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Journal of Taibah University for Science 11 (2017) 90100

ZnAl layered double hydroxides intercalated with carbonate,

nitrate, chloride and sulphate ions: Synthesis, characterisation and
dye removal properties
Fatima Zahra Mahjoubi a,b , Abderrahim Khalidi b , Mohamed Abdennouri a ,
Noureddine Barka a,
a Univ Hassan 1, Laboratoire des Sciences des Matriaux, des Milieux et de la Modlisation (LS3M), BP 145, 25000 Khouribga, Morocco
bUniversit Hassan II de Casablanca, Facult des Sciences et Techniques, Laboratoire de Chimie Physique et de Chimie Bioorganique,
BP 146, Mohammedia, Morocco
Received 10 July 2015; received in revised form 10 September 2015; accepted 8 October 2015
Available online 11 November 2015

Abstract
In this work, ZnAl layered double hydroxides intercalated with carbonate, nitrate, chloride and sulphate ions were synthe-
sised via a co-precipitation method at a constant solution pH. The as-synthesised samples were characterised by X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and simultaneous thermogravi-
metric/differential thermal analysis (TGA-DTA). The XRD patterns showed that Zn-Al-SO4 had the greatest interlayer spacing,
followed by Zn-Al-Cl, Zn-Al-NO3 and Zn-Al-CO3 . The FTIR spectra clearly confirmed the presence of intercalated anions in the
structure of the LDHs. Batch experiments for methyl orange (MO) adsorption onto synthesised samples were investigated under
various conditions such as contact time, initial dye concentration and solution pH. The experimental results show that pH is the
most influencing factor. The effective pH range for the MO removal was found to be 3.54.5. The kinetics data can be described
accurately by a pseudo-second-order kinetic model instead of a pseudo-first-order model. The equilibrium data were analysed using
the Langmuir, Freundlich and DubininRadushkevich models. The results showed that the Langmuir and DubininRadushkevich
isotherm models fit well to the experimental data. The Zn-Al-LDH samples exhibited exceptional Langmuir maximum adsorption
capacities of 2758, 2455, 2270 and 1684 mg/g for Zn-Al-SO4 , Zn-Al-Cl, Zn-Al-NO3 and Zn-Al-CO3 , respectively.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Layered double hydroxide; Dye removal; Chemical synthesis; Surface properties

