Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278

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Journal of the Taiwan Institute of Chemical Engineers

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Photocatalytic activity of a nitrogen-doped TiO2 modied zeolite in the

degradation of Reactive Yellow 125 azo dye
Elida Cristina Ilinoiu a, Rodica Pode a,*, Florica Manea a, Liliana Andreea Colar a, Agnes Jakab a,
Corina Orha b, Cornelia Ratiu b,c, Carmen Lazau b, Paula Sfarloaga b
a
Department of Applied Chemistry and Engineering of Inorganic Compounds and Environment, Politehnica University of Timisoara Victoriei Sq. 2, 300006 Timisoara, Romania
b
Department of Condensed Matter, National Institute of Research-Development for Electrochemistry and Condensed Matter Timisoara, Plautius Andronescu 1, 300224 Timisoara,
Romania
c
National Institute for Research and Development in Microtechnologies, Bucharest, Romania

ARTICLEINFO ABSTRACT

Article history: In this study, the hybrid material based on natural zeolite modied with nitrogen-doped TiO2
Received 7 May 2012 photocatalyst (Z-TiO2-N) was synthesized by solid-state reaction under microwave-assisted hydrother-
Received in revised form 16 July 2012 mal conditions. The surface characterization of hybrid material has been investigated by X-ray
Accepted 2 September 2012 diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) analysis, and FT-IR
Available online 27 December 2012
spectroscopy. The photocatalytic activity of Z-TiO2-N photocatalyst under UV and VIS irradiation was
determined for the degradation of Reactive Yellow 125 (RY 125) dye solution. Also, UVVIS diffuse
Keywords: reectance (DRUVVIS) spectroscopy was used to determine the light absorption properties of the
Nitrogen-doped TiO2-modied zeolite
hybrid material. The operational conditions using photocatalyst dose of 1 g/L at pH 3 were established as
Photocatalysis
optimal conditions for photocatalytic application in RY 125 dye solution degradation. The experimental
UV irradiation
VIS irradiation studies revealed that the degradation efciency expressed in terms of discoloration, aromatic ring-
RY 125 dye opening and mineralization depended strongly on the initial RY 125 dye solution concentrations. The
photocatalyst exhibited a good performance for discoloration and aromatic-ring opening processes at all
studied concentrations (25, 50 and 100 mg/L) but an effective mineralization was reached only for
25 mg/L RY 125 dye solution. Also, the degradation of low concentrations of RY 125 dye solution was
achieved using Z-TiO2-N catalyst under VIS irradiation.
2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction coagulation [7,8], adsorption [911], advanced oxidation processes

(AOPs) [12,13] and membrane ltrations [14] have been employed.
Industrial dyestuffs including textile dyes represent a major All these processes exhibit some specic advantages or drawbacks.
threat for environment [1]. The most typical characteristic is their Advanced oxidation processes can be regarded as a potential
color, which is responsible for a non-esthetic visual pollution [2,3]. alternative to decolorate and reduce recalcitrant wastewater loads
In this way, the presence of dyes in wastewaters is visible even at from textile dyeing industry [5] based on the generation of some
low concentrations. Another characteristic of these efuents very reactive species, such as hydroxyl radicals (OH), which
consists of their variable composition, which are in general oxidize quickly and non-selectively a broad range of pollutants
represented by relatively low biological oxygen demand (BOD) and [1517].
high chemical oxygen demand (COD) values. Due to their complex Among AOPs, heterogeneous photocatalysis is considered to be
structure, most of dyes are recalcitrant [4] and possible carcino- one of the most emerging oxidation technology due to the lack of
genic, especially azo dyes through their aromatic amines resulted limitations in mass transfer, the ability to be carried out under
as degradation products [5,6]. All these characteristics make dyes ambient conditions (atmospheric oxygen is used as oxidant), and
to be ineffectively treated by biological methods. may lead to complete mineralization of organic carbon to CO2. The
In order to handle the dye removal from water, various methods most common semiconductor catalyst used in this process is
have been investigated. Among biodegradation, methods like titanium dioxide (TiO2) because it is inexpensive, wide-available,
non-toxic and water insoluble [18].
The oxidation process involving TiO2 consists of the absorption
* Corresponding author. Tel.: +40 256 403070; fax: +40 256 403060. of an energy photon that is equal to or grater than its band gap
E-mail address: [email protected] (R. Pode). width, and an electron (e) is promoted from the valence band (VB)

