterogenic systems based Rads+ h+→ R•ads+ (5)
on high dispersion TiO2 with a crystalline modification of anatase
HO−ads + h+→•OHads+ (6)
(Degussa P25, Hombriat UV-100, Aldrich, etc.) as a result of their
high photocatalytic activity and widespread uses for large-scale water H2Oads + h+→•OHads+ H+ (7)
treatment. However, the relatively elevated intrinsic band gap of anatase
The hydroxylic, peroxide and hydroperoxide radicals are the main
TiO2 (3.2 eV), limited their efficiencies under solar light, so that the
effective utilization of solar energy is limited to about 4% of total solar oxidizing agents in the heterogeneous photocatalytic systems used in
spectrum. In order to meet the requirement of future environment the water treatment technologies. The heterogeneous photocatalytic
and energy technologies, it is necessary to develop highly efficient, processes substantially depend on a variety of environment conditions
non toxic and chemically stable photocatalyst. Various semiconductor such as surface charge and electronic structure of catalyst, the nature
catalysts such as MO2 (M= CeO2, ZrO2, SnO2), M’2O3 (M’=α-Fe2O3, of surface-active center, the localization degree of photogenerated
Bi2O3, Al2O3, Sb2O3 ect..) metal oxide and DS (D=Zn, Cd, Bp) metal charges, the amphoteric properties of photocatalyst, pH, temperature,
chalcogenide groups were investigated, but their practical uses have nature of pollutant, photocongeners, crystalline structure, synthesis
been constrained by their low photocatalytic activity under solar light, method and photorector dimension [7].
short-term stability against photo- and chemical corrosion as well as
potential toxicity [2]. Many attempts have been made to study ZnO- Aggregation is one of the features of dyes in solution. Based on
mediated photocatalytic degradation of organic compounds [3-6]. literature, Congo red dye tends to aggregate in aqueous and organic
Semiconductor, on irradiation with photon of sufficient energy, greater
than or equal to the band gap energy of the semiconductor (hν ≥ Eg),
a free electron (e-) and electronic vacancy-a hole (h+) are generated *Corresponding author: Elaziouti, LCPCE Laboratory, Faculty of sciences,
Department of industrial Chemistry, University of the Science and the technology
and recombine or migrate in the semiconductor surface being partially of Oran (USTO M.B) BP 1505 El M’naouar 31000 Oran, Algeria, Tel: (213)
localized on structural defective centers of its crystalline lattice 0551723590; Fax: (213) 041 56 00 50; E-mail: [email protected]
Equation (1). The photogenerated electrons take part in the reduction Received March 10, 2011; Accepted April 25, 2011; Published May 13, 2011
reaction with dissolved oxygen, producing superoxide anion (O.-2ads),
Citation: Elaziouti, Laouedj N, Ahmed B (2011) ZnO-Assisted Photocatalytic
hydroperoxide (HO2ads) radicals and hydrogen peroxide (H2O2ads) Degradation of Congo Red and Benzopurpurine 4B in Aqueous Solution. J Chem
Equation (2-4), while the photogenerated holes can oxidize either the Eng Process Technol 2:106. doi:10.4172/2157-7048.1000106
organic compound directly Equation (5) or both hydroxylic ions and Copyright: © 2011 Elaziouti, et al. This is an open-access article distributed under
water molecules adsorbed on the photocatalyst surface Equation (6- the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and
7) forming the organic cation-radicals (R.+ads) and hydroxylic radicals source are credited.
J Chem Eng Process Technol