Corresponding author. Tel.: +212 661 66 66 22;
fax: +212 523 49 03 54.
E-mail address: barkanoureddine@yahoo.fr (N. Barka).
Peer review under responsibility of Taibah University.
http://dx.doi.org/10.1016/j.jtusci.2015.10.007
1658-3655 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
Wastewater from the dyestuff manufacturing, dye-
ing, printing and textile industries presents a serious
problem all over the world because dyes and pigments
in wastewater undergo chemical changes and destroy
aquatic life and can even endanger human health. Most of
these dyes are toxic, mutagenic and carcinogenic [14].
According to a survey of the ecological and toxicological
 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
Table 1
Physicochemical characteristics of methyl orange.
Name Molecular
structure
NaO3S
Methyl orange (Acid orange 52)
Fig. 1. XRD patterns of Zn-Al-CO3 (a), Zn-Al-NO3 (b), Zn-Al-Cl (c) and Z-nAl-SO4 (d).
association of the dyestuffs manufacturing industry
(ETAD), over 90% of some 4000 dyes have LD50
values greater than 2000 mg/kg [5,6]. From an environ-
mental point of view, the remediation of wastewater is
a great challenge and has attracted tremendous atten-
tion in recent years. Different methods have been used
for dye removal from wastewaters such as biological
degradation [7], photodegradation [8], coagulation [9],
membrane filtration [10], reverse osmosis [11], adsorp-
tion [12], or the synergic treatment using different
methods. Among these methods, the adsorption process
is one of the most effective techniques that has been
successfully employed for colour removal because it is
considered to be less expensive, more efficient and less
likely to generate secondary waste [13]. Most conven-
tional adsorption systems use activated carbon despite
its high production costs and regeneration difficulty [14].
Recently, many low-cost adsorbents have been investi-
gated in the removal of dyes such as agricultural wastes
[15], clays [16], chitosan [17], silica [18], kaolinite [19],
91
Solubility pKa MW (g/mol) max (nm)
in water
(g/L)
CH3
N N N
CH3
5.2 3.47 327.33 465
perlite [20], sepiolite [21], montmorillonite [22] and
some natural biosorbents [23]. However, these materi-
als generally have low adsorption capacities, and hence,
a large adsorbent dosage is required to achieve a low dye
concentration in the treated effluents.
Layered double hydroxides (LDHs), including
hydrotalcite and hydrotalcite-like compounds, have
received considerable attention due to their potential
applications in catalysis, photochemistry, electrochem-
istry, polymerisation, magnetisation, biomedical science
and environmental applications [2428]. LDHs are
host-guest materials consisting of positively charged
metal oxide/hydroxide sheets with intercalated anions
and water molecules. They can be represented by the
general formula: [M1x 2+ Mx 3+ (OH)2 ] (An )x/n mH2 O,
where M2+ is a divalent cation such as Mg2+ , Zn2+ , Cu2+ ,
etc., and M3+ is a trivalent cation such as Al3+ , Cr3+ ,
Fe3+ , etc. Due to the partial substitutions of M3+ for M2+ ,
the hydroxide sheets are positively charged and require
the intercalation of anions (An ), such as CO3 2 , NO3 ,
92 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
Table 2
Unit cell parameters and interlamellar distance of Zn-Al-LDHs.
Sample a (A) c (A) Interlamellar distance (A)
Zn-Al-CO3 3.05 22.71 7.57
Zn-Al-NO3 3.05 26.53 8.84
Zn-Al-Cl 3.05 26.58 8.86
Zn-Al-SO4 3.05 33.48 11.16
Cl , or SO4 2 , to retain the overall charge neutrality.
The composition of LDH materials is tunable. That is,
the divalent cation or trivalent cation can be replaced or
partly replaced by other cations, and the interlayer anion
can also be replaced by other anions; thus, their physi-
cal and chemical properties can be altered [29]. LDHs
exhibit favourable characteristics for the adsorption of
pollutants such as large surface areas, good thermal sta-
bilities, and high sorption and regeneration efficiencies
[3033]. Moreover, LDHs are regarded as a class of
materials that are simple and economical to synthesise
in the laboratory.
In the present work, zinc aluminium-layered double
