Journal of Hazardous Materials 288 (2015) 158–167

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

The layered double hydroxide route to Bi–Zn co-doped TiO2 with high
photocatalytic activity under visible light
Bahia Benalioua a , Meriem Mansour a , Abdelhadi Bentouami a,∗ , Bruno Boury b,∗ ,
El Hadj Elandaloussi a
a
Laboratoire de Valorisation des Matériaux, Université de Mostaganem BP 227, Mostaganem 27000 Algeria
b
ICG–CMOS–UMR 5253, Université Montpellier 2, Place Eugène Bataillon CC 1702, 34095 Montpellier Cedex 05, France

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• The Synthesis of a new and efficient

photocatalyst by a LDH pathway is
described.
• The obtained photocatalyst is based
on TiO2 doped with association of Zn
and Bi.
• The efficiency of this photocatalyst is
much higher than that of the bench-
mark P25.
• This photocatalyst exhibits a high sta-
bility after five cycles.

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a co-doped Bi–Zn–TiO2 photocatalist is synthesized by an original synthesis route of layered
Received 20 November 2014 double hydroxide followed by heat treatment at 670 ◦ C. After characterization the photocatalyst efficiency
Received in revised form 7 January 2015 is estimated by the photo-discoloration of an anionic dye (indigo carmine) under visible light and compare
Accepted 4 February 2015
to TiO2 –P25 as reference material. In this new photocatalyst, anatase and ZnO wurtzite are the only iden-
Available online 7 February 2015
tified crystalline phase, rutile and Bi2 O3 being undetected. Moreover, the binding energy of Bi determined
(XPS analysis) is different from the one of Bi in Bi2 O3 . Compared to TiO2 –P25, the absorption is red shifted
Keywords:
(UV–vis DRS) and the Bi–Zn–TiO2 photocatalyst showed sorption capacity toward indigo carmine higher
Photocatalyst
LDH than that TiO2 –P25. The kinetics of the photo-discoloration is faster with Bi–Zn–TiO2 than with TiO2 –P25.
Bi–Zn–TiO2 Indeed, a complete discoloration is obtained after 70 min and 120 min in the presence of Bi–Zn–TiO2 and
Visible Light TiO2 –P25 respectively. The identification of the responsible species on photo-discoloration was carried
Indigo Carmine out in the presence of different scavengers. The study showed that the first responsible is h+ specie with
a moderate contribution of superoxide anion radical and a minor contribution of the hydroxyl radical.
The material showed high stability after five uses with the same rate of photo-discoloration.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction intention of many research groups as a method for the removal

Heterogeneous photocatalysis is a technique belonging to the
class of advanced oxidation processes (AOPs) which attracted the
∗ Corresponding author. Tel.: +213 771 90 61 44.
E-mail address: bentouami@gmail.com (A. Bentouami).
of refractory pollutants from industrial wastewaters. This method
has the ability to convert refractory pollutants into harmless end
products such as CO2 , H2 O and mineral acids [1–3].
The principle of heterogeneous photocatalysis using semicon-
ducting materials is based on the production of electron-hole
pairs at their surfaces upon UV irradiation. These species react
with physisorbed molecules such as pollutants, oxygen, water, and