ISSN: 2157-7048 JCEPT, an open access journal Volume 2 • Issue 2 • 1000106
Citation: Elaziouti, Laouedj N, Ahmed B (2011) ZnO-Assisted Photocatalytic Degradation of Congo Red and Benzopurpurine 4B in Aqueous Solution.
J Chem Eng Process Technol 2:106. doi:10.4172/2157-7048.1000106
Page 2 of 9
solutions leading to dimer formation and sometimes even higher order Before irradiation, photocatalyst/substrate suspension was
aggregates due to hydrophobic interactions between aromatic rings of stirred in the dark for 30 minutes at 298K to ensure the adsorption
dye molecules. This aggregation phenomenon is more noticed for high equilibrium was established. Next, the lamp was switched on to
Congo red concentrations, at high salinity and/or low pH. The formed initiate the photocatalytic degradation reaction. During irradiation,
aggregates (micelles) separate and precipitate onto solid surfaces. agitation was maintained by a magnetic stirrer to keep the suspension
In the present work, the potential ability of ZnO-assisted homogeneous. The suspension was sampled at regular intervals of
photocatalytic degradation of Congo red (CR) and benzopurpurine 4B time and immediately centrifuged using (EBA-Hetlich) at 3500 rpm
(BP4B) was assessed in terms of evolution of the photodecomposition for 15 min to completely remove photocatalyst particles. The residual
efficiency at different operating parameters such as, irradiation time, concentration of the solution samples was monitored using UV-Vis
pH solution, initial dye concentration, amount of catalyst, light Spectrophotometer (Shimadzu UV mini-1240) at λ = 497 and 500 nm
intensity and as well as band gap of other semiconductor groups. The for CR and BP4B respectively, as a function of irradiation time.
experimental data were quantified by applying the pseudo-first order The effect of initial pH on the photocatalytic degradation of
kinetic and Langmuir-Hinshelwood (L-H) model to accommodate
Benzopurpurine 4B was researched over a range of pH values from 2
reactions occurring at a solid-liquid interface.
to 10. But for Congo red, the experiments were only conducted from
Materials and Methods pH 6 to 10 for avoiding dye aggregation. The experiments were also
performed by varying the initial dye concentration from 20 to 60 mg/L,
Nanoparticle semiconductors ZnO (BET surface area, S= 10
amount of photocatalyst from 0.25 to 3 g/L and light intensity from 50
m2/g and particle size D=60 nm, 99.99%), TiO2 (anatase 99.99%),
Al2O3(99.99%), CeO2 (99.99%), and Fe2O3 (99.99%), were obtained to 90 j/ cm2 as well as band gap of semiconductors by replacing ZnO
from Merck, and were used without further purification. Congo red with TiO2, Al2O3, CeO2 and Fe2O3 nanoparticles.
(C.I. 22 120, MW = 696.67 g mol-1, C32H24N6O6S2.2Na, λ max =497 The data obtained from the photocatalytic degradation experiments
nm and pKa=4) and benzopurpurine 4B (C.I.23500, MW =724.74 g were then used to calculate the degradation efficiency η (%) of the
mol-1, C34H26N6O6S2Na2 λ max=500 nm and pKa=6.8). The molecular substrate Equation (8):
structure of the dye is illustrated in Figure 1. Distilled water was used
for preparation of various solutions. η(%) = [
( C i − C f ) ]100 (8)
Ci
Photocatalytic reactions were carried out inside a (BLX-E365)
photoreactor equipped with 6UV-A lamps with an emission maximum where Ci: dye initial concentration (mg·L-1) and Cf : dye residual
at λ of 365 nm. The suspension was irradiated perpendicularly to the concentration after certain intervals (mg·L-1).
surface of solution, and the distance between the UV source and vessel
To calculate the corresponding energy at UV-A wavelength. The
containing reaction mixture was fixed at 15 cm. The experiments were
energy of an electro-volt, E (eV), at a given wavelength, λ (nm), is given
performed at 298K. In all photocatalytic degradation experiments,
by Equation. (9):
300mL CR solution of appropriate concentration was taken in
photocatalytic reactor vessel of 600 ml capacity. A known quantity of hc
semiconductor was added and mixture was stirred to obtain uniform E ( eV ) = (9)
λj
suspension. The suspension pH values were previous adjusted using where h is Planck’s constant (6.626 10-34 J s); c is the speed of light (3
NaOH/ H2SO4 solutions via pH meter (HANNA HI 83141). 108 m/s); and j is the number of electro-volt per joule (joule=1.6 10-
19
electro-volt). The corresponding light energy at UV-A (365 nm)
wavelength was estimated to E UV-A = 3.4 eV.
The photocatalytic degradation efficiency of ZnO catalyst for the
degradation of CR and BP4B was quantified by measurement of dyes
apparent first order rate constants under operating parameters and
Langmuir–Hinshelwood modified kinetic analysis to accommodate
reactions occurring at a solid-liquid interface. Surface catalyzed
reactions can often be adequately described by a monomolecular
Langmuir–Hinshelwood mechanism, in which an adsorbed substrate
(a)
with fractional surface coverage θ is consumed at an initial rate given
as follow Equation (10) [8]:
 dC  KKC
−   = r0 = K appθ = 1 2 0 (10)
 dt  1 + K1C 0
where K1 is a specific rate constant that changes with photocatalytic
activity, K2 the adsorption equilibrium constant, and C0 is the initial
concentration of the substrate (Congo Red and Benzopurpurine 4B in
our cases). Inversion of the above rate equation is given by Equation
(b) (11):
Figure 1: Molecular structures of basic dyes: (a) Congo red (CR); (b) 1 1 C
Benzopurpurine 4B (BP4B).
= + 0 (11)
K appC 0 K1K 2 K1

Page 3 of 9
Thus, a plot of reciprocal of the apparent first order rate constant 1/

