Anda di halaman 1dari 11

Available online at www.sciencedirect.


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

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 (

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

1. Introduction
Corresponding author. Tel.: +212 661 66 66 22;
Wastewater from the dyestuff manufacturing, dye-
fax: +212 523 49 03 54.
E-mail address: (N. Barka). ing, printing and textile industries presents a serious
Peer review under responsibility of Taibah University. 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
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 (
F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100 91

Table 1
Physicochemical characteristics of methyl orange.
Name Molecular Solubility pKa MW (g/mol) max (nm)
structure in water

Methyl orange (Acid orange 52) 5.2 3.47 327.33 465

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 perlite [20], sepiolite [21], montmorillonite [22] and
(ETAD), over 90% of some 4000 dyes have LD50 some natural biosorbents [23]. However, these materi-
values greater than 2000 mg/kg [5,6]. From an environ- als generally have low adsorption capacities, and hence,
mental point of view, the remediation of wastewater is a large adsorbent dosage is required to achieve a low dye
a great challenge and has attracted tremendous atten- concentration in the treated effluents.
tion in recent years. Different methods have been used Layered double hydroxides (LDHs), including
for dye removal from wastewaters such as biological hydrotalcite and hydrotalcite-like compounds, have
degradation [7], photodegradation [8], coagulation [9], received considerable attention due to their potential
membrane filtration [10], reverse osmosis [11], adsorp- applications in catalysis, photochemistry, electrochem-
tion [12], or the synergic treatment using different istry, polymerisation, magnetisation, biomedical science
methods. Among these methods, the adsorption process and environmental applications [2428]. LDHs are
is one of the most effective techniques that has been host-guest materials consisting of positively charged
successfully employed for colour removal because it is metal oxide/hydroxide sheets with intercalated anions
considered to be less expensive, more efficient and less and water molecules. They can be represented by the
likely to generate secondary waste [13]. Most conven- general formula: [M1x 2+ Mx 3+ (OH)2 ] (An )x/n mH2 O,
tional adsorption systems use activated carbon despite where M2+ is a divalent cation such as Mg2+ , Zn2+ , Cu2+ ,
its high production costs and regeneration difficulty [14]. etc., and M3+ is a trivalent cation such as Al3+ , Cr3+ ,
Recently, many low-cost adsorbents have been investi- Fe3+ , etc. Due to the partial substitutions of M3+ for M2+ ,
gated in the removal of dyes such as agricultural wastes the hydroxide sheets are positively charged and require
[15], clays [16], chitosan [17], silica [18], kaolinite [19], 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 aqueous solution containing Zn(NO3 )2 6H2 O (0.75 M)

Unit cell parameters and interlamellar distance of Zn-Al-LDHs. and Al(NO3 )3 9H2 O (0.25 M) was added dropwise to
Sample a (A) c (A) Interlamellar distance (A) a vigorously stirred solution of NaOH (2 M) and 0.2 M
Zn-Al-CO3 3.05 22.71 7.57
of the desired anion (CO3 2 , NO3 , Cl , or SO4 2 ).
Zn-Al-NO3 3.05 26.53 8.84 The resulting gels were hydrothermally treated at 80 C
Zn-Al-Cl 3.05 26.58 8.86 for 24 h to improve their crystallinities, were filtered,
Zn-Al-SO4 3.05 33.48 11.16 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
Cl , or SO4 2 , to retain the overall charge neutrality. and Zn-Al-SO4 .
The composition of LDH materials is tunable. That is,
the divalent cation or trivalent cation can be replaced or 2.3. Characterisation of the samples
partly replaced by other cations, and the interlayer anion
can also be replaced by other anions; thus, their physi- The powder X-ray diffraction (XRD) patterns were
cal and chemical properties can be altered [29]. LDHs recorded from 2 = 570 using a Bruker-axs D2-phaser
exhibit favourable characteristics for the adsorption of advance diffractometer operating at 30 kV and 10 mA
pollutants such as large surface areas, good thermal sta- with Cu K1 (1.54056 A) and K2 (1.54439 A) radia-
bilities, and high sorption and regeneration efficiencies tions. The FTIR spectra were collected on a Nicolet
[3033]. Moreover, LDHs are regarded as a class of Avatar 330 Fourier transform IR spectrophotometer. The
materials that are simple and economical to synthesise samples were mixed with KBr at a mass ratio of 1:100
in the laboratory. and finely powdered to prepare pellets. The spectra
In the present work, zinc aluminium-layered double were recorded with a 2 cm1 resolution in the range
hydroxides intercalated with carbonate, nitrate, chlo- of 4000400 cm1 . Transmission electron microscopy
ride, or sulphate were synthesised via a co-precipitation (TEM) images were obtained on a TEM TECNAI
method. The samples were characterