JOURNAL OF THE CHINESE

Article CHEMICAL SOCIETY

Synthesis and Characterization of [Zn-Al] Layered Double Hydroxides: Effect of the

Operating Parameters

Kaouther Abderrazek,a,b* Najoua Frini Srasraa,b and Ezzeddine Srasraa

a
Centre National de Recherches en Sciences des Matériaux, Technopôle de Borj Cedria, Tunisia
b
Département de chimie, Faculté des sciences de Tunis, Université de Tunis El Manar, Tunis Tunisia

(Received: July 15, 2016; Accepted: December 27, 2016; DOI: 10.1002/jccs.201600258)

In this study, [Zn-Al] layered double hydroxides (LDHs) were prepared using the coprecipitation
method at constant pH. The synthesis parameters (including the aging time, synthesis pH, nature
of the alkali, concentration of metallic salts, and the cationic molar ratio R = Zn/Al) were varied
in order to elucidate their effect on the properties of the obtained materials. Different characteriza-
tion techniques, namely X-ray diffraction, Fourier transform infrared, thermogravimetric
analysis-differential thermogravimetry, transmission electron microscopy, energy-dispersive X-ray,
inductively coupled plasma, and photoluminescence, were used in this study. It was found that
obtaining well-crystallized LDHs requires (i) an aging time of 24 h and (ii) a synthesis pH value in
the range 8–12. Our results also show that the concentration of the cationic metallic salts has no
influence on the structural properties of the LDHs. The use of NH4OH as alkali for adjusting the
pH value during the synthesis favors the formation of nitrated LDH phases while NaOH gives rise
to carbonated ones. Moreover, it was found that irrespective of the molar cationic ratio used
(between 1 and 5), [Zn-Al] LDHs could be obtained. The sample synthesized at R = 2 exhibited
the best crystallinity.

Keywords: [Zn-Al] layered double hydroxide; Synthesis; Characterization.

INTRODUCTION at suitable temperatures allows the formation of oxides

Layered double hydroxides (LDHs) are anionic
clays. The structure of LDHs can be derived from the
brucite structure Mg(OH)2 where each Mg2+ ion is octa-
hedrally surrounded by six OH− ions. The hydrotalcite-
type structure is obtained when some of the divalent
Mg2+ ions or other divalent cations are replaced by tri-
valent cations with a similar radius. The higher charge
of trivalent cations imposes an overall positive charge
on the brucite-type layer, which is compensated by the
incorporation of generally hydrated interlayer anions.1–3
Coprecipitation at constant pH is probably the
best technique for the synthesis of LDHs, as it leads to
materials with high chemical homogeneity and uniform
particles.4
LDHs have attracted increasing interest in the last
few years and been widely applied in many fields
including catalysis,5,6 photocatalysis,7–9 adsorption,10–13
pharmaceuticals,14 and polymer reinforcement.15 The
derived forms of LDHs obtained after their calcination
and mixed oxides, which are useful catalysts and find
potential applications in many catalytic processes, for
example, for the decomposition of nitrous oxides,16,17
hydrogenation,18 condensation19,20 and alkylation
reactions,21 or wet oxidations.22,23 However, the prop-
erties and the performance of these materials are
strongly related to the synthesis method and the oper-
ating conditions adopted for the preparation of the
starting LDH. Therefore, the optimization of the syn-
thesis parameters is important to obtain the suitable
material.
Aiming at understanding the influence of the syn-
thesis parameters on some properties of LDH phases,
our investigation focuses on the preparation of [Zn-Al]
LDHs and the study of the effect of some parameters
including the aging time, the synthesis pH, the nature
of the alkali, the initial metallic salts concentrations,
and the molar cationic ratio (R = MII/MIII) on the
obtained phases.

*Corresponding author. Email: kaoutherabderrazek@yahoo.fr

J. Chin. Chem. Soc. 2017 © 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1
Article
EXPERIMENTAL
The [Zn-Al] LDHs were prepared by the copreci-
pitation method at constant pH, with low supersatura-
tion and at room temperature. The synthesis was
Relative intensity
carried out by the slow addition of a solution of the
mixed metal nitrates, prepared from Zn(NO3)2.6H2O
and Al(NO3)3.9H2O to a Na2CO3 solution with mag-
netic stirring. During the synthesis, the pH was kept
constant by adding suitable amounts of 2 M alkaline
solution. The resulting suspension was aged at room
temperature and then centrifuged. The final product
was washed with distilled water and dried for 24 h
at 80
C.
The content of Zn and Al in the LDH was deter-
mined by inductively coupled plasma-optical emission spec-
troscopy (ICP-OES, iCAP 6000 ICPSpectrometer, Thermo
Fisher). X-ray diffraction (XRD) traces were recorded on a
PANalyticalX’PERT High Score Plus diffractometer using
monochromatic Cu Kα radiation. Transmission electron
microscopy (TEM) images were obtained using a JEOL
JEM-2100 microscope. Energy-dispersive X-ray (EDX)
analyses were performed using a 3D Quanta Field Emis-
sion Gun (FEG) electron microscope.
Thermogravimetric (TG) and differential thermo-
gravimetric (DTG) analyses were carried out on a TG
analyzer (TA Instruments, Q500). Fourier transform
infrared (FTIR) analyses were performed on a Perkin
Elmer Spectrum BX FTIR spectrophotometer, over the
range 400–4000 cm−1, using the KBr pellet technique.
Each spectrum obtained was the average of 20 scans at
a resolution of 2 cm−1. The emission spectra of all the
samples were recorded at room temperature under exci-
tation at 325 nm using a LabRAM HR
800 spectrometer.
RESULTS AND DISCUSSION
Effect of the aging time
Figure 1 shows the XRD patterns of different [Zn-
Al] LDH phases prepared at different aging times: 1, 2,
4, 12, and 24 h and at R = nZn/nAl = 3, pH = 10, and
C = 1 M. All diffractograms show several (00l) reflec-
tions characteristic of LDHs with bidimensional struc-
ture according to the ASTM card number 48-1021.24,25
The basal spacing corresponding to the (003) reflection
was ~7.6 Å for all the prepared LDHs. However, the
sample obtained after an aging time of 24 h (denoted
Zn-Al-3-10 where 3 is the cationic ratio R and 10 is the
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Abderrazek et al.
(003)
* ZnO
(006)
(012)
(015)
(018)
(110)
24 h * *
12 h * *
4h
2h
1h
0 10 20 30 40 50 60 70
2θ (°)
Fig. 1. XRD patterns of [Zn-Al] LDH samples pre-
pared at different aging times.
synthesis pH) exhibited the highest intensity of the
(003) reflection, indicating a better stacking of the LDH
layers. Furthermore, low-intensity reflections attributed
to a secondary phase (ZnO) were observed at
2θ = 31.64
(ASTM card number 89-7102) for samples
prepared with both aging times 12 and 24 h. Crystalline
ZnO is commonly obtained with the brucite-like
layer.26,27 As Zn-Al-3-10 presented the best crystallin-
ity, further studies on the structural, thermal, and opti-
cal properties were carried out on this sample.
The FTIR spectrum of the sample Zn-Al-3-10,
given in Figure 2, is typical of an LDH phase. A very
broad band between 3000 and 3500 cm−1 is observed,
which is attributed to the O–H stretching mode. The
1640 cm−1 band is assigned to the bending vibration of
H2O. The band at 1364 cm−1 corresponds to the ν3
mode of the interlayer carbonate anions. The assign-
ment of the band at 1384 cm−1 is somewhat controver-
sial. Some authors28 attribute this band to the
carbonate stretching mode, but others report that it
could be attributed also to nitrate anions.28,29 As the
amount of nitrate provided by the precursors used for
the synthesis of LDHs is important (molar ratio nitrate/
carbonate ~20), we expect that nitrate peaks to appear.
The band at 606 cm−1 can be assigned to Zn–O transla-
tion, while the bands at 430 and 760 cm−1 can be
assigned to Al–O translation.
TG and its differential curves of Zn-Al-3-10 are
given in Figure 3. As already reported in the
J. Chin. Chem. Soc. 2017
 JOURNAL OF THE CHINESE
Synthesis and Characterization of [Zn-Al] LDH CHEMICAL SOCIETY

to be a deep level emission caused by impurities, oxygen

vacancies, and the structural defects on the crystals such
as Zn interstitials.32–34

435
All LDH materials investigated in the following
Relative intensity

1632
paragraphs were prepared at an aging time of 24 h.