Kapp against initial concentration of the dye C0 should be a straight line 1
with a slope of 1/K1 and an intercept of 1/K1K2. Such analysis allows 0.9
one to quantify the photocatalytic activity of ZnO catalyst through 0.8
the specific rate constant K1 (with larger K1 values corresponding to 0.7
higher photocatalytic activity) and adsorption equilibrium constant K2 0.6
C/Co
(K2 expresses the equilibrium constant for fast adsorption-desorption
0.5
processes between surface of catalyst and substrates). The integrated
0.4
form of the above equation (Equation 10) yields to the following
Equation (12): 0.3 BP4B/UV-A
0.2 BP4B/ZnO
1 C 1
t= ln 0 + (C0 − C ) (12) 0.1 BP4B/ZnO/UV-A
K1K 2 C K 2
0
where t is the time in minutes required for the initial concentration 0 10 20 30 40 50 60 70 80
of the dye C0 to decrease to C. Since the dye concentration is very low, t /min
the second term of the expression becomes small when compared with
Figure 3: Photocatalytic degradation of BP4B under different experimental
the first one and under these conditions the above equation reduces to conditions ([ZnO]=1/L, [BP4B]=20mg/l, natural pH =8, T=298K, λmax=365 nm
Equation (13): and I=90j/cm2).
C0
ln ≈ K1K 2 t = K app t (13)
C
100
where kapp is the apparent pseudo-first order rate constant, C and C0 are
Photocatalytic degradation
the concentration at time ‘t’ and ‘t=0’, respectively. The plot of ln C0/C 90
against irradiation time t should give straight lines, whose slope is equal
rate η /%
to Kapp. The half-life of dye degradation at various process parameters 80

was raised from Equation (14):
0.5C 0 0.693 70
t1/2 = + (14)
K2 K1K 2
60
CR
where half-life time, t1/2, is defined as the amount of time required for
BP4B
the photocatalytic degradation of 50% of the RC and BP4B dyes in 50
aqueous solution by ZnO catalyst. 1 3 5 7 9 11
Results Initial pH
Figure 4: Effect of pH on photocatalytic degradation of dyes ([ZnO]= 0.5g/L(for
Effect of UV light and catalyst CR) and 1g/L (for BP4B), [CR]= [BP4B]= 20mg/l, T=298K, λmax=365 nm and
I=90j/cm2).
Figures 2 and 3 illustrate the photocatalytic degradation kinetics of
20 mg/L of dyes in aqueous solution under three different experimental
conditions through UV-A alone, dark/ ZnO and UV-A/ZnO. The and 95.02 and 97.24% of degradation were achieved within 60 and 80
degradation rate was found to increase with increase in irradiation time min for CR and BP4B respectively (curve Dye/ZnO/UV-A). When 20
mg/L of both dyes along with ZnO were magnetically stirred for the
1
same optimum irradiation times in the absence of light, lower (20.78
0.9
and 13.17 %) degradation were observed (curve Dye/ZnO) for CR
and BP4B respectively, whereas, disappearance of dyes was negligible
0.8
(0.49% for CR and 4.45% for BP4B) in the direct photolysis (curve Dye/
0.7
UV-A) indicating that the observed high decomposition of both dyes
0.6
in the UV/ZnO process is exclusively attributed to the photocatalytic
C/Co
0.5
reaction of the semiconductor particles. Similar results have been
0.4
reported for ZnO-assisted photocatalytic degradation of azo dyes such
0.3 CR/UV-A
as Congo red [9] and Reactive Black 5 [10].
0.2 CR/ZnO
0.1 CR/ZnO/UV-A Effect of pH solution

0
In order to study the effect of initial pH on the degradation
0 10 20 30 40 50 60
efficiency of ZnO catalyst on photodecomposition of both dyes,
t/min
experiments were carried out at various pH, ranging from 2 to10,
Figure 2: Photocatalytic degradation of CR under different experimental except for CR, where tests were done from 6 to 10 for avoiding dye
conditions ([ZnO]=0.5g/L, [CR]= 20mg/l, natural pH =8, T=298K, λmax=365 nm aggregation. The results showed that the pH significantly affected the
and I=90j/cm2).
degradation efficiency for both dyes. As shown in Figure 4 and Table