hydroxides intercalated with carbonate, nitrate, chlo-
ride, or sulphate were synthesised via a co-precipitation
method. The samples were characterised by powder
XRD, FTIR, TEM and TGA-DTA. The effects of var-
ious parameters such as solution pH, contact time and
dye concentration on the removal of methyl orange by
these precursors were studied in detail. The adsorp-
tion kinetic data were tested by pseudo-first-order and
pseudo-second-order kinetic models. The equilibrium
data were analysed using the Langmuir, Freundlich and
DubininRadushkevich isotherm models.
2. Experimental
2.1. Materials
All of the chemicals used in this study were of analyti-
cal grade. Zn(NO3 )2 6H2 O, Al(NO3 )3 9H2 O, Na2 CO3 ,
Na2 SO4 , NaCl, NaNO3 and methyl orange were pur-
chased from SigmaAldrich (Germany). NaOH was
purchased from Merck (Germany) and HNO3 from
Scharlau (Spain). The chemical structure and some other
specific characteristics of methyl orange are summarised
in Table 1.
2.2. Synthesis of ZnAl layered double hydroxides
ZnAl layered double hydroxides intercalated with
CO3 2 , NO3 , Cl , or SO4 2 were synthesised via a co-
precipitation method at a constant solution pH of 10. An
aqueous solution containing Zn(NO3 )2 6H2 O (0.75 M)
and Al(NO3 )3 9H2 O (0.25 M) was added dropwise to
a vigorously stirred solution of NaOH (2 M) and 0.2 M
of the desired anion (CO3 2 , NO3 , Cl , or SO4 2 ).
The resulting gels were hydrothermally treated at 80 C
for 24 h to improve their crystallinities, were filtered,
and then were washed repeatedly with deionised water.
Finally, they were dried at 60 C for 24 h. The obtained
products were called Zn-Al-CO3 , Zn-Al-NO3 , Zn-Al-Cl
and Zn-Al-SO4 .
2.3. Characterisation of the samples
The powder X-ray diffraction (XRD) patterns were
recorded from 2 = 570 using a Bruker-axs D2-phaser
advance diffractometer operating at 30 kV and 10 mA
with Cu K1 (1.54056 A) and K2 (1.54439 A) radia-
tions. The FTIR spectra were collected on a Nicolet
Avatar 330 Fourier transform IR spectrophotometer. The
samples were mixed with KBr at a mass ratio of 1:100
and finely powdered to prepare pellets. The spectra
were recorded with a 2 cm1 resolution in the range
of 4000400 cm1 . Transmission electron microscopy
(TEM) images were obtained on a TEM TECNAI
G2/FEI instrument at an accelerating voltage of 120 kV.
The simultaneous thermogravimetric-differential ther-
mal analysis (TGA-DTA) curves were recorded on a
SETARAM LabsysTM Evo model instrument under
argon atmosphere in the temperature range of 30700 C
and with a heating rate of 10 C/min.
2.4. Adsorption experiments
Stock solutions of 1 g/L of MO were prepared by
dissolving the appropriate amount of the dye in dis-
tilled water, and the concentrations that were used were
obtained by dilution. The adsorption experiments were
performed in a series of 250-mL beakers containing the
desired weight (20 mg) of each LDH and 250 mL of
the methyl orange solution at the desired concentration.
These experiments were carried out at a constant agita-
tion speed of 500 rpm by varying the pH of the solution
from 2 to 12, the contact time from 5 to 360 min and
the initial dye concentration from 20 to 1000 mg/L. The
solution pH was adjusted to a given value with the addi-
tion of HCl (1 N) or NaOH (1 N), and it was measured
using a SensION+ PH31 pH meter.
After each adsorption experiment was completed,
the solid phase was separated from the liquid phase
by centrifugation at 3000 rpm for 15 min. The resid-
ual concentrations were determined from UVVis
characteristics at a maximum absorption wavelength of
 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
Fig. 2. FTIR spectra of Zn-Al-CO3 (a), Zn-Al-NO3 (b), Zn-Al-Cl (c) and Zn-Al-SO4 (d) LDHs.
465 nm using a TOMOS V-1100 UVvis spectropho-
tometer.
The adsorbed amounts at equilibrium (qe ) and at any
time (qt ) were calculated using the following equation:
(C0 Ce,t ) V
qe,t = , (1)
m
where qe,t (mg/g) is the adsorbed quantity at equilib-
rium (qe ) or at any time (qt ), C0 (mg/L) is the initial dye
concentration, Ce,t (mg/L) is the dye concentration at
equilibrium (Ce ) or at any time (Ct ), V (L) is the volume