618
Effect of the synthesis pH
Two forms of pH control can be used in the
coprecipitation method. In one case, the pH is kept
constant during the synthesis, and in the other the pH
1384
1364 is varied.
3500

Although the latter procedure is easier, a suitable

4000 3000
Wavenumber
Fig. 2. FTIR spectrum of Zn-Al-3-10.
literature,30,31 the results show two major mass losses.
The first one occurs below 350
C and is ~25%. Accord-
ing to the DTG curve, this mass loss results from the
overlap of the following steps: the removal of physi-
sorbed and interlayer water below 165
C and the loss
of structural water due to the dehydroxylation of the
layers between 165 and 350
C. The second mass loss
(about 5%) occurring in the temperature range
400–700
C corresponds to the amount of CO2 released
from the decomposition of carbonates. Beyond 700
C,
a small mass loss (~1%) is observed, which is probably
due to the removal of the strongly bonded carbonates.
Figure 4 shows the photoluminescence
(PL) spectrum of Zn-Al-3 excited at 325 nm. A strong
ultraviolet emission at ~380 nm is observed. This
accounts for the free excitation recombination. A green
emission at ~550 nm is also observed, which is known
100
158,5°C
95
choice of the synthesis pH in the former gives rise to
2000 1000 0
materials with more interesting properties. In fact,
(cm-1)
LDHs with higher crystallinity, smaller particle size,
higher specific surface, area and higher pore diameter
have been obtained.4
In order to determine the influence of the synthesis
pH on the structural and textural properties of the
obtained materials, a series of [Zn-Al] LDHs were pre-
pared at different pH values between 5 and 12. The
samples were denoted Zn-Al-3-pH, where pH stands
for the synthesis pH. The initial concentration C of the
metallic salts was fixed as 1 M and R = 3. The XRD
patterns of the prepared samples (Figure 5) show that,
when the synthesis pH ≥ 8, sharp and symmetric reflec-
tions of well-crystallized [Zn-Al] LDHs are obtained.
The secondary phase ZnO is observed with samples pre-
pared at pH ≥ 10. For synthesis pH < 8, the obtained
materials are a mixture of low-crystalline [Zn-Al] LDH
and (Al2O3)4.H2O phases (ASTM card number 00-
025-0017).
The unit cell parameters evaluated using standard
relationships and the crystallite size of the samples pre-
3
pared at pH ≥ 8 are given in Table 1. The results show
a small decrease of the unit cell parameter a, suggesting
that less Zn is incorporated in the layers of the LDH
Deriv.weight change (%/min)

90
when the synthesis pH value increases. As chemical
2
85 analysis showed similar molar cationic ratios in the
Weight (%)

80 samples (Table 2), the amount of the secondary phase

75 224,08°C
ZnO is probably more important at higher pH values.
1
70
The variation of the c parameter can be due to the dif-
551,96°C ferent arrangements of carbonate anions in the inter-
65
layer space of the LDH. The crystallite size of the
60 0
0 200 400 600 800 1000 different samples increased with the synthesis pH, sug-
Temperature (°C) gesting that a basic pH favors the growth at the expense
Fig. 3. TG-DTG curves of Zn-Al-3-10. of the nucleation. The increase in the reflection

J. Chin. Chem. Soc. 2017 © 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.jccs.wiley-vch.de 3
 Article Abderrazek et al.

35000 necessary to ensure the detection of these planes. The

378 nm intensity of these reflections increased with the synthesis
30000
pH, indicating that more layers are formed.
25000
PL intensity (a.u)

Effect of metallic salt concentration

20000
Figure 6 presents the XRD patterns of samples
15000 prepared at pH = 10, R = 3 and at different initial con-
559 nm centrations of metallic salts: C = 0.1, 0.5, and 1 M,
10000
where C = [Zn2+] + [Al3+]. The results show that irre-
5000
spective of the concentration used, well-crystallized [Zn-
Al] LDHs were obtained, suggesting only a minor effect
0 of the concentration on the structural properties of the
300 350 400 450 500 550 600 650 700 750
obtained materials. The reflections of ZnO were only
Wavelengh (nm)
observed in the diffractogram of the sample synthesized
Fig. 4. Photoluminescence spectrum of Zn-Al-3-10.
at C = 1 M. However, in samples prepared at C = 0.1
intensities demonstrates this growth phenomenon. and 0.5 M, the ZnO phase could be present but not
Indeed, the XRD technique is based on the interference observed in the diffractograms. In fact, to observe a
phenomenon between planes, so a certain periodicity is compound by XRD, it has to be present in more than
3% and its crystallite size has to be larger than ~25 Å
and on the surface.35