Page 4 of 9
Experimental Pseudo-first order

Experimental Experimental results Pseudo-first order model
results model
parameters
CR BP4B
RC BP4B ADS / % PCD /% kapp /min-1 t1/2 /min R2/% ADS/% PCD/% kapp/min-1 t1/2/min R2 /%
6 2 18.19 70.25 0.014 49.511 79.8 86.09 80.70 0.023 9.57 32.2
Initial pH 7 4 16.13 75.68 0.025 27.726 96.8 41.51 94.19 0.037 14.29 98.3
solution 8 6 10.50 95.02 0.041 16.906 88.1 32.84 93.07 0.035 128.36 98.0
(pH)
9 8 14.94 89.38 0.038 18.241 79.0 3.89 97.24 0.026 26.45 95.6
10 10 11.81 86.339 0.035 19.804 74.7 24.84 91.69 0.036 144.40 88.0
R2: Regression coefficient, ADS: Adsorption and PCD: Photocatalytic degradation
Table 1: Kinetic parameters of photocatalytic degradation of dyes in aqueous solution as a function of pH ([ZnO]=0.5g/L(for CR) and 1g/L (for BP4B), [CR]=[BP4B]=20mg/L,
T=298K, λmax=365 nm and I=90j/cm2).
1, for CR, the degradation rate increased from 70.25 to 95.02% as the at pH lower than 4 Equation (17) In particular, ZnO can be photo-
pH value was increased from 6 to 8, and then decreased to 86.34% at oxidized with decreasing the pH Equation (18)
pH 10, whereas, for BP4B, the degradation activity raised from 80.70 to
ZnO + 2h+ (VB) → Zn2+ + 1/2O2 (17)
97.24% when the pH was increased from 2 to 8 and then decreased to
91.69 % at pH 10. The maximum degradation rate of CR (95.02%) and ZnO + 2H+ → Zn2+ + H2O (acidic dissolution) (18)
BP4B (97.24%) were achieved at pH 8. For this reason, for both dyes,
Photocatalytic activity of anionic dyes (mainly sulfonated groups)
the pH 8 was selected for subsequent experiments.
such as CR and BP4B reaches a maximum value in lower pH zpc (i.e.
It is commonly accepted that in photocatalyst/aqueous systems, pH =8). At alkaline mediums, excess of hydroxyl anions facilitate
the potential of the surface charge is determined by the activity of ions photogeneration of •OH radicals which is accepted as primary
(e.g. H+ or pH). A convenient index of the tendency of a surface to oxidizing species responsible for photocatalytic degradation, resulting
become either positively or negatively charged as a function of pH is in enhancement of the efficiency of the process. Furthermore we found
the value of the pH required to give zero net charge (pH zpc) [11,12]. that, where the adsorption of dyes was weak, degradation scarcely
pH zpc is a critical value for determining the sign and magnitude of occurred. The adsorption affects strongly the accessibility of the surface
the net charge carried on the photocatalyst surface during adsorption reducing species to the CR and BP4B reduction kinetics. However,
and photocatalytic degradation process. Most of the semiconductor adsorption is not the only factor that controls the photocatalytic
oxides are amphoteric in nature, can associate (Equation 15) or degradation of dyes. Although the adsorption extents of both dyes were
dissociate (Equation 16) proton. To explain the relationship between lower, the degradation rates were in the reverse order.
the layer charge density and the adsorption, so-called Models of
Surface Complexation (SCM) was developed [13], which consequently At pH higher than pH zpc value (i.e. pH =10), a dramatically
affects the sorption–desorption processes and the separation and decrease in the degradation efficiency could be explained on the basis
transfer of the photogenerated electron–hole pairs at the surface of of amphoteric behaviors of ZnO catalyst. The negatively surface of
the semiconductor particles. In the 2-pK approach we assume two ZnO catalyst (highly concentration of hydroxide ions) and the great
reactions for surface protonation. negatively charged RC and BP4B dye anions results in electrostatic
repulsion electrostatic.
The zero point charge pH zpc for ZnO is 9.0. For pH values lower
than the pH zpc of ZnO, the surface becomes positively charged, Moreover, the stability of ZnO may not be guaranteed at this high
according to the following reaction Equation (15):
pH < pH zpc Zn-OH + H+ → ZnOH2 (15)
ZnO surface becomes negatively charged for pH values higher than 100
pHpzc, given by the following reaction Equation (16):

80
pH > pH zpc Zn-OH + OH- → ZnO- + H2O (16)
rate η /%
60
The experimental data revealed that higher degradation rate of
BP4B was observed in acidic medium. Since BP4B is an anionic dye, its
40
adsorption mainly performed via an electrostatic interactions between
the positive ZnO surface and BP4B anions, leading to a maximum 20 CR
extent at pH 2. Thus, a strong adsorption can lead to a drastic decrease
BP4B
in the active centers on the catalyst surface, which results in decrease 0
in the absorption of the light quanta by the catalyst and consequently 0 0.5 1 1.5 2 2.5 3
to a reducing of the kinetic reaction. As a result, the high degradation
m/v g/L
efficiency cannot be ascribed to the photocatalytic oxidation of
the BP4B dye, but to catalyst behavior under strong acid pH. ZnO Figure 5: Effect of amount of catalyst on photocatalytic degradation of dyes
([CR]=[BP4B]=20mg/L, pH =8, T=298K, λmax=365 nm and I=90j/cm2).
nanoparticles can undergo photo-corrosion through self-oxidation