http://dx.doi.org/10.1016/j.jhazmat.2015.02.013
0304-3894/© 2015 Elsevier B.V. All rights reserved.
 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167
•
hydroxyl ions to produce radicals such as O2 − and hydroxyl (• OH).
These radicals known to be strong oxidants, they contribute to
the oxidation and mineralization of organic pollutants [1–3]. Many
studies have shown the efficiency of TiO2 , and Evonik-Degussa P25
is still considered as benchmark in this field [1–3]. The major draw-
back is the wide band gap (3.23 eV for anatase phase, excitation
wavelength < 387.5 nm, less than 5% of solar light) that limits its
application under visible light [4]. To overcome this limit, TiO2 is
combined with either metal nanoparticles [5] or carbon nanostruc-
tures (graphene, CNT) [6] or by doping with metal and non-metal
ions [7–9] the main advantage of the latter is to reduce the energy
of the band gap, creating energy levels to promote electronic
excitation under visible light illumination and/or reduce the recom-
bination of electron-hole pairs. Many solar experiments [10–12]
were performed by means of sunbeams as irradiation source for
the degradation of several pollutants when their concentrations
are low.
The first work on the extension of the absorption of TiO2 from UV
to visible region is dating back to the 60 s and focused on the doping
with noble metals [13–15] such as platinum [16], gold [17,18] and
silver [19,20].
The choice of noble metals for doping TiO2 remains expensive.
Recently, the doping of TiO2 with metals (Ce, Mn, Fe, Co, Ni, Cu, Zn,
Bi, La) [21–23] or non-metals (N, C, S, B, P or F) [24–27] has been
widely reported. To further improve the photocatalytic activity,
several authors have reported the co-doping of TiO2 with metal and
non-metal like carbon (C–Bi–TiO2 [28,29]), nitrogen (N–Bi–TiO2
[30], N–Zn–TiO2 ) [31,32], Sulphur (S–Bi–TiO2 [33] S–Zn–TiO2 [34])
or Boron (B–Bi–TiO2 [35]). Doping TiO2 by the association of two or
more transition metals was not widely explored other than Bi–M
Co-doped TiO2 (M Y, [36], Fe or Co, [37]) or Zn–M co-doped TiO2
(M Sn, [38] V, [39] La, [40] Fe [41]).
We found interesting to target the synthesis and properties of
Bi–Zn co-doped TiO2 that has never been reported so far to the best
of our knowledge. Although, the doping of TiO2 by one of these
two metals is known and proven to improve the photocatalytic
activity of TiO2 . However, the use of Bi and Zn together has never
been reported. To synthesize this material, we used the LDH route
synthesis, a process less common than sol-gel but already known
as an efficient route for doped-TiO2 [42–51]. Bi–Zn co-doped TiO2
exhibits a high photocatalytic activity under visible light. The latter
is demonstrated by the comparison of its photocatalytic activity
with commercial TiO2 –P25 in the degradation of indigo carmine, a
very resistant dye to photolysis under UV-B, UV-A and visible light.
2. Experimental
2.1. Preparation of Materials
All chemicals are of analytical grade and are directly used
as received. A typical synthetic procedure is as follows: solu-
tion A was made by dilution of 12 mL of TiCl4 in 30 mL of
aqueous HCl (32% wt), solution B: 5.36 g of Bi(NO3 )3 5H2 O dis-
solved in 15 mL of nitric acid, solution C: Zn(CH3 COO)2 ×2H2 O
(31.57 g) was dissolved in 200 mL of aqueous 0.1 M CH3 COOH
and solution D: urea (80.04 g) was dissolved in 200 mL of H2 O.
The molar ratios of Ti4+ /Bi3+ = 9.65, (Bi3+ + Zn2+ )/Ti4+ = 1.45 and
urea/(Ti4+ + Bi3+ + Zn2+ ) = 5.09, assuming a theoretical composition
for the metal: Ti1 Zn0.75 Bi0.1 . Solutions A, B and C were mixed in
a one-liter flask in which solution D was added drop wise. The
resulting transparent mixture was heated under gentle reflux with
vigorous stirring for 96 h. The obtained white material was sep-
arated by vacuum filtration, washed several times with double
distilled water until negative chloride test with AgNO3 , dried at
80 ◦ C for 24 h and finally heat-treated in a muffle furnace at 670 ◦ C
159
TiCl4 in HCl (32%) Bi(NO3)35H2 in HNO3(5%) ZnAc2O in 0.1 M AcOH
Solution A Solution B Solution C
Urea aqueous solution
Drop wise
Solution D
Reflux at 90°/96H
White suspension
1-Filtration 3-Drying
2-Washing
White powder
Bi-Zn-Ti LDH
4-Calcination
Pale yellow powder
Bi-Zn-TiO2
Scheme 1. Schematic diagram for the Bi–Zn–TiO2 by LDH synthesis route.
for 2 h. Scheme 1 summarizes the general approach of this prepa-
ration.
2.2. Characterization of the prepared materials
Powder X-ray diffraction data were collected with monochro-
´ at 40 kV and 30 mA using a
matic Cu K␣1 radiation ( = 1.54056 Å)
XPERT PRO PHILIPS diffractometer. Thermogravimetric (TG) analy-
ses were performed with a Netzsch TGA 409 PC thermo balance
with a heating rate of 20 ◦ C/min from 25 to 900 ◦ C. The N2
adsorption–desorption experiments at 77 K were carried out using
a Micromeritics Tristar 3000. Samples were first treated to desorp-
tion at reduced pressure (< 10−2 Torr) at 150 ◦ C for five hours. The
specific surface area (SSa) was calculated using the BET method
based on the adsorption isotherm and pore size distribution was
calculated using the BJH method on desorption isotherm branch.
The morphologies of the prepared materials were observed by
scan-electron microscope (SEM) on HITACHI S-4800. The diffuse
reflectance spectra (DRS) of the powder samples were recorded
in the region of 200–1000 nm on a UV–visible spectrophotome-
ter (JASCO V670) equipped with an integrating sphere (JASCO PIN
757) using BaSO4 as reference. X-ray photoelectron spectroscopy
(XPS) data were obtained using an ESCALAB 250 Thermo Elec-
tron spectrometer with monochromatic source of Al K␣ (1486.6 eV)
radiation. The binding energies were referenced to the Ti2p of TiO2
at 458.9 eV.
2.3. Adsorption study in the absence of light
The adsorption kinetics experiments were performed in a
500 mL open Pyrex cell in the absence of light. This study was car-
ried out in the presence of Bi–Zn–TiO2 or commercial TiO2 –P25
with 1 g L−1 of solid/solution ratio and initial dye concentration
of 16 mg L−1 at natural pH 6.1. Aliquots of the suspension were
taken at regular times and centrifuged. The dye concentration in
the supernatants was determined at 610 nm by UV–visible spec-
trophotometer HACH DR/4000U.
2.4. Photocatalytic activity study
The photocatalytic activity of Bi–Zn–TiO2 was studied in
comparison with the commercial TiO2 –P25 Degussa. The photo-
discoloration kinetics studies were undertaken with initial
160 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167

4
6x10 102
120
λ=659.9 nm
2
I=114.8 µW/cm 100
4
(c) 98
5x10 105
96
4 90 94

Weight loss (%)

4x10

Irradiance µW/cm
92
75 90
ADC counts

4
3x10 20.5 %
88
60
86
4
2x10 45 84
82
1x10
4 30 80

2
78 3.1 %
15
76

°C
0
1.4%

0
74

12
0

C
0°
240 300 360 420 480 540 600 660 720 780 840 900 960 72

67
70
Wavelength (nm) 70 140 210 280 350 420 490 560 630 700 770 840

Fig. 1. Emission spectrum of visible lamp and its irradiance distribution. T (°C)

Fig. 2. TGA curve of Bi–Zn–Ti LDH in air.

concentration ranging from 10 to 24 mg L−1 of indigo carmine aque-
ous solution at natural pH 6.1 and with 1 g L−1 of solid/solution
ratio. A 500 mL open Pyrex cylindrical beaker was used as photo- lyst was separated by centrifugation, dried at 110 ◦ C during two
reactor to provide photocatalytic degradation experiments of hours, not crunched and then added to a fresh 16 mg L−1 solution
200 mL of dye solution under visible light irradiation. The pH was of dye in similar conditions as above. The process was repeated four
measured at the beginning but not adjusted during the test. No times.
oxygenation was introduced in the solution. The photo-reactor was
placed in cooled bath with circulating water in order to keep the
3. Results and discussion
room temperature stable. Aliquots were taken, centrifuged and the
dye concentration in the supernatants was determined as above.
Generally, doping can be done by simultaneous co-precipitation
The calibration curve was established on indigo carmine solutions
of titanium and the dopant with an alkaline solution (NaOH,
ranging from 0 to 24 mg L−1 at natural pH 6.1.
NH4 OH). In the present case, the first step of the synthesis is the
A 500 Watts tungsten lamp (TUNGSRAM trademark) without
preparation of the Bi–Zn–Ti lamellar double hydroxide material
any cut-off filter was used as visible light source which emits
obtained by co-precipitation of the metallic hydroxides at 90 ◦ C
more than 400 nm. The irradiance of a 500 W tungsten lamp was
during 96 h to form the lamellar double hydroxide material. Dif-
measured by the spectrometer AvaSpec-2048 equipped with a
ferent molar ratios of Ti(IV)/Zn(II)/Bi(III) were investigated, but we
symmetrical Czerny–Turner monochromator coupled to a CCD
only present here the material that lead to the best photocatalytic
detector with 2048 pixels. The distance between the lamp and the
activity, namely, Ti1 Zn0.75 Bi0.1 . In this process, urea was introduced
detector was 10 cm. The spectrometer is connected via an opti-
as reactant to allow a better control of the precipitation by control-
cal fiber (FC-UV-400-2) to a diaphragm (FOA-Inline) for reducing
ling the pH evolution upon decomposition into cyanide leading to
the intensity of the luminous flux received by the detector. Mea-
carbonate and ammonia [54]. Then, the resulting Bi–Zn–Ti LDH is
surements are acquired by the software Avasoft 7.0. The maximum
transformed into the doped Bi–Zn–TiO2 upon direct calcination at
intensity of irradiance measured was 114.8 ␮W/cm2 at 659.9 nm
670 ◦ C in muffle furnace. This temperature was selected on the basis
(the lamp spectrum distribution is presented in Fig. 1). The distance
of the TGA results and also the results of the photocatalytic tests
between the lamp and the liquid surface was 17 cm.
show that this temperature is determining. The calcination lead to
two important changes: a weight loss and a variation of the color of
2.5. Active species identification the solid which turns from white for Bi–Zn–Ti LDH to pale yellow
for Bi–Zn–TiO2 .
In order to identify the active species in the photo-degradation
of indigo carmine under visible light, radical-trapping study were
3.1. TG analysis
conducted by using four scavengers: ascorbic acid (2 mmol L−1 )
as a superoxide anion radical scavenger, ethanol (2 mmol L−1 )
The thermogravimetric plot (Fig. 2) shows three main weight
as a HO• radical scavenger, disodium ethylenediaminetetraac-
losses: up to 110 ◦ C (20.5%, loss of adsorbed water) from 110 to
etate (Na2 EDTA, 1 mmol L−1 ) as a hole scavenger) and AgNO3
660 ◦ C (3.1%, dehydroxylation), above 660 ◦ C (1.4%, possible final
(1 mmol L−1 ) as an electron scavenger [52,53]. The experiments
dehydroxylation and/or phase changes).
were carried out with 100 mg of Bi–Zn–TiO2 and 100 mL of dye
solution with initial concentration of 16 mg L−1 at natural pH 6.1.
Aliquots were collected, centrifuged and the dye concentration in 3.2. Surface morphology analysis
the supernatants was determined as above.
Before any thermal treatment, thin lamellar structures typical of
2.6. Reusability study hydrotalcite and with different sizes are observed by SEM analysis
of Bi–Zn–Ti LDH (Fig. 3a–c). However, the most part of the solid is
The reusability experiments of Bi–Zn–TiO2 in the photo- homogeneous and made of nanoparticles with ∅<30 nm, ascribed to
discoloration of indigo carmine solution was carried out with initial TiO2 in agreement with DRX analysis. After calcination at 670 ◦ C, the
dye concentration of 16 mg L−1 , at pH 6.1, and with a solid/solution material Bi–Zn–TiO2 is also very homogeneous, no different type of
ratio of 1 g L−1 . After total discoloration was achieved by exposing particles can be distinguished and the average size of the particles is
the mixture to visible light irradiation for 70 min, the photocata- lower than 60 nm; no lamellar structures being observed (Fig. 3d–f)
 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167 161