of the solution, and m (g) is the mass of the LDH sample
(g).
3. Results and discussion
3.1. Characterisation
3.1.1. XRD analysis
The XRD patterns of the samples, shown in Fig. 1,
exhibit the characteristic reflections of layered double
hydroxides. The diffraction peaks were indexed to a
hexagonal lattice with rhombohedral 3R symmetry [24].
The basal peaks for the (003) and (006) planes at 2 val-
ues between 7 and 26 and the non-basal peaks for the
93
(101), (015), (018), (110) and (113) planes at higher 2
values can be observed from the figure. The (003) peak
indicates the basal reflection of an interlayer anion in
LDH materials. The first peak of the doublet close to a
2 of approximately 60 is due to the orientation from
the (110) planes, and its spacing corresponds to the lat-
tice parameter a, which coincides with the closest MM
distance in the brucite-like layers. The unit cell param-
eters a and c can be calculated from the positions of
these reflections: a = 2d110 and c = 3d003 . The obtained
parameters are presented in Table 2. These lattice param-
eters agree well with those reported for hydrotalcite-like
compounds [34]. The interlamellar distances (d003 ) of
the samples were found to be 7.57, 8.84, 8.86 and 11.16
for Zn-Al-CO3 , Zn-Al-NO3 , Zn-Al-Cl and Zn-Al-SO4 ,
respectively. The difference in the values of the inter-
lamellar distances is evidence of the size and charge
of the corresponding anions intercalated between the
layers.
3.1.2. FTIR
The FTIR spectra of the LDHs shown in
Fig. 2 reveal bands characteristic of hydrotalcite-like
compounds. The broad and strong band centred at
94 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
Fig. 3. TEM micrographs of the LDHs samples: (a) Zn-Al-CO3 , (b) Zn-Al-NO3 , (c) Zn-Al-Cl and (d) Zn-Al-SO4 .
3400 cm1 is attributed to the stretching of the OH bond
of the hydroxyl groups and H2 O molecules. The weak
band at 1630 cm1 can be assigned to the H2 O bending
vibration of the interlayer water. The bands recorded
at 460, 550, and 790 cm1 are ascribed to the Al-O
condensed groups, the Zn/Al-OH translation and the
Al-OH deformation, respectively. For the Zn-Al-CO3
sample, the band around 1365 cm1 can be attributed
to the anti-symmetric stretching mode (3 ) of carbon-
ate, and bands observed around 870 and 680 cm1
are attributed to the weak non-planar bending mode
(2 ) and the angular bending mode (4 ) of carbonate,
respectively. The FTIR spectra of Zn-Al-NO3 reveal a
strong peak around 1380 cm1 attributed to the anti-
symmetric stretching mode (3 ) of the nitrate anion
present in the LDH [35]. The bands observed around
839 and 670 cm1 can be attributed to the weak out-
of-plane symmetric deformation mode (2 ) and the
anti-symmetric deformation mode (4 ) of nitrate, respec-
tively. The distortion of Cl in the interlayer of Zn-Al-Cl
is reflected in the IR spectra with both 3 and 4 bands
split at 11001145 cm1 and 626635 cm1 , respec-
tively. For Zn-Al-SO4 , the band observed at 1112 cm1
can be attributed to the stretching mode (3 ) of sul-
phate, and the weak bands observed around 619 and
989 cm1 can be attributed to the weak bending modes
(2 ) and the symmetric stretching mode (1 ), respec-
tively, for the sulphate anion present in the LDH
[35].
3.1.3. TEM observation
Fig. 3 presents TEM images of different LDH
samples. As shown, the Zn-Al-CO3 and Zn-Al-SO4
samples consisted of hexagonal platelets having some
small cracks at the edge of the hexagonal sheets and
part of the sheets presenting a vertical crossing at
the hexagonal sides. The particle size varied from 20
to 150 nm. The spherical particles can be observed
in Zn-Al-NO3. The TEM micrograph of the Zn-Al-
Cl sample indicates the formation of agglomerates.
This difference in the size and morphology could be
attributed to the nature and amount of the interlayer
anions.
3.1.4. TGA-DTA analysis
The thermogravimetric analysis of the synthesised
LDHs is shown in Fig. 4. All of the TGA-DTA pat-
terns are characterised by a weight loss between 10
and 14% due to the loss of the interlayer water in
the temperature range of 50250 C. For Zn-Al-CO3 ,
 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100 95