Page 5 of 9
Pseudo-first order
Experimental results Experimental results Pseudo-first order model
model
Experimental parameters CR BP4B
ADS / % PCD /% kapp /min-1 t1/2 /min R2/% ADS/% PCD/% kapp/min-1 t1/2/min R2 /%
0.25 8.93 68.73 0.030 23.105 82.6 38.31 46.29 0.014 49.511 46.1
0.5 10.50 95.02 0.041 16.906 88.1 2.34 64.21 0.018 38.508 68.4
Catalyst amount 1 33.59 83.80 0.037 18.734 93.0 3.89 97.24 0.026 26.456 95.6
ZnO/g/L
2 41.98 85.45 0.040 17.329 79.0 35.54 95.26 0.037 18.734 96.7
3 53.40 92.68 0.048 14.441 93.0 60.85 86.97 0.026 26.660 96.2
Table 2: Kinetic parameters of photocatalytic degradation of dyes in aqueous solution as a function of amount of photocatalyst ([CR]=[BP4B]=20mg/L, pH =8, T=298K,
λmax=365 nm and I=90j/cm2).
pH due to possibility of alkaline dissolution of ZnO Equation (19):

100
ZnO + H2O + 2OH-→ Zn(OH)4+ (alkaline dissolution) (19)
90
Effect of the amount of catalyst 80
70
rate η /%
The effect of the amount of catalyst (m/v) on photocatalytic 60
degradation of dyes was conducted over a range of catalyst amount 50
40
from 0.25 to 3g/L. As observed in Figure 5 and Table 2, the degradation
30
rate of CR increased from 68.73 to 95.02 % in CR and from 46.29 to 20
CR
97.24% in BP4B when the ZnO amount was raised from 0.25 to 0.5 10 BP4B
g/L for CR and from 0.25 to 1g/L for BP4B respectively. This increase 0
10 20 30 40 50 60 70
in degradation rate with the photocatalyst amount can be explained
in terms of availability of active sites on the catalyst surface and the C0 /mg/L
penetration of UV light into the suspension as a result of increased
Figure 7: Langmuir–Hinshelwood analysis for photo catalytic degradation of
screening effect and scattering of light. Further increase in the catalyst CR and BP4B ([ZnO]=0.5g/L (for CR) and 1g/L (for BP4B) pH =8, T=298K,
amount beyond of 0.5 g/L for CR and 1g/L for BP4B, the rate of λmax=365 nm and I=90j/cm2.
degradation remains nearly constant for CR, but it slightly decreased for
BP4B due to overlapping of adsorption sites as a result of overcrowding Effect of initial dye concentration
of adsorbent and deactivation of activated catalyst particles owing to Figure 6 illustrates the effect of initial dye concentration on the
collision with ground state catalyst as shown below Eq. (20) [14]: photo catalytic degradation rate of dyes in the range of 20 to 60 mg/L. As
it can be observed, disappearance rate was found to be inversely affected
ZnO* + ZnO → ZnO# + ZnO (20)
by initial concentration of dyes. The drastic decrease in the degradation
where ZnO* is ZnO with active species adsorbed on its surface; ZnO# activity with dyes concentration is ascribed to the increase in the local
deactivated form of ZnO* shielding by ZnO may also take place. The concentration of CR as well as BP4B on the ZnO surface, while the
adsorbent dose of 0.5 and 1 g/L for CR and BP4B were used in all other UV light irradiation time and photocatalyst amount are kept constant,
parameter experiments. leading to the formation of dimer and higher order aggregates owing
to hydrophobic interactions between aromatic rings and hence the rate
formation of hydroxylic and superoxide anion radicals are dramatically
600 y (CR) = 11,734x - 242,28 reduced thereby decreasing rate of degradation. The maximum
CR BP4B R² = 0,9565
concentration of both dyes that could be degraded by 0.5 and 1g/L of
500
ZnO for CR and BP4B respectively is found to be 20mg/L. Similar trend
was observed in the photocatalytic degradation of Reactive Black 5 and
1/Kapp /min-1
400
Reactive Orange 4 dyes using ZnO and TiO2 as photocatalysts [15].
300
Thus 20 mg/L CR and BP4B was selected as optimum concentration
200 for the study of other experiments.
y (BP4B)= 1,0793x + 14,806
R² = 0,6809
100
The photocatalytic degradation process profiles of both dyes by
ZnO catalyst at low dye concentrations and under pH solution, amount
0 of catalyst and initial dye concentration follow apparently pseudo-
10 20 30 40 50 60 70 first-order kinetics. The linear plot of lnC0/C against irradiation time
C0 /mg/L t (Table 1, 2 and 3) should give a straight line with relatively high
regression coefficients, whose slope is equal to the apparent first order
Figure 6: Effect of initial dye concentration on photo catalytic degradation of
dyes ([ZnO]=0.5g/L (for CR) and 1g/L (for BP4B) pH =8, T=298K, λmax=365 nm
rate constant Kapp.
and I=90j/cm2.
On the other hand, the effect of initial concentrations of both dyes