1876-1070/$ see front matter 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2012.09.006
 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278 271

to the conduction band (CB) generating an electron vacancy or hole company (Timisoara city, Romania). It was used without further
(h+) in the valence band. The electron and the hole can migrate to purication. The molecular structure of this dye is presented in
the catalysts surface, where they participate in redox reactions Fig. 1.
with different species adsorbed on the catalyst surface. Holes can The chemicals used for synthesis, i.e., titanium (IV) isoprop-
oxidize the dye and/or react with surface-bound H2O or HO to oxide (TTIP, 98%), ethanol, urea, hydrochloric acid (HCl), sodium
produce the hydroxyl radical (OH). The photo-generated electrons nitrate (NaNO3) and nitric acid (HNO3), were purchased from
could reduce the dye or react with electron acceptors, such as O2 ALDRICH Company. The dye solution pH was adjusted with 0.1 N
adsorbed on the catalyst surface or dissolved in water, which is H2SO4 and 0.1 N NaOH of analytical grade.
reduced to superoxide radical anion O2. The hydroxyl radicals Romanian zeolitic mineral from Mirsid, used as support for TiO2
(OH) and superoxide radical anion O2 are supposed to be the loading, was supplied by CEMACON Company, Romania. The
primary oxidizing species in the photocatalytic oxidation process mineral was powdered and sieved with a Multilab sieve shaker.
[18,19]. The process economics can be improved by using sunlight The diameter of grains size selected to carry out the experiments
instead of UV light for the semiconductor photo-excitation. ranged between 0.8 and 1.2 mm with the mass composition:
Methods of the TiO2 absorption spectrum shifting to the main 62.20% SiO2, 11.65% Al2O3, 1.30% Fe2O3, 3.74% CaO, 0.67% MgO,
part of solar spectrum (l > 360 nm) have been also investigated 3.30% K2O, 0.72% Na2O, 0.28% TiO2.
[2024]. It has been found that one of the most feasible and the
simplest is nitrogen doping [25,26], which is based on a changed 2.2. Preparation of nitrogen-doped TiO2
mechanism that prevents the electron/hole recombination on the
semiconductor. Nitrogen-doped TiO2 (N-doped TiO2) nanocrystals were syn-
There are several limitations to use bare TiO2 in photo- thesized by solgel method. An amount of ethanol (30 mL) was
catalytic reactors. The fast aggregation of TiO2 in suspension leads mixed under stirring with 5 mL of titanium isopropoxide (TiO 2
to effective surface area decrease and further its catalytic efciency precursor), which was added dropwisely. After a few minutes of
reduction. In addition, a ltration step after photocatalytic reaction stirring, distilled water was added. After pH adjusting at 8 using
is required because of TiO2 suspension. Attempts have been made ammonia solution, 0.0463 g urea (N precursor) was added. After
to immobilize TiO2 on different supports like glass beds [27], silica 1 h of continuous stirring the obtained material was ltered,
[28], activated carbon [29], biodegradable polymer [30] and washed several times and dried at 60 8C for 1 h. The resulted solid
zeolites [31]. was calcinated at 400 8C for 2 h.
Combining TiO2 with the adsorption properties of organic
molecules onto some adequate adsorbents, e.g., clays, zeolites with 2.3. Preparation of photocatalyst
large surface areas, a synergism is gained, which leads to an
enhancement of the reaction rate. Among the mentioned supports, The preparation of the chemically modied zeolite presumes
zeolites are supposed to provide an effective separation of two stages to reach acid form (H form) by using 2 M HCl solution
photogenerated electrons and holes due to the electric eld of and sodium form (Na form) with 2 M NaNO 3 solution for a more
their framework [19,32]. efcient ion-exchange. Consequently, Na forms of clinoptilolite are
This study aimed to obtain a hybrid materials based on the expected to remove easily other cations in ion-exchange applica-
natural zeolite modied with nitrogen-doped TiO2 (Z-TiO2-N) tions. For this reason, Na forms are the forms most frequently
suitable for photocatalysis application under VIS irradiation. prepared for clinoptilolite functionalization [33].
Reactive Yellow 125 azo dye was chosen a target pollutant, taking The hybrid material based on natural zeolite modied with
into account its negative impact potential on environment. To the nitrogen-doped TiO2 (Z-TiO2-N) was prepared by solid-state
best of our knowledge, there is no information about the obtaining reaction under microwave-assisted hydrothermal conditions.
and application of this kind of catalyst for dye degradation. The The microwave synthesis was performed in a microwave reaction
catalyst was characterized structurally and the photocatalytic system Multiwave 300, produced by Anton Paar at 2.45 GHz for a
activity was determined for RY 125 azo dye degradation under continuous power of 1000 W. The temperature measurements are
both UV and VIS irradiation. recorded with an IR sensor depending on autoclave solution
content. Therefore, an amount of 5 g of natural zeolite as Na-form
2. Materials and methods was mixed with 40 mL distilled water and N-doped TiO2
nanocrystals (2 wt%) under continuous stirring for 4 h. The
2.1. Chemicals obtained solutions were introduced into a Teon autoclave with
a 50% degree of fullness, for 30 min to 180 8C, under microwave
Reactive Yellow 125 (RY 125) (commercial grade) with a radiations. After autoclaving, the Z-TiO2-N hybrid material was
molecular weight of 681.5 g/mol was supplied by a local textile washed with distilled water and dried at 60 8C for 5 h.

Fig. 1. Molecular structure of Reactive Yellow 125 dye.

272 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278

2.4. Characterization of the photocatalyst

The crystalline structure of the prepared samples was

determined by X-ray diffraction (XRD) using PANalytical
XPertPRO MPD Difractometer with Cu tube. The morphological
characterization of the catalyst was carried out by scanning
electron microscopy (SEM) coupled with the energy dispersive
X-ray (EDX) analysis using Inspect S PANalytical model, and by
Fourier transform infrared spectrometry (FT-IR) using a JASCO
FT/IR-430 spectrometer. The light absorption properties of the
hybrid materials were studied by UVVIS diffuse reectance
(DRUVVIS) spectroscopy, performed under ambient conditions
using Lambda 950 Perkin Elmer in the wavelength ranged
between 200 and 430 nm. The blank board was used as the
reference.
Fig. 2. XRD spectrum for natural zeolite (a) and Z-TiO2-N photocatalyst (b); inset:
2.5. Photocatalytic experiments XRD spectrum of TiO2-N.

All experiments regarding adsorption and photocatalysis

processes were carried out under magnetic stirring at 20 8C into
a RS-1 photo-catalytic reactor (Heraeus, Germany), which consists TiO2-N. The peaks recorded at 2u ~ 108, 22.58, 308 correspond to
of a submerged lamp surrounded by a quartz shield. Solutions of the presence of clinoptilolite as major component of the natural
RY 125 dye at different concentrations (prepared from an initial zeolite [36], and also smaller amounts of illite, quartz and albite
stock solution of 10 g/L) were placed in the photoreactor and were identied [37]. The presence of anatase form of TiO2 was
irradiated with an UV light set between 280 and 360 nm when UV evidenced by the peak recorded at 2u = 25.28. No signicant
photocatalytic process was employed and a VIS light was set changes of the main peaks characteristics of the natural zeolite
between 460 and 510 nm in the case of VIS photocatalytic process, were noticed, which informed about the stability of the zeolite in
for 240 min. A system of water recirculation maintained a constant the hydrothermal synthesis conditions under microwave eld.
temperature of 20 8C for the whole period of photocatalytic Also, no phase transition of TiO2 occurred at the temperature of
experiments. 180 8C for 30 min.
The catalyst dose ranging between 0.5 and 2 g/L was placed into
400 mL RY 125 solution. Prior to irradiation, the suspension was 3.1.2. Scanning electron microscopy (SEM) and energy dispersive X-
stirred continuously in the dark for 30 min to reach the steady- ray (EDX) analysis results
state conditions. Samples were periodically collected from the The comparative SEM images and EDX spectra of the natural
reactor to evaluate the degree of RY 125 adsorption on the catalyst. zeolite modied as Na form, Z-TiO2-N photocatalyst and TiO2-N are
The concentration of the dye in the bulk solution at the end point of presented in Fig. 3.
the adsorption step was considered as the initial concentration The SEM image of natural zeolite shown in Fig. 3a presents the