Fig. 3. SEM images of -Bi–Zn–Ti LDH (a, b and c) and of Bi–Zn–TiO2 (d–f).

Table 1
(006)
(003)

Textural properties of samples obtained from adsorption–desorption of N2 at 77 K.

(LDH(Bi-Zn-Ti))
Samples SBET (m2 g−1 ) Dmoy (nm) V pore (cm3 g−1 )
(012)

A
N.I Bi–Zn– Ti (LDH) 246.1 8.2 0.431
(Bi-Zn-TiO2)
Bi–Zn–TiO2 45.7 22.9 0.328
TiO2 –P25 49.3 8.3 0.09
(018)

(110)

A AA A
N.I N.I
(113)

N.I
A
: ZnO A A
of two peaks, d006 normally at 23.6 Å of LDH and d101 of anatase
A
A: Anatase A
(JCPDSN◦ 21–1272) at 25.5◦ . The presence of the latter can also
R: Rutile N.I
N.I: Not Identfied explain less intense peaks in Bi–Zn–Ti LDH attributed to anatase
phase of TiO2 compared to diffractogram of TiO2 –P25. However,
A some signals of Bi–Zn–Ti LDH pattern could not be attributed. For
(TiO2 P25) R A AA
R R A
A the Bi–Zn–TiO2 the following were identified: anatase (tetragonal
phase, space group 41/amd) (JCPDSN◦ 21–1272) and ZnO wurtzite
5 10 15 20 25 30 35 40 45 50 55 60 65 70 (hexagonal phase, space group P63mc) (JCPDS card 36–1451), no
2θ (degree) Bi2 O3 phase was identified, either because it is not present or
because of the lack of crystallinity.
Fig. 4. XRD patterns of Bi–Zn–Ti LDH, Bi–Zn–TiO2 and TiO2 –P25 materials.

3.4. Surface area analysis.

3.3. XRD analysis
Fig. 5 shows adsorption/desorption isothermal of N2 which
The powder X-ray diffraction patterns (Fig. 4) shows peaks at belongs to the type IV isotherm category characterized by the hys-
7.379 Å (d003 ), 3.440 Å (d006 ), 2.675 Å (d012 ) and the reflections teresis loop. The values of SSa, pore size and pore volume are
of (110) and (113) which can be indexed to typical hydrotalcite given in Table 1. Before thermal treatment the Bi–Zn–Ti LDH mate-
materials reported by several authors [43–51,54–59], however, the rial is mesoporous with a narrow pore distribution centered at
broadness of the peak at 7.379 Å (d003 ) indicates the low crys- 8.2 nm (the inset of Fig. 5), mesoporous volume (0.431 cm3 g−1 )
tallinity of the Bi–Zn–Ti LDH. Moreover, the high intensity of the and specific surface area around 245 m2 g−1 are a pretty high values
broad peak at 3.440 (25.87◦ ) can be explained by the superposition compared to what is observed for LDHs in general.
162 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167

0,012 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
120 4
300 0,010
Bi-Zn-Ti (LDH) 110 (a) 394 nm
0,008
Bi-Zn-Ti (LDH)
TiO2 P25
Bi-Zn-TiO 100 3
250
STP)

0,006
90
0,004 Bi-Zn-TiO2 80 2

Reflectance (%)
200

Differential
-1

0,002 70
Volume ads (cm³g

0,000 60 1
150 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
50
Pore size (Å)
40 0
100 30
20 -1
50 10
0 -2
0 120 3

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 110 (b) 402 nm
100
Relative Pressure (P/P0)
90 2

80 Bi-Zn-TiO2
Fig. 5. N2 adsorption–desorption isotherms of Bi–Zn–Ti LDH and Bi–Zn–TiO2 . Inset:

Reflectance (%)