Page 6 of 9
Pseudo-first order
model
20 10.50 95.02 0.041 16.906 88.1 3.89 97.24 0.026 26.456 95.6
30 20.93 47.87 0.009 77.016 91.0 11.25 72.85 0.022 31.651 82.6
Initial dye concentration 40 15.26 34.10 0.006 115.525 91.0 2.12 68.87 0.015 45.904 98.2
Dye/mg/L 50 1.95 20.15 0.003 231.049 95.0 1.18 74.24 0.020 34.485 81.9
60 3.86 14.25 0.002 346.574 86.00 33.11 51.71 0.011 62.446 95.9
R : Regression coefficient, ADS: Adsorption and PCD: Photo catalytic degradation

2
Table 3: Kinetic parameters of photo catalytic degradation of dyes in aqueous solution as a function of initial dye concentrations.([ZnO]=0.5g/L (for CR) and 1g/L (for BP4B),
pH =8, [CR]=[BP4B]=20-60mg/L, PH =8 T=298K, λmax=365 nm and I=90j/cm2).
in the photocatalytic degradation rate can be assessed in terms of the

Langmuir–Hinshelwood (LH) kinetic model modified. 100
90 CR BP4B
The plot of 1/Kapp against C0 (Figure 7) should yield a straight line
80
with high regression coefficients (R2=0.96 and 0.68 for CR and BP4B
respectively). The K1 and K2 values were calculated from the slope (1/ 70
rate η / %
K1) and the intercept (1/K1K2) respectively. The values of K1 and K2 60
were found to be 0.048 L/g and 0.085g/L.min for CR and 0.073L/g 50
and 0.927g/L.min for BP4B respectively. The product of K1K2 = 0.004 40
and 0.068 min–1 for CR and BP4B respectively which represent the 30
apparent rate constant Kapp for low initial concentrations of dye and is
20
in agreement with the experimental results obtained from (Equation
10
13) for BP4B.This results suggest that the photocatalytic degradation
data were satisfactorily described by Langmuir–Hinshelwood (LH) 0
kinetic model in a wide range of dye concentration. However, that CeO2 TiO2 ZnO Fe2O3 Al2O3
of CR are not sufficient to conclude that the L-H mechanism is the Semiconducteurs
most suitable one to describe the photocatalytic process of CR, since
Figure 9: Effect of band gap of semiconductors on photocatalytic degradation
the calculated Kapp (Kapp=K1K2) value deduced from pseudo-first-order of dyes [Catalyst]=0.5g/L (for CR) and 1g/L (for BP4B), [CR]=[BP4B]=20mg/L,
kinetic equation was much different compared with experimental Kapp, pH =8, T=298K, λmax=365 nm and I=90j/cm2).
despite its regression coefficient is higher than of BP4B.
Effect of the UV-A light intensity 8 and Table 4, depicts that the degradation efficiency of BP4B increased
linearly with the light intensity, whereas that of CR it increased up to
Intensity of the irradiation has been reported to be an important 70j/cm2 and after no changes are observed. The linear increase of the
parameter influencing the degradation of organic chemicals by photo degradation efficiency for CR and BP4B at light intensity, ranging from
catalytic activity. The effect of light intensity on the rate of photo 50 to70 j/cm2 and from of 50 to90 j/cm2 for CR and BP4B respectively
catalytic degradation of dyes was investigated by varying the light is assigned by more photons would be available for excitation at the
intensity of UV-A between 50 and 90 j/ cm2. Results reported in Figure semiconductor surface and in turn more electron hole pairs will be
generated. Thus this resulted in enhanced rate of degradation. The
100 value of k1 was found to increase with the increase in light intensity,
a typical characteristic of a photo catalytic reaction. At a higher light
intensity than 70 j/cm2 for CR, there is no effect on degradation activity
Photocatalytc degradation
90
on further increase in light intensity. The results indicate that maximum
numbers of photons which are required for excitation are available in
80
rate η / %
specific constant range of irradiating light intensity. Further increase

in light intensity no significant changes are observed in photocatalytic
70
degradation efficiency because all photo catalyst particles are exited, so,
the rate of degradation remains unchanged [16].
60 CR
BP4B Effect of the band gap of semiconductors
50
The photocatalytic degradation reactions were further performed
40 50 60 70 80 90 100
in four other semiconductors having different band gap values (Figure
I / j/cm2 9 and Table 5). It is evident that the photocatalytic degradation
Figure 8: Effect of light intensity on photocatalytic degradation of dyes of dyes greatly depends on the electronic structure and properties
[Catalyst]=0.5g/L (for CR) and 1g/L (for BP4B), [CR]=[BP4B]=20mg/L, pH =8, of semiconductor surface/solvent. Generally, semiconductor on
T=298K and λmax=365 nm).
irradiation with light energy greater than or equal to band gap