value for the investigation of the photocatalytic process. At regular lamellar texture of clinoptilolite, according to the literature data
time intervals of irradiation, samples were collected and ltered [38] and EDX spectrum (inset of Fig. 3a) evidenced its major
through a Milipore lter (pore size of 0.45 mm) in order to elements. The results of morphological analysis for Z-TiO2-N
remove photocatalyst are in accordance with XRD, the lamelar structure of
the zeolite from the aqueous solution. The concentration of RY 125 zeolite being observed also from SEM image (Fig. 3b). No changes
solutions was measured with a Varian Cary 100 UV-VIS of the form and dimensions of TiO2 particles were noticed (see
spectrophotometer. Fig. 3c), which are distributed randomized and form cluster
The assessment of the photocatalysis performance was carried agglomerate groups on the surface and in site of zeolite channels,
out as discoloration, aromatic ring-opening and mineralization but not into the pores. EDX spectrum (inset of Fig. 3b) allowed
efciencies. The discoloration and aromatic ring-opening efcien- evidencing N and TiO2 on the natural zeolite. For comparison, SEM
cies were determined based on the absorbance recorded at 388 nm image and EDX spectrum of TiO2-N synthesized by solgel method
and 225 nm, respectively. The absorbances were selected from and used to functionalize the natural zeolite are shown in Fig. 3c.
UVVIS spectrum prole (see Section 3.2.1). Total organic carbon TiO2-N exhibited a very good stability during the hydrothermal
(TOC) parameter measured with Shimadzu TOC analyzer was used treatment under microwave eld, which allows obtaining Z-TiO2-
to assess the mineralization process. The experiments were N photocatalyst.
conducted at the pH values of 3, 6 and 9, respectively. The pH
of dye solutions was adjusted by adding diluted HCl and NaOH 3.1.3. FT-IR spectroscopy results
solutions (analytical grade), using an Inolab pH-meter. Fig. 4 presents the FT-IR spectrum of Z-TiO2-N in comparison
with Z-Na to evidence the possible bonds of TiO2 with the zeolite.
3. Results and discussion The stretching vibration of TiOSi and TiOAl groups is noticed
by the absorption band ranged from 945 to 905 cm1 [39]. The
3.1. Characterization of the catalyst similar tetrahedral loadings bands from 450 to 900 cm1 recorded
for both materials informed that the zeolite network was not
3.1.1. XRD analysis of the photocatalyst affected by the presence of TiO2-N.
In Fig. 2 are shown XRD spectra for natural zeolite (a) and Z-
TiO2-N photocatalyst (b) and for comparison, the inset presents 3.1.4. DRUVVIS spectroscopy
XRD spectrum for titanium dioxide doped with 2% N that was used DRUVVIS patterns are examined to determine the light
for photocatalyst synthesis. absorption quantication and absorption wavelength range
The specic peaks corresponding to anatase TiO2 form recorded correlated with band gap energy. The reectance was converted
at 2u ~ 25.28, 37.878, 48.018, 53.818 [34,35] were identied for
 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278 273