Differential
Pore-size distributions of the as-prepared materials. 70
60 1

The thermally treated Bi–Zn-TiO2 is a mesoporous material dis- 50

tribution centered at 23 nm (the inset of Fig. 5) with a much lower 40

SSa ≈ (45 m2 g−1 ), and with a good mesoporous volume 0.328 30 0

(cm3 g−1 ). At first, the mesoporosity is ascribed to inter-particle 20

space between agglomerates particles [57]. It is known that the 10
heat treatment of the LDH results not only in changes in their struc- 0 -1
200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
ture but also in their specific surface areas and pore development
[58,59]. Indeed, the elimination of carbonate can lead to an increase Wavelength (nm)
of the SSa, but above 350–400 ◦ C, the transformation of the hydro-
Fig. 6. UV–vis DRS and their derivatives of samples (a) TiO2 –P25 and (b) Bi–Zn–TiO2 .
talcite structure into the oxide one, especially for Zn and part of
Ti, result in an important decrease of the SSa, similar to the one of
TiO2 –P25 [60]. 4f5/2 at 166.8 eV and 164.9 eV (at 163.9 eV for pure Bi2 O3 ). These
data confirmed the absence of crystallized Bi2 O3 phase suggested
3.5. UV–vis DRS analysis by DRX analysis. The positive shift in binding energies values com-
pared to those of pure Bi2 O3 could be attributed to some valence
Fig. 6a and b show the UV–vis diffuse reflectance spectra and states higher than Bi3+ , as observed and proposed by Shamaila et al.
their derivatives of TiO2 –P25 and Bi–Zn-TiO2 respectively. The [64]. This strengthens the unusual character of the environment
maximum of two derivatives plots correspond to wavelengths of of Bi in this material at this temperature. On the other hand, the
402 nm for Bi–Zn–TiO2 and of 394 nm for TiO2 –P25. The band gap Bi–O bound lead to a contribution in the XPS spectrum for O1s at
energy Eg of Bi–Zn–TiO2 and TiO2 –P25 were determined from the 531.4 eV.
maximum of their derivatives and their values are 3.04 and 3.15 eV,
respectively. From this values and Fig. 6-b, the Bi–Zn–TiO2 exhibits
3.7. Adsorption study in the absence of light
enhanced absorption in visible light region (centred at 402 nm) in
comparison with TiO2 –P25 (centred at 394 nm).
The amounts of indigo carmine adsorbed per gram of solid (Qt )
versus contact time is presented in Fig. 8. The equilibrium time of
3.6. XPS analysis
indigo carmine adsorption on both of Bi–Zn–TiO2 and TiO2 –P25
was found to be 30 min. The maximum amount of indigo carmine
A classical TiO2 spectrum is evidenced by XPS (Fig. 7) with sig-
adsorbed was 6 and 10 m g g−1 on TiO2 –P25 and Bi–Zn–TiO2 respec-
nals of Ti 2p3/2 at 459 eV and Ti 2p1/2 at 465 eV. This is confirmed
tively. Those values are very low but the higher adsorbed capacity
by a contribution at 530.4 eV to the XPS spectrum for O1s. For Zn,
of Bi–Zn–TiO2 (10 m g g−1 ) can be ascribed to its higher mesoporous
beside the signal for the Zn 2p1/2 at 1044.6 eV, two contributions
volume (0.328 cm3 g−1 instead of 0.09 cm3 g−1 for TiO2 –P25).
seem present for Zn 2p3/2 : at 1023 eV and 1021 eV. The latter is
composed of a ZnO phase and is confirmed by a contribution at
533 eV to the XPS spectrum of O1s. However, the contribution at 3.8. Photocatalytic discoloration study
1023 eV indicates a different environment for the Zn2+ atoms, the
positive shift suggesting a decrease of the electron density around Dye solution discoloration test was used here to evaluate the
Zn atom probably in relation with the other metal combined with photocatalytic activity of the material in the visible and to compare
oxygen, namely Ti and Bi, eventually due to Zn–O–Ti or Zn–O–Bi it with P25 and using indigo carmine as a convenient dye. Although
binding. this test allows a first evaluation and comparison, one should be
Concerning the environment of bismuth, two different environ- aware of the possible limitations of such test [65].
ment oxidation states can be identified from the signal of the Bi Fig. 9-a and 9-b show the plots of Ct /C0 ratio of dye pho-
4f7/2 at 159.6 and 161.6 eV, however, they are too positively shifted tocatalytic discoloration versus contact time in the presence of
and this cannot be in agreement with a well-defined Bi2 O3 phase TiO2 –P25 and Bi–Zn–TiO2 respectively. In the absence of photo-
(at 158.6 eV for pure Bi2 O3 [61–63]). This is also observed for Bi catalyst (Fig. 9), indigo carmine dye is very resistant to photolysis
 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167 163

(a) 459 12000 (b) Bi4f7/2 A

18000 Ti2p3/2 Bi4f5/2 A 159.6
16000 164.9
10000
14000
8000
12000 Ti2p1/2
Counts/s

465

Counts/s
Bi4f7/2 B
10000 6000 Bi4f5/2 B
161.6
166.8
8000
4000
6000

4000 2000

2000
475 470 465 460 455 450 445 175 173 170
170 168 165
165 163 160
160 158 155
155 153
Binding Energy (eV) Binding Energy (eV)

(c) O1s B Zn2p3/2 A

O1s A 26000 (d)
0.5 1021.7
53

53
0.