Page 7 of 9
energy of the semiconductor (hν ≥ Eg), a free electron (e-) and system was much lower than ZnO and TiO2 catalysts, although it band
electronic vacancy-a hole (h+) are formed and recombine or migrate gap being smaller than of EUV-A light energy. The CeO2 system might
in the semiconductor surface. Probability of electron transfer in the reduce the life of electron-hole pairs, and enhance the opportunities
semiconductor/adsorbate system is determined by a relative position of their recombination. The order of the photocatalytic degradation
of the valence band, the photocatalyst conductance band and the efficiency is ZnO > TiO2 > CeO2> Al2O3> Fe2O3. Consequently, the
value of the oxidation-reduction potential (ORP) of the oxidant and photocatalytic ability of semiconductor is significantly dependent on
the substrate. The photogeneration of electrical charge is in dynamic their band gap values.
equilibrium with their recombination substantially reducing the
quantum yield of the photocatalytic process. The ORP of water Table 4 and 5 record the kinetic parameters of photocatalytic
oxidation, hydroxylic ions, and most of organic compounds below of degradation of CR and BP4B in aqueous solution.
reducing photogenerated holes within a wide interval of the pH due to The results show that the photocatalytic decolorization of both
which the formation of hydroxylic radicals and organic cation-radicals the dyes in aqueous solutions under light intensity and band gap of
of photocatalyst surface are thermodynamically possible processes. catalysts can be described by the pseudo-first-order kinetic model.
It has already reported that semiconductors such as ZnO and TiO2 The semi-logarithmic plots of the experimental data under optimized
having band gaps larger than 3 eV are excellent photocatalysts. conditions (lnC0/C against t) yielding to a straight line. The regression
Obviously, ZnO and TiO2 semiconductors exhibit a higher degradation coefficients for the fitted lines were calculated to be R2 = 0.881 and
activity than that of the other systems because their band gaps (Eg = 3.2 0.956 for CR and BP4B respectively. The apparent rate constants, Kapp
and 3.3 eV for ZnO and TiO2 respectively) are slightly equal to that of and the half-life time, t1/2 were calculated to be 0.041 min-1and 16.906
UV-A irradiation source (E UV-A =3.4 eV). The photogenerated electron min for CR and 0.026 min-1 and 26.46 min for BP4B.
(e-)-hole (h+) pairs can be easily separated and transferred to the
semiconductor/adsorbate interface efficiently, consequently improving Table 4 and 5 report the kinetic parameters of the photo
the photocatalytic activity [17]. decomposition of both dyes in aqueous solution using ZnO catalyst
at low dyes concentration and under light intensity and band gap of
On the other hand, Al2O3 and Fe2O3 catalysts showed lower activity catalysts.
for the photocatalytic activity of dyes than ZnO and TiO2, since their
conductance bands of 5.6 and 3.7 eV respectively, are much higher Mechanism
than of the E UV-A light irradiation source as a result of low light energy
Photocatalyic degradation schemes for an azo-dye are characterized
conversion efficiency, so the photogenerated electrical charge in
by nitrogen to nitrogen double bonds (N= N) that are usually attached
semiconductor cannot efficiently transfer in the surface and are lost
to two radicals of which at least one but usually both are aromatic groups
due to recombination.
(benzene or naphthalene rings). The color of azo-dyes is determined by
The minimum energy required for excitation of an electron from the azo bonds and their associated chromophores and auxochromes.
the valence band to conductance band for the semiconductor such as Azo bonds are the most active bonds in azo-dye molecules and can be
CeO2 is 2.7 eV. The photodecomposition process of both dyes in CeO2 oxidized by positive hole or hydroxyl radical or reduced by electron
Pseudo-first order
model
50 12.20 77.11 0, 029 16.906 83.7 50.65 77.35 0.022 31.364 92.8
60 11.19 83.78 0.027 12.603 64.7 32.41 80.24 0.022 31.364 96.9
Light Intensity
70 17.93 94.33 0.045 15.403 98.6 34.95 87.57 0.032 21.661 75.2
I/ J/cm2
80 24.07 98.69 0.055 12.603 83.1 26.14 86.52 1.032 0.672 75.2
90 10.50 95.02 0.041 16.906 88.1 3.89 97.24 0.026 26.456 95.6
Table 4: Kinetic parameters of photocatalytic degradation of dyes in aqueous solution as a function of light intensity ([ZnO]=0.5g/L (for CR) and 1g/L (for BP4B), pH =8,
[CR]=[BP4B]=20-60mg/L, pH =8, T=298K and λmax=365 nm).
Experimental results Pseudo-first order model Experimental results Pseudo-first order model
Experimental CR BP4B
parameters
Zn O 10.50 95.02 0.041 16.906 88.1 3.89 97.24 0.026 26.456 95.6
Band gap of Ti O2 13.47 93.34 0.045 15.40 98.5 28, 52 68.54 0.002 346.57 78.2
catalyst
[Eg ] Ce O2 8.00 14.93 0.003 231.05 49.0 25, 59 47.19 0.033 20.94 70.7
(eV) Al2O3 4.21 7.91 0.001 693.15 88.7 13, 73 50.21 0.011 63.01 46.4
Fe2O3 5.15 4.72 0.001 693.15 34.0 1, 74 12.77 0.018 38.08 95.0
Table 5: Kinetic parameters of photocatalytic degradation of dyes in aqueous solution as a function of band gap of semiconductors.([Catalyst]=0.5g/L (for CR) and 1g/L (for
BP4B), [CR]=20mg/l, pH =8, T=298K, λmax=365 nm and I=90j/cm2).