By comparative analysis of the absorption spectra for Z-Na and

Z-TiO2-N (Fig. 5), it can be noticed more intense absorption in UV
and a slight shifting of the absorption band to the visible range for
Z-TiO2-N, which allows to design it for further photocatalytic use
under UV and VIS irradiation.
The further experiments will be carried out to determine the
photocatalytic activity under UV and VIS irradiation of Z-TiO2-N for
the degradation of RY 125 dye solution.

3.2. UV photocatalytic degradation

3.2.1. UVVIS spectra prole of RY 125 dye solution

The UVVIS spectra proles of RY 125 solution containing Z-
TiO2-N catalyst recorded during UV irradiation are presented in
Fig. 6. The spectrum of the dye before irradiation exhibits two
major absorption peaks, due to the different units and groups
present in the dye molecule, which absorb the light in different
regions: one in the visible region at 388 nm and the second one at
225 nm in the UV region. Based on the literature data [24,40], the
absorption in the UV region can be attributed to aromatic (benzene
and naphthalene) rings, whereas the peak observed in the VIS
region can be assigned to azo linkage containing chromophore
group.
It can be noticed that after 30 min adsorption of the dye on the
catalyst, a small decrease in absorbance of both peaks appeared.
When irradiation is employed, a rapid discoloration of the dye
solution occurs, as well as a signicant decrease of the absorbance
recorded at 255 nm that is associated to aromatic ring-opening.
Both peaks became plat at the nal time of irradiation, respectively
at 240 min, although the remaining absorbance intensity can be
attributed to the organic intermediaries resulted during the
photocatalytic process. It has to be mentioned that the discolor-
ation and aromatic ring-opening of the dye solution does not
assume a complete azo-dye degradation and mineralization.
Monitoring total organic carbon (TOC) parameter is required to
assess the mineralization degree.

3.2.2. pH inuence
pH is one of the main factors that inuences the rate of
degradation of some organic compounds in the photocatalytic
process [40]. Fig. 6 presents the discoloration and aromatic ring-
opening efciencies of 100 mg/L RY 125 solution at different pH
values, i.e., pH 3, 6, and 9. It is obviously that the best discoloration
and aromatic ring-opening efciencies are reached at pH 3, which
was selected as optimum pH for further experiments.
First of all, pH inuence is related to the ionization state of the
catalyst surface including TiO2 and zeolite behavior in alkaline
and acidic media [3], as well as to that of the dye structure and
forms, e.g., acids and amines. pH changes can inuence the
adsorption of the dye molecules onto the catalyst surface, an
important step for the photocatalytic oxidation. Based on the
results of the prior step of adsorption for 30 min required to reach
the steady-state, it can be noticed a low extent of the dye is
adsorbed on the Z-TiO2-N surface, with a maximum of adsorption
degree at pH 3. 10.2 mg dye/g catalyst was adsorbed at pH 3 in
comparison with 1.5 mg dye/g catalyst at pHs 6 and 9. This can be
explained by the repulsion decrease between the RY 125 anionic
azo dye, which contains the sulphonate groups as anionic form
within the whole range of investigated pH and the negatively
Fig. 3. SEM images and EDX spectra (inset) of: Z-Na (a), Z-TiO2-N (b) and TiO2-N (c).
charged catalyst. This fact indicates that the photocatalytic
into absorbance using KubelkaMunk (Eq. (1)): reaction occurred both on the catalyst surface and through
reaction of the dye with the photogenerated holes or hydroxyl
1 R2 radicals in the bulk solution in the proximity of the catalyst
FR (1) surface.
2R
Also, taking into account the general mechanism of photo-
where R represents the reectance. catalytic oxidation process, the generation of hydroxyl radicals can
274 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278

Fig. 4. FT-IR spectra of: (a) Z-TiO2-N and (b) Z-Na.

be favored during the reaction of positive holes with hydroxyl

anions (OH).
From Fig. 7, it is noticed that at pH 3 and in comparison with
aromatic ring-opening, the discoloration process reaches its
maximum efciency value in a shorter time of irradiation, and
no further changes in efciency is observed after 150 min of
irradiation. At low pH value, the positive holes are considered the
major oxidative species that could form hydroxyl radicals (HO )
and interact with azo linkage, which is particularly susceptible to
be electrophilic attacked by hydroxyl radicals through decreasing
the electron densities at azo group [23]. Also, dissolved O2 itself can
accept conduction band electron and generate O2, which in turn
can be protonated to form HO2, favored by the acidic pH. At pH
values of 6 and 9, the efciency of aromatic ring-opening is
exceeded by the discoloration efciency only after 120 min
irradiation for pH 6, and after 180 min for pH 9. The discoloration
reaches its maximum efciency after the formation of some
intermediary species, which require a longer time of reaction to be
Fig. 5. DRUVVIS spectra of Z-Na (a) and Z-TiO2-N (b). further degraded. Also, the mineralization efciency reaches the

Fig. 6. Changes of UVVIS spectra of RY 125 dye solutions containing Z-TiO2-N Fig. 7. Efciencies of RY 125 solution discoloration and aromatic ring-opening at pH
catalyst during UV irradiation: (1) initial RY 125 solution; (2) after 30 min 3, 6 and 9 during UV irradiation; initial dye concentration is 100 mg/L; 1 g/L catalyst
adsorption; (3) after 50 min irradiation; (4) after 120 min irradiation; (5) after loading; reaction temperature 20 8C. & aromatic ring-opening, pH 3; &
240 min irradiation; 100 mg/L initial dye concentration; 1 g/L catalyst loading; decolorisation, pH 3; ~ aromatic ring-opening, pH 6; D decolorisation, pH 6;
reaction temperature 20 8C; solution pH = 3.
aromatic ring-opening, pH 9; o decolorisation, pH 9.
 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278 275

Table 1
TOC efciencies and mineralization coefcients for 100 mg/L RY 125 dye solution at
different pH values.

pH value hTOC (%) hTOC/h225 nm

3 35.79 0.59
6 20.18 0.43
9 12.77 0.29

highest value of 35.79% at pH 3 compared to 20.18% at pH 6 and

respective, 12.77% at pH 9 (see Table 1).
The effective mineralization performance was assessed as the
ratio between the TOC and the aromatic ring-opening efciency
(hTOC/h225 nm). The value of this ratio close to 1 indicates that the
effective mineralization was achieved. In our study, the highest
ratio value of 0.59 is obtained for pH 3, which informed that the Fig. 9. Inuence of initial dye concentration on discoloration and aromatic ring-
mineralization process is not effectively under the studied opening efciency under UV irradiation; 1 g/L catalyst loading; reaction
conditions. temperature 20 8C; solution pH = 3; & aromatic ring-opening, 100 mg/L
RY125; & decolorisation, 100 mg/L RY125; ~ aromatic ring-opening, 50 mg/
3.2.3. Effect of the catalyst dose L RY125; D decolorisation, 50 mg/L RY125; aromatic ring-opening, 25 mg/L
In order to determine the optimum catalyst loading, the RY125; o decolorisation, 25 mg/L RY125.