Fig. 4. TGA-DTA curves of Zn-Al-CO3 (a), Zn-Al-NO3 (b), Zn-Al-Cl (c) and Zn-Al-SO4 (d).

250 150

Zn-Al-CO3
200 Zn-Al-NO3 120
Zn-Al-Cl
Zn-Al-SO4
q (mg/g)

150
qe (mg/g)

90
Zn-Al-CO3
Zn-Al-NO3
100 60 Zn-Al-Cl
Zn-Al-SO4

50 30

0 0
0 2 4 6 8 10 12 0 60 120 180 240 300 360

pH Contact time (min)

Fig. 5. Effect of solution pH on the adsorption of MO by the LDHs. Fig. 6. Effect of contact time on the adsorption of MO by LDHs
(C0 = 20 mg/L; V = 250 mL; m = 20 mg; agitation speed = 500 rpm; (C0 = 20 mg/L; V = 250 mL; m = 20 mg; agitation speed = 500 rpm;
T = 25 C, contact time = 8 h). T = 25 C, pHsol = 8).
96 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
the dehydration takes place in two steps, at 150 and
250 C. These steps can be interpreted as resulting from
the loss of adsorbed and interlayer water followed by
water loosely coordinated to the interlayer carbonate.
The interlayer carbonate is released as CO2 at approx-
imately 350 C. The total mass loss was 20.86%. For
Zn-Al-NO3 , there are mass losses at 150, 250, 350 and
450 C. The mass losses at 150 and 250 are accom-
panied by a change in the heat flow; it should result
from the removal of the adsorbed surface water and the
interlayer water. The second distinct mass loss region
of 350460 C resulted from two processes, namely
the dehydroxylation of the Zn-Al-LDH layers and the
decomposition of the interlayer NO3 anions. The total
mass loss was 21.5%. TGA-DTA analysis for Zn-Al-Cl
shows a similar dehydration behaviour to that of Zn-
Al-NO3 , but Cl was lost in the temperature range of
400500 C. The total mass loss at 700 C was 18.84%.
The decomposition of Zn-Al-SO4 occurred in the fol-
lowing steps: the first mass loss at 150 C corresponded
to the evaporation of surface-adsorbed water followed
by evaporation of the interlayer water at 250 C; a third
loss of mass occurring at 350 C is attributed to the
dehydroxylation of the brucite-like octahedral layers.
The fourth step at 600 C was likely due to the elim-
ination of the intercalated SO4 2 in the ZnAl LDH
interlayers.
3.2. Effect of solution pH on the adsorption of MO
Generally, pH is considered to be an important param-
eter controlling the adsorption at the water-adsorbent
interface. Adsorption experiments were carried out
under the same experimental conditions by varying the
solution pH from 2 to 12. The obtained results are illus-
trated in Fig. 5. From the figure, it can be observed that
the amounts of MO adsorbed at equilibrium (qe ) were
higher under acidic conditions. The maximum adsorp-
tion was observed at a pH of approximately 4.5 and
steadily decreased as the solution pH increased. The
equilibrium was difficult to establish in alkaline con-
ditions because of the competition between the excess
OH in the solution and the anionic molecules of MO.
However, under acidic conditions, the equilibrium was
easy to establish because the rate of adsorption strongly
depends on the chemical adsorption effect. The disso-
ciation constant (pKa ) of the MO is 3.46; therefore, the
monovalent anions of MO were predominantly present
at these equilibrium pHs. Furthermore, the structure of
the LDH materials was destroyed when the pH was
below 4 [36]. In this case, the adsorption of MO strongly
decreased.
3.3. Kinetics
The variation with contact time in the amounts of
MO adsorbed is shown in Fig. 6. The figure indicates
that the adsorbed amounts increased rapidly in the first
hour. Then, it slowed until equilibrium was established
after 4 h for Mg-Al-CO3 and Mg-Al-Cl and 5 h for Mg-
Al-NO3 and Mg-Al-SO4 . The figure also indicates that
the adsorption affinity increased in the following order:
Zn-Al-CO3 , Zn-Al-NO3 , Zn-Al-Cl and Zn-Al-SO4 . This
result correlates with the differences in the structural
properties of each LDH, essentially the interlayer spac-
ing, as confirmed by XRD analysis.
To characterise the kinetics involved in the process of
adsorption, pseudo-first-order and pseudo-second-order
kinetic models were proposed, and the kinetics data were
analysed based on the regression coefficient (r2 ) and the
amount of dye adsorbed per unit weight of the adsorbent.
The first-order rate expression of Lagergren based on
the solid capacity is generally expressed as follows [37]:
q = qe (1 ek1 t ), (2)
where qe and q (both in mg/g) are, respectively, the
amounts of dye adsorbed at equilibrium and at any time
t, and k1 (1/min) is the adsorption rate constant.
The pseudo-second-order model proposed by Ho and
McKay [38] was used to explain the adsorption kinetics.
This model is based on the assumption that the adsorp-
tion follows a second-order chemisorption mechanism.
The pseudo-second-order model can be expressed as:
k2 qe 2 t
q= , (3)
1 + k2 q e t
where k2 (g/mg min) is the rate constant of the pseudo-
second-order adsorption.
Parameters of the pseudo-first-order and pseudo-
second-order models were estimated with the aid of a
non-linear regression. The obtained data and the corre-
lation coefficients, r2 , are given in Table 3. The table
shows that the correlation coefficient for the pseudo-
second-order kinetic model is closer to unity than that of
the pseudo-first-order models. From these results, it was
concluded that the pseudo-second-order model was bet-
ter than the Lagergren first-order model for the systems
investigated in this work. Because ion adsorption fol-
lows pseudo-second-order kinetics, this suggested that
the boundary layer resistance was not the rate-limiting
step [36]. The rate of MO adsorption may be con-
trolled largely by a chemisorption process in conjunction
with the chemical characteristics of the LDHs and MO
molecules. A similar phenomenon is observed in the
 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100 97

Table 3
Kinetic constants for methyl orange adsorption onto LDHs.
LDH qexp Pseudo-first-order Pseudo-second-order

qe (mg/g) k1 (1/min) r2 qe (mg/g) k2 (g/mg min) r2

Zn-Al-CO3 18.67 018.50 0.01476 0.975 22.32 0.00072 0.987

Zn-Al-NO3 116.77 106.07 0.05855 0.927 116.19 0.00070 0.984
Zn-Al-Cl 124.68 115.77 0.04838 0.909 127.32 0.00053 0.972
Zn-Al-SO4 140.50 136.14 0.01563 0.973 163.16 0.00011 0.989

Fig. 7. Experimental points and nonlinear fitted isotherm curves for the adsorption of MO onto LDHs.

Table 4
Isotherm models constants for the MO adsorption onto LDHs.
LDH Langmuir Freundlich DubininRadushkevich
qm (mg/g) KL (L/mg) r2 KF (mg11/n /g/Ln ) n r2 qm (mg/g) B (mol J1 ) r2

Zn-Al-CO3 1684.170 0.022 0.979 492.028 6.331 0.858 1418.593 0.00006 0.696
Zn-Al-NO3 2270.576 0.013 0.984 379.769 3.803 0.924 1916.550 0.00033 0.940
Zn-Al-Cl 2455.315 0.010 0.984 295.752 3.259 0.926 1974.428 0.00037 0.954
Zn-Al-SO4 2758.139 0.028 0.995 799.406 5.303 0.950 2447.876 0.00008 0.859
98 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
adsorption of methyl orange onto Mg/Ni-Al layered dou-
ble hydroxides [39].
3.4. Adsorption isotherms
The isotherms of the adsorption of methyl orange by
LDHs are shown in Fig. 7. They all display the typical
L shape according to Giless classification [40]. MO
is highly concentration dependent. The increase in the
adsorption capacity with the dye concentration in the
solution is probably due to a high driving force for the
mass transfer. In fact, a high concentration in the solution
implicates a large number of dye molecules fixed at the
surface of the adsorbent. The Langmuir, Freundlich and
Dubinin Redushkevich isotherm models were applied for
the analysis of the obtained equilibrium sorption data.
The Langmuir adsorption model is based on the
assumption that the maximum adsorption corresponds
to a saturated monolayer of solute molecules on the
adsorbent surface. Therefore, The Langmuir isotherm
assumes that sorption comes from the monolayer cov-
erage of the adsorbate over a homogenous adsorbent
surface [41]. This model supposes that sorption occurs
on specific homogeneous sites within the adsorbent and
that all of the sorption sites are energetically identical.
The Langmuir isotherm can be written in the following
form:
qm KL Ce
qe = , (4)
1 + KL C e
where qm (mg/g) is the maximum amount of dye
adsorbed per unit mass of adsorbent, and KL (L/mg) is
the Langmuir constant related to the rate of adsorption.
Ce is the equilibrium concentration.
The Freundlich isotherm is an empirical model of a
heterogeneous surface with a non-uniform distribution
of heat sorption and affinities by means of multilayer
adsorption [42].
The form of the Freundlich equation can be stated as
follows:
qe = KF Ce1/n , (5)
where KF (mg11/n /g/Ln ) and n are Freundlich constants,
n indicates whether the adsorption process is favourable,
and KF is related to the adsorption capacity of the adsor-
bent.
The DubininRadushkevich isotherm model does not
assume a homogenous surface or a constant sorption
potential, as other models do. It can be noted that this
isotherm model is more general than the Langmuir
model [43]. The DubininRadushkevich isotherm has
been written by the following equations:
qe = qm exp(B2 ) (6)
 
1
= RT ln 1 +
2
(7)
Ce
where B is a constant related to the adsorption energy,
qmax is the theoretical saturation capacity, and is the
Polanyi potential.
A non-linear regression is used to determine the best-
fitting isotherm, and the applicability of the isotherm
equations is compared by comparing the correlation
coefficients, r2 . Table 4 shows the obtained results. The
table indicates that the Langmuir equation gives the
best satisfactory fitting to the adsorption isotherms of
the MO adsorption onto the LDH samples with higher
correlation coefficients than the others, indicating the
homogeneous nature of all the surfaces and the for-
mation of a monolayer of methyl orange molecules
on the surface of the adsorbents. The Langmuir maxi-
mum adsorption capacities were 2758, 2455, 2270 and
1684 mg/g for Zn-Al-SO4 , Zn-Al-Cl, Zn-Al-NO3 and
Zn-Al-CO3 , respectively.
The adsorption capacities decreased in the follow-
ing order: Zn-Al-SO4 > Zn-Al-Cl > Zn-Al-NO3 > Zn-
Al-CO3 . This behaviour can be attributed to the peculiar
structural properties of each LDH. As confirmed by
XRD, the interlayer spacing decreased in the same order.
The main mechanism for the MO adsorption on the
LDHs could be the ion exchange between the MO anions
and previously intercalated anions, although the surface
adsorption is also presumed to be involved [44].
4. Conclusion
ZnAl layered double hydroxides intercalated with
CO3 2 , NO3 , Cl or SO4 2 were successfully pre-
pared via a co-precipitation method. The presence
of the anions in the hydrotalcite structure was con-
firmed by infrared spectroscopy. The XRD analyses
showed that the interlayer spacing followed this order:
Zn-Al-SO4 > Zn-Al-Cl > Zn-Al-NO3 > Zn-Al-CO3 . All
TGA-DTA curves are characterised by a weight loss
between 10 and 14% due to a loss of interlayer water
in the temperature range of 50250 C. The maximum
adsorption capacity of MO was obtained in an acidic
pH medium. The equilibrium adsorption was increased
by increasing the initial dye concentration in the
solution. Adsorption kinetics data fitted well to a pseudo-
second-order kinetic model. The adsorption equilibrium
data fitted best to the Langmuir isotherm model. The
 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100
adsorption affinity correlated with the structural prop-
erties, essentially the interlayer spacing, in each LDH.
The precursors exhibited exceptional adsorption capaci-
ties indicating that these materials could be a potentially
efficient broad-spectrum adsorbent for dye removal from
wastewater. With respect to the selection of sorbents,
these results are of practical interest for the optimisation
of aquatic environment remediation technologies.
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