Page 8 of 9
in the conduction band. The cleavage of N= N bonds leads to the which have been shown to be the primary cause of organic matter
decoloration of dyes [18]. mineralization (Equation 30).
When a semiconductor is irradiated with light having energy •OH + Dye → degradation of the dye (30)
equal to or more than band gap energy (hν≥ Eg), a heterogeneous
These observations clearly demonstrate the involvement of holes
photocatalytic reaction occurs at the photocatalyst/adsorbate interface. (h+), hydroxyl (OH•) and superoxide anion (O2•_) radicals as highly
The conduction band electrons (e–) and valence band holes (h+) are oxidizing agents in the ZnO-mediated photocatalytic oxidation of
formed Equation (21). A part of the photogenerated charge carriers Congo red as well as Benzopurpurine 4B.
recombines in the bulk of the semiconductor, while the rest transfer
in the photocatalyst surface, where the holes as well as the electrons act Conclusion
as powerful oxidants, respectively. The photogenerated electrons react Congo red dye tends to aggregate in acidic aqueous solutions
with the adsorbed molecular O2 on the ZnO photocatalyst particle sites, leading to dimer and higher order aggregates due to hydrophobic
reducing it to a superoxide radical anion O2•– Equation (22), while the interactions between aromatic rings of dye molecules. Degradation
photogenerated holes can oxidize either the dye molecule directly or photocatalytique of CR and BP4B was negligible when ZnO catalyst
the OH– ions and the water molecules adsorbed the ZnO surface to and UV light were used on their own, whereas, the observed high
•
OH radicals Equation (23). decomposition in the UV/ZnO process is exclusively attributed to the
photocatalytic reaction of the semiconductor particles. The degradation
In the photocatalytic oxidation process, the generation of hydroxyl
kinetics of both dyes were fast with maximum efficiencies of 95.02%
radicals occurs in two different pathways.
for CR and 97.24 % for BP4B have been achieved within 60 and 80
First pathway: In the first pathway, where U.V light is used in the min using 0.5 and 1g/L of ZnO catalyst for CR and BP4B respectively
photocatalytic reaction, electrons in the semiconductor are excited at a pH of 8 and 298K. The degradation rate of dyes was obviously
from the valence band to the conduction band leaving positive holes in affected by the operating parameters (illumination time, initial dye
the valance band. The photogenerated electrons react with the adsorbed concentration, and amount of photocatalyst, light intensity, pH and the
oxygen molecules to form O•−2ads species, while the photogenerated band gap of semiconductors). L-H mechanism is the most suitable to
holes that are able to migrate to the hydroxylated surface can create a describe the photocatalytic process of BP4B, so the oxidants involved in
highly reactive and short-lived hydroxyl radicals •OH. These processes the photodegradation reactions were identified as holes (h+), hydroxyl
could be represented in the following equations: radicals (•OH) and superoxide anion radicals (O2•−). However the
present kinetic data are not sufficient to conclude the validity of the
ZnO + hν → ZnO (e−+ h+) (21) L-H model in interpreting the results of heterogeneous photocatalysis
O2ads + e− → O•− 2ads (22) of CR dye.
Acknowledgments
h + OH → OH
+ − •
(23)
We greatly acknowledge the material support obtained from DR T.M.
Second pathway: In the second pathway where a solar radiation University.
is used a photosensitization process takes place. In this process, the
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ZnO-Assisted Photocatalytic Degradation of Congo Red and Benzopurpurine

J Chem Eng Process Technol

J Chem Eng Process Technol

Thus, a plot of reciprocal of the apparent first order rate constant 1/

to Kapp. The half-life of dye degradation at various process parameters 80

0.1 CR/ZnO/UV-A Effect of pH solution

J Chem Eng Process Technol

Experimental Pseudo-first order

pHpzc, given by the following reaction Equation (16):

J Chem Eng Process Technol

pH due to possibility of alkaline dissolution of ZnO Equation (19):

J Chem Eng Process Technol

R : Regression coefficient, ADS: Adsorption and PCD: Photo catalytic degradation

in the photocatalytic degradation rate can be assessed in terms of the

specific constant range of irradiating light intensity. Further increase

J Chem Eng Process Technol

J Chem Eng Process Technol

4. Sushil K, Kansal N K, Sukhmehar S (2009) Photocatalytic Degradation of

5. Kansal SK, Singh M, Sud D (2007) Studies on photodegradation of two

J Chem Eng Process Technol

Submit your next manuscript and get advantages of OMICS

• User friendly/feasible website-translation of your paper to 50 world’s leading languages

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J Chem Eng Process Technol

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