Effect of the nature of the alkali

The XRD patterns of two [Zn-Al] LDH phases
synthesized under the same conditions (R = 3, pH =
10, C = 1 M) using either NaOH or NH4OH as alkali
(denoted Zn-Al-3-10 and Zn-Al-3-100 , respectively) are
shown in Figure 7. The diffractogram of the sample
synthesized with NH4OH shows two additional reflec-
tions at 2θ values of 10.74
and 20.020
. These reflec-
tions correspond to d(003) and d(006) of nitrated LDH,
respectively.36 The basal reflections (003) and (006) of
carbonated LDHs are also present in the same diffrac-
togram. The obtaining of nitrated LDHs are due to the
complexation of CO2− 3 anions by ammonium keeping
them in solution, which reduced their intercalation in
the interlayer space of the LDH.
Chemical analysis (Table 2) showed that the molar
cationic ratio R is lower than the initial ratio (R = 3)
for the sample Zn-Al-3-100 , which is due to the small
intercalation of Zn in the LDH layers. This might be
due to the complexation of Zn2+ in solution by ammo-
nium species following the reactions.37

Zn2 + + NH3 = ½ZnðNH3 Þ2 + ð1Þ

 2 +
Fig. 5. XRD patterns of [Zn-Al] LDH prepared at Zn2 + + 2NH3 = ZnðNH3 Þ2 ð2Þ
different pH values.

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Synthesis and Characterization of [Zn-Al] LDH CHEMICAL SOCIETY

Table 1. Cell parameters and crystallite size of samples prepared at pH ≥ 8

Synthesis pH Zn-Al-3-8 Zn-Al-3-9 Zn-Al-3-10 Zn-Al-3-11 Zn-Al-3-12

a = 2.d(110) (Å) 3.089 3.084 3.083 3.082 3.075
c = 3:d ð00l Þ (Å) 22.888 22.869 22.859 22.814 22.843
E = d ð00l Þ − 4:8 (Å) 2.828 2.823 2.819 2.803 2.814
Crystallite size (nm) 15 22 34 48 37
E, thickness of the lamellar space; 4.8, thickness of the brucite layer.

 2 +
* ZnO

(003)
Zn2 + + 3NH3 = ZnðNH3 Þ3 ð3Þ

Effect of the molar cationic ratio (R = Zn/Al)

(006)

(012)
Relative intensity

(015)
[Zn-Al] LDHs were synthesized at different molar
cationic ratios and denoted Zn-Al-R-10 where R is the

(110)
* 1M
molar cationic ratio and 10 is the synthesis pH. The *
XRD patterns of these samples, shown in Figure 8,
indicate that irrespective of the cationic ratio used,
0.5M
sharp and symmetric reflections characteristic of
hydrotalcite-like compounds were obtained. The crys-
0.1M
tallinity and the purity of the samples were dependent
on the cationic ratio. In fact, the intensity of the (00l) 0 10 20 30 40 50 60 70
peaks decreases with increase of the cationic ratio R. 2θ (°)
However, Zn-Al-2-10 exhibited the best crystallinity. Fig. 6. XRD patterns of [Zn-Al] LDH prepared at
For R ≥ 3, very low diffractions of the ZnO phase were different initial concentrations C = [Zn2+]/
present in the XRD patterns in the range of [Al3+].
2θ = 32
–37
.
The crystallographic parameters and the crystallite isomorphous substitution of Al3+ (with ionic radius
size determined for the different Zn-Al-R-10 are shown r = 0.5 Å) by Zn2+ (with a higher ionic radius
in Table 3. The results show a variation of the para- r = 0.74 Å). The increase of c parameter with
meters a and c, indicating the effective incorporation of
Zn2+ in the structure of the LDH. The increase of the
* ZnO
7,600 A°

value of the parameter a is probably due to the

Table 2. Chemical analysis of the different [Zn-Al] LDHs

Relative intensity

nZn nAl Rexp = nZn/

Sample (mmol/g) (mmol/g) nAl REDX

Zn-Al-1-10 4.76 4.58 1.04 1.2

8.780 A°

4.419 A°

Zn-Al-2-10 5.57 2.66 2.09 2.18 Zn-Al-3-10

* *
Zn-Al-3-10 7.21 2.44 2.95 3.31
Zn-Al-4-10 8.05 2.06 3.90 3.98
Zn-Al-5-10 8.13 1.64 4.95 5.17
Zn-Al-3-10 5.94 3.62 1.64 Zn-Al-3-10'
Zn-Al-3-8 6.68 2.24 2.98
Zn-Al-3-9 6.34 2.06 3.06 0 10 20 30 40 50 60 70
Zn-Al-3-11 6.83 2.37 2.90 2θ (°)
Zn-Al-3-12 6.52 2.22 2.93
Fig. 7. XRD patterns of Zn-Al-3-10 and Zn-Al-3-100 .