degradation of RY 125 dye was investigated using different

catalyst concentrations in the range of 0.52 g/L. The results are 3.2.4. Effect of the initial dye concentration
presented in Fig. 8, and it can be observed that increasing the The photodegradation efciency depends on the initial dye
catalyst dose from 0.5 to 2 g/L lead to increasing the dye concentration based on two main aspects. The amount of dye
discoloration efciency from 70.75% to 89.62%. This may be adsorbed on the catalytic surface increases with the dye
attributed to the enhanced generation of HO from the photo- concentration in relation with the available surface, which
catalyst surface based on increasing the photocatalyst amount in enhances the catalytic efciency of the photocatalyst. On the
the reaction solution. It must be noticed that the same nal other hand, higher concentration of the dye affects negatively the
discoloration efciency after 240 min irradiation was reached for UV light penetrability in the dye solution. Also, the dye molecules
1 and 2 g/L photocatalyst, and the dye discoloration rate was may absorb a signicant amount of light required for the catalyst
higher for 1 g/L photocatalyst. surface irradiation, which diminishes the catalytic activity [41].
A similar behavior is noticed in the case of aromatic ring- The inuence of various initial dye concentrations on the
opening efciency, where the efciency increases with the photocatalytic discoloration and degradation has been investigat-
catalyst dose increasing up to 1 g/L. At higher catalyst dose of ed in the concentration range of 25100 mg/L RY 125 dye. The
2 g/L the efciency decreases to 63.11% versus 77.92% reached results are presented in Fig. 9, which are in accordance with other
at 1 g/L photocatalyst. This behavior might be due to the literature data [3,4]. The increasing dye concentration leads to
enhancement of light reectance by the catalyst and decreas- decreasing degradation efciency.
ing the light penetration [4]. A similar behavior under the Also, TOC monitoring for all initial dye concentrations showed
condition of the catalyst excess was reported in other studies that the best mineralization efciency is obtained for 25 mg/L RY
[18]. Based on these results, the catalyst dose of 1 g/L was 125 (Table 2).
chosen as optimum for an efcient photodegradation of RY 125 Based on the values of the ratio between mineralization and
dye solution. degradation efciency, the ratio value of 0.83 informs about an
effective mineralization process in the case of low dye concentra-
tion, in comparison with higher dye concentrations.

3.2.5. Photodegradation kinetics

The dependencies of the dye aromatic ring opening, discolor-
ation and mineralization rate on the irradiation time have been
described by the LangmuirHinshelwood kinetic model [42]
described by Eq. (2), which can be simplied to a pseudo-rst-
order equation, as presented in Eq. (3):

dC kKC (2)
r dt 1 KC

.
C0
ln kKt kapp t (3)
Ct

Table 2
TOC efciencies and mineralization coefcients for different initial RY 125 dye
concentrations.
Fig. 8. Inuence of catalyst dose on discoloration and aromatic ring-opening
efciency under UV irradiation; 50 mg/L initial RY 125 dye concentration; reaction Initial RY 125 dye concentration (mg/L) hTOC (%) hTOC/h225 nm
temperature 20 8C; solution pH = 3; & aromatic ring-opening, 2 g Z-TiO 2-N/L; &
100 35.79 0.59
decolorisation, 2 g Z-TiO 2-N/L; ~ aromatic ring-opening, 1 g Z-TiO 2-N/L; D
50 48.00 0.61
decolorisation, 1 g Z-TiO2-N/L; aromatic ring-opening, 0.5 g Z-TiO2-N/L; o
25 76.29 0.83

decolorisation, 0.5 g Z-TiO2-N/L.

276 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278

Fig. 11. The photodegradation efciencies of RY 125 dye solution under UV and VIS
irradiation. & aromatic ring-opening by UV irradiation; & decolorisation by
UV irradiation; aromatic ring-opening by VIS irradiation; o decolorisation by
VIS irradiation.