24000
4

25000
22000 Zn2p1/2
1044.6
20000 20000
Counts/s

O1s C Zn2p3/2 B
Counts/s

18000 1023.3
53

15000
1.

O1s D
6

16000
53

10000
3

14000

12000
5000
545 543 540 538 535 533 530 528 525 523 520 1060 1050 1040 1030 1020 1010
Binding Energy (eV) Binding Energy (eV)

Fig. 7. XPS spectra of (a) Ti2p, (b) Bi4f, (c) O1s and (d) Zn2p in Bi–Zn–TiO2 .

under visible light irradiation even at concentration as low as
5 mg L−1 as previously studied [66].
The discoloration time increases with increasing initial dye con-
centration, for example at 16 mg L−1 as initial dye concentration at
natural pH 6.1, the complete discoloration time was 120 min (Fig. 9-
a) and 70 min (Fig. 9-b) for TiO2 –P25 and Bi–Zn–TiO2 , respectively.
Fig. 9-c and 9-d show a decrease of absorption intensity of
indigo carmine in UV–vis spectra after 120 min and 70 min as
time of photo-degradation under visible light with TiO2 –P25 and
Bi–Zn–TiO2 , respectively.

10 3.8.1. Kinetic modelling

9
The kinetic of photocatalytic degradation rate of most of organic
8
species can be described by the pseudo-first order model which can
7 be used on linear form presented by the following equation.
6  
Ci,
Qt(mg.g )

Ln = Kt (1)
-1

5
Ct
4
3 Where, kapp (min−1 ) is the apparent rate constant, Ci,corr (initial
TiO2-P25 dye concentration corrected after adsorption in dark) and Ct is the
2
Bi-Zn-TiO2 concentration at time t.
1 The plots of Ln (Ci,corr /Ct ) versus reaction time are shown in
0 Fig. 9e and f for TiO2 –P25 and Bi–Zn–TiO2 respectively. The photo-
-1 catalytic discoloration kinetic data fitted well the pseudo-first order
0 20 40 60 80 100 120 kinetic according to the good values of the correlation coefficient
(R2 > 0.9568), for dye concentration ranging from 10 to 24 mg L−1 .
Contact Time (min)
The values of kapp , half-lives (t1/2 ) and initial discoloration rates
Fig. 8. Sorption kinetics of indigo carmine on TiO2 –P25 and Bi–Zn–TiO2 at various initial concentrations of indigo carmine are given in
(Ci = 16 mg L−1 pHi = 6.1 and 1 g L−1 of solid/solution ratio). Table 2. The highest discoloration rate and the shortest half-life
164 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167

a In Dark Under illumination b In Dark Under illumination

1,0 1,0

-1
0,8 5 mg L photolysis 0,8 -1
-1 5 mg L photolysis
10 mg L -1
-1 10 mg L
12.5 mg L -1
0,6 -1 0,6 12.5 mg L
16 mg L -1
Ct/C0

Ct/C0
-1 16 mg L
20 mg L -1
-1 20 mg L
0,4 24 mg L 0,4 -1
24 mg L

0,2 0,2

0,0 0,0
-30 0 30 60 90 120 150 180 210 -30 0 30 60 90 120 150 180 210
Contact Time (min) Contact Time (min)

c 1,0 d
1,0
0,9 t = -30
0,9
t=0
0,8 t = 10 0,8 t = -30
t = 20 t =0
0,7 0,7
t = 30 t = 10
0,6 t = 40 0,6 t = 20
Abs (a.u)

Abs (a.u)

t = 50 t = 30
0,5 t = 60 0,5 t = 40
0,4 t = 70 0,4 t = 50
t = 90 t = 60
0,3 t = 120 min 0,3 t = 70 min
0,2 0,2
0,1 0,1
0,0 0,0
250 300 350 400 450 500 550 600 650 700 250 300 350 400 450 500 550 600 650 700
Wavelength (nm) Wavelength (nm)

e f 3,0
1,4 -1
24 mg.L 24 mg L
-1

-1
1,2 20 mg.L 2,5 20 mg L
-1

-1
16 mg.L 16 mg L
-1

-1 -1
1,0 12.5 mg.L 2,0 12.5 mg L
-1 -1
10 mg.L 10 mg L
Ln(Ci,cor/Ct)

Ln(Ci, cor/Ct)

0,8
1,5
0,6
1,0
0,4

0,5
0,2

0,0 0,0
0 10 20 30 40 50 60 70 80 90 0 10 20 30 40 50 60 70 80 90
Contact Time (min) Contact Time (min)

Fig. 9. (a and b) photo-discoloration under visible light at different concentrations of indigo carmine with TiO2 –P25 and Bi–Zn–TiO2 respectively. (c and d) spectral evolution
of indigo carmine solution vs irradiation time in the presence of TiO2 –P25 and Bi–Zn–TiO2 respectively. (e and f) first-kinetic linear plots of indigo carmine photocatalytic
discoloration at various initial dye concentrations under visible light in the presence of TiO2 –P25 and Bi–Zn–TiO2 respectively.

were observed at low dye concentration for both photocatalysts used for heterogeneous photocatalytic degradation [48–50] and
under visible light irradiation. expressed by equation (2).
The relationship between the initial photo-degradation rate
and the initial concentration of indigo carmine can be success- kL−H Kads Ci,corr
fully described by the Langmuir–Hinshelwood (L–H) kinetic model ro = kapp Ci,corr = (2)
1 + Kads Ci,corr
 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167 165

Table 2
Kinetics parameters of photo discoloration of indigo carmine with Bi–Zn–TiO2 and TiO2 –P25 under visible light.

Photocatalyst Ci (mg L−1 ) Ci.cor (mg L−1 ) kapp (min−1 ) t1/2 (min) r0 (mg L−1 min−1 ) R2

TiO2 –P25 10.0 5.57396 0.02186 31.71 0.12185 0.9922

12.5 7.91596 0.01751 39.57 0.13861 0.9894
16.0 12.43602 0.01448 47.87 0.18007 0.9953
20.0 14.9888 0.01294 53.57 0.19396 0.9848
24.0 18.29102 0.01089 63.65 0.19919 0.9975
Bi–Zn–TiO2 10.0 3.18512 0.03812 18.18 0.12142 0.9568
12.5 4.07508 0.03492 19.85 0.14230 0.9836
16.0 6.11418 0.02888 24.00 0.17658 0.9885
20.0 9.53194 0.02174 31.88 0.20722 0.9937
24.0 14.7787 0.01597 43.40 0.23602 0.9862

10,0
y(TiO2 P25) = 27.2231 x + 3.4669 Without Scavenger
9,5 TiO2 P25 2
Light off Light on
R = 0.9815 With EDTA
9,0 Bi-Zn-TiO2 1,0 With AgNO3
8,5 With Ethanol
8,0 With Ascorbic acid
0,8
7,5
7,0
6,5 0,6
1/r0

6,0

Ct/C0
5,5
0,4
5,0
4,5 y(Bi-Zn-TiO2) = 16.3129 x + 3.0928
2
4,0 R = 0.9987 0,2
3,5
3,0
0,0
0,05 0,10 0,15 0,20 0,25 0,30 0,35
1/Ci,cor
-30 -20 -10 0 10 20 30 40 50 60 70 80

Fig. 10. Langmuir–Hinshelwood plots of indigo carmine photo-discoloration with
B–Zn–TiO2 and TiO2 –P25 under visible light (pHi = 6.1 and solid/solution ratio:
1 g L−1 ).
Table 3
Langmuir–Hinshelwood kinetic parameters for indigo carmine photo-discoloration
under visible light by TiO2 –P25 and Bi–Zn–TiO2 .
Samples kL–H (mg L−1 min−1 ) Kads (L mg−1 )
TiO2 -P25 0.288 0.1274
Bi-Zn-TiO2 0.323 0.1896
The linearization of Eq. (2) gives the following equation (Eq. (3)),
which indicates the relationship between 1/r0 and 1/Ci,corr .
1 1 1 1
= +
r0 kL−H kL−H Kads Ci,corr
where, r0 (mg L−1 min−1 ) is the initial rate of the photocatalytic dis-
coloration, kL–H (mgL−1 min−1 ) is the Langmuir–Hinshelwood rate
constant, Kads is the adsorption equilibrium constant on photocata-
lyst in (mg/L)−1 , and Ci,corr is the initial dye concentration corrected
after adsorption in dark (mg/L).
Fig. 10 exhibits a good linear plot obtained by plotting 1/r0
against 1/Ci,corr indicating that the photocatalytic reaction follows
well the L–H model. The values of the rate constant kL–H and of
the adsorption equilibrium constant Kads obtained from intercepts
and the slopes of Fig. 10 are reported in Table 3. The kL–H val-
ues are 0.323 mg L−1 min−1 for Bi–Zn–TiO2 and 0.288 mg L−1 min−1
for TiO2 –P25. This indicates that the photocatalytic activity under
visible light of Bi–Zn–TiO2 is better than that of TiO2 –P25.
Contact Time (min)
Fig. 11. Identification of the active species with different scavengers on the pho-
tocatalytic discoloration of indigo carmine under visible light in the presence of
Bi–Zn–TiO2 .
degradation of organic pollutants. The addition of specific scav-
R2 enger has been proposed to possibly identify active species [52,53].
Fig. 11 shows the role of different scavenger used in photocatalytic
0.9815
0.9987
discoloration under visible light with Bi–Zn–TiO2 as photocatalyst.
A complete discoloration achieved in 70 min without any scav-
enger. The addition of Na2 -EDTA (as a hole scavenger) decreases
on rate discoloration; indeed after 70 min of irradiation only 30%
was obtained. Moreover, about 45% of discoloration was attained
during the same time of irradiation when ascorbic acid (as super-
oxide anion radical scavenger) is used. In addition, the presence of
(3)
ethanol (as HO• radicals scavenger) causes a small decline in photo
discoloration rate compared in the case of without scavenger. On
the other hand, a total discoloration was obtained in 30 min when
AgNO3 (as e− trapping) was used. This result indicates that h+ is the
major active species responsible on a complete discoloration with
•
a moderate and minor contribution of O2 − and HO• respectively.
A short recombination of the photo-generated electron-hole pairs
exists; this is proved when AgNO3 is added, so the complete discol-
oration is achieved with h+ after 30 min irradiation indicating that
Ag+ inhibits the recombination e− /h+ pairs.
The presence of bismuth and zinc together causes the redshift
of TiO2 and inhibits or retards the recombination electron-hole
pairs. The mechanism for the photo discoloration of indigo carmine
with the four active species under visible light irradiation can be
described by the following reactions.

3.8.2. Active species identification Bi − Zn − TiO2 + hv → Bi − Zn − TiO2 (e− , h+ ) (4)

+
h + Indigo carmine → Degradation products (Major reaction)
Superoxide anion radicals O2 •− , HO• radicals and photo-
generated holes and electron are active species in photocatalytic (5)
166 B. Benalioua et al. / Journal of Hazardous Materials 288 (2015) 158–167

Adsorption/desorption, UV–vis DRS, and XPS. The obtained mate-

100 rial was investigated for the photocatalytic discoloration of indigo
carmine under visible light irradiation in comparison of commer-
cial TiO2 –P25. The kinetic data were found in a good accordance
80
with pseudo-first order and Langmuir–Hinshelwood kinetic mod-
Discoloration (%)

els. Total discoloration of 16 mg L−1 of indigo carmine aqueous

60 solution was obtained after 70 min and 120 min in the presence of
Bi–Zn–TiO2 and TiO2 –P25 respectively. Active species identifica-
tion study indicates that h+ is the major responsible for a complete
40 discoloration with a minor and moderate contribution of HO• and
O2 •− respectively.
The prepared material had been subjected to four reuses with-
20 out loss of efficiency after the first use.

0 Acknowledgements
1st Use 2nd Use 3rd use 4th Use 5th Use
The authors acknowledge the assistance provided by Profes-
Fig. 12. Stability study of Bi–Zn–TiO2 for indigo carmine photocatalytic discol- sor Chantal Guillard and engineer Frederic DAPPOZZE of IRCELYON
oration after five uses under visible light irradiation (Ci = 16 mg L−1 , pHi = 6.1 and
(France) for the measurement of the emission spectrum and the
solid/solution ration 1 g L−1 ).
irradiance of the visible lamp model E40 (TUNGSRAM trademark).

• References
e− + O2 → O−
2 (6)
• semiconductor photocatalyst, Chem. Rev. 95 (1995) 69–96.
O−
2 +Indigo carmine → Degradation products(Moderate reaction)
• •
O−
2 + 2H2 O → 2HO + 2OH
−
•
+
h+ + H2 O → HO + H
• titanium (iv) dioxide, Chem. Soc. Rev. 38 (2009) 1849–1858.
HO + Indigo carmine → Degradation products(Minor reaction)
h+ + e− → (e− , h+ )(Negligible recombination reaction)
Indigo carmine an anionic dye is adsorbed preferentially on the
surface of the photocatalyst carrier by a positive charge as the hole
h+ . Thus, this dye reacts directly with the hole h+ . This reaction
seems to be as dominant.
The adsorbed oxygen on the surface of the photocatalyst will
react with the negative charge carrier e− to become a radical anion.
The superoxide radical anion, without leaving the surface of the
photocatalyst, reacts directly with the dye. Few hydroxyl radicals
are generated from adsorbed of few water molecules. This is prob-
ably due to the occupancy of the total surface of the material by
the dye molecules. Therefore, it can be said that the adsorption of
contaminant on the surface of the photocatalyst is very important
for the photocatalytic process.
3.8.3. Photocatalyst reuse study
The stability of Bi–Zn–TiO2 as photocatalyst under visible light
irradiation was tested after five cycles (Fig. 12). The photocatalyst
exhibits a very good stable efficiency even after five uses. Indeed,
the rate photo discoloration (100%) after 70 min in each cycle was
unchanged and stay effective even after five uses.
4. Conclusion
In the present work, Bi–Zn–TiO2 was prepared by layered double
hydroxide synthesis route and characterized by TGA, SEM, XRD, N2
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