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 Article Abderrazek et al.

of the shape of some platelets was produced when the

(003)

(006)

(012)
sample was subjected to the electron beam.40 (2) The

(110)
Zn-Al-1-10 nanorods were assigned to the secondary phase ZnO,
which is present in all samples. Reflections of ZnO
Relative intensity

phase are not observed in the diffractograms of Zn-Al-

1-10 and Zn-Al-2-10, which is due probably to its low
amount in these samples. The average crystallite size of
Zn-Al-2-10 ZnO particles was calculated for the different samples
from the TEM micrographs. Results given in Figure 10
Zn-Al-3-10 show that the ratio R does not seem to affect the parti-
* *
Zn-Al-4-10 cle size of ZnO particles, which is in the order of
* *
* * Zn-Al-5-10 200 nm. However, for R = 1 and 2, the average of the
crystallite size is slightly lower.
10 20 30 40 50 60 70

2θ (°)

Fig. 8. XRD patterns of Zn-Al-R-10.

R indicates an increase in the interlayer spacing, which
may be due to the change of arrangement of the carbo-
nate anions. The crystallite size decreased slightly when
the ratio R increased.
Chemical analyses given in Table 2 show that,
irrespective of the sample, the experimental ratio R is
in agreement with the theoretical ratios, suggesting
that the coprecipitation is nearly total. The different
cationic ratios determined by EDX analyses (also
given in Table 3) are higher than the ratios determined
by ICP, which may be due to the presence of dispersed
ZnO particles on the surface of LDH layers. Thus, the
chemical formulas could not be calculated since the
obtained products were a mixture of LDH and ZnO
phases.
The morphologies of the synthesized LDH phases
determined with TEM are given in Figure 9. For all
samples Zn-Al-R-10, two different morphologies were
observed: (1) The hexagonal platelets were attributed to
the carbonated brucite-like sheets.38,39 The irregularity
CONCLUSIONS
Different [Zn-Al] LDHs were synthesized using
the coprecipitation method at constant pH. Many oper-
ating conditions (including the aging time, the synthesis
pH, the nature of the alkali, and the molar cationic
ratio R = Zn/Al) were varied during the synthesis in
order to investigate their effect on the properties of the
obtained samples. It was found that well-crystallized
LDHs can be obtained when (1) an aging time of 24 h
was chosen, and (2) the synthesis pH was carried out
between pH values 8 and 12.
The variation of the concentration of the metallic
salts between 0.1 and 1 M does not have a significant
effect on the structure of the obtained materials. The
use of NH4OH as alkali to adjust the pH favors the
formation of nitrated LDH phases. The cationic ratio
(varied between 1 and 5) influences the crystallinity of
the samples, which is the best for R = 2. Samples Zn-
Al-R-10 showed the presence of two different
morphologies: hexagonal platelets and fibers, which
can be attributed to LDH particles and to the ZnO
phase, respectively.

Table 3. Cell parameters and crystallite size of Zn-Al-R-10 samples

Sample Zn-Al-1-10 Zn-Al-2-10 Zn-Al-3-10 Zn-Al-4-10 Zn-Al-5-10

a = 2.d(110) (Å) 3.046 3.067 3.083 3.086 3.088

c = 3:d ð00l Þ (Å) 22.675 22.799 23.028 23.016 22.799
E = d ð00l Þ − 4:8 (Å) 2.758 2.799 2.876 2.872 2.800
Crystallite size (nm) 48 40 34 27 30

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250 225 225 220

200
Zn-Al-1-10 170

Particles size
150
120

100

50

0
Zn-Al-1-10 Zn-Al-2-10 Zn-Al-3-10 Zn-Al-4-10 Zn-Al-5-10
Sample

Zn-Al-2-10 Fig. 10. ZnO particle size determined from TEM

micrographs.

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