Fig. 10. The pseudo-rst-order kinetics of 25 mg/L RY 125 photodegradation on Z-

TiO2-N, pH = 3. Fig. 11 illustrates the photodegradation efciency under VIS in
comparison with UV light, and it can be observed that the results
are comparable.
where r is the rate of dye degradation, discoloration and For an initial dye concentration of 25 mg/L, at pH 3 after
mineralization (mg/L/min), C0 is the initial dye concentration 240 min irradiation time, the aromatic-ring opening efciency of
(mg/L), Ct is the concentration of the dye at time t (mg/L), t is the 91.64% and the discoloration efciency of 91.60% were reached
irradiation time (min), k is the reaction rate constant (min1) and under UV irradiation, and the aromatic-ring opening efciency of
kapp is the apparent rate constant (min1). 85.91% and the discoloration efciency of 94.85% were achieved
The apparent rate constant for each dye degradation, discolor- under VIS irradiation.
ation and mineralization, kapp, was calculated from the intercept of The photocatalytic activity of the Z-TiO2-N hybrid material was
the plot of ln(C0/Ct) against time, t (Fig. 10). compared with Z-Na and TiO2-N for 25 mg/L RY 125 dye solution
The kinetics results presented in Tables 3 and 4 showed that the in terms of degradation efciency, and the results are gathered in
rates of the aromatic ring-opening, discoloration and mineraliza- Table 5. It can be noticed a synergic effect of the hybrid material for
tion processes depend on pH and dye initial concentration. the photocatalytic degradation of RY 125 dye solution taking into
For all the experiments, the discoloration occurred the fastest, account the content of 2 wt%, TiO2.
and the mineralization process was the slowest. Though, the rate of Though, a signicant difference between the two irradiation
the mineralization process was better for low dye concentration domains was noticed for the photodegradation rate. The dye
than for higher dye concentrations. photodegradation process under UV irradiation occurred faster
than VIS irradiation, the rate constants are gathered in Table 6.
3.3. VIS photocatalytic degradation Degradation efciency under VIS light is achieved not only by
the catalyst absorption band shifting into the visible region,
Because ultraviolet photons are limited in both solar light and capable to generate pairs of electronsholes, which can participate
indoor illumination, the VIS irradiation was performed in order to directly in the photocatalytic reactions, but also by the so-called
assess the effectiveness of the Z-TiO2-N in the photocatalytic photosensitized oxidation mechanism, which provides a differ-
degradation of RY 125 dye solution. ent pathway versus that involved under UV light irradiation
[19,43]. The photocatalytic oxidation is superior to the photo-
sensitizing oxidation mechanism, but the later can help in
improving the overall efciency and can also provide a synergism
Table 3 effect when VIS light is involved. This aspect is proved by the
Apparent rate constants for discoloration, aromatic ring-opening and mineraliza-
tion (100 mg/L RY 125 dye solution).

pH kapp,225 nm R2 kapp,388 nm R2 kapp,TOC R2 Table 5

value (min 1) (min 1) (min 1) Degradation and discoloration efciencies for different types of catalysts.

3 0.0053 0.9844 0.0110 0.9894 0.0015 0.9872 Catalyst type h225 nm (%) h388 nm (%)
6 0.0043 0.9689 0.0044 0.9914 0.0011 0.9634
TiO2-N 92.23 98.10
9 0.0038 0.9823 0.0025 0.9973 0.0002 0.9956
Z-TiO2-N 85.91 94.85
Z-Na 35.85 36.03
Table 4
Apparent rate constants for discoloration, aromatic ring-opening and mineraliza-
tion (pH = 3). Table 6
2
Apparent rate constants for UV and VIS degradation processes at pH 3 for 25 mg/L
RY initial kapp,225 nm R2 k app,388 nm R2 kapp,TOC R RY 125 dye solution.
concentration (min 1) (min 1) (min 1)
(mg/L) Irradiation kapp,225 nm R2 kapp,388 nm R2
type (min 1) (min 1)
100 0.0053 0.9844 0.0110 0.9894 0.0015 0.9872
50 0.0078 0.9851 0.0164 0.9917 0.0023 0.9761 UV 0.0196 0.9896 0.0239 0.9410
25 0.0196 0.9896 0.0239 0.9410 0.0060 0.9785 VIS 0.0071 0.9852 0.0126 0.9385
 E.C. Ilinoiu et al. / Journal of the Taiwan Institute of Chemical Engineers 44 (2013) 270278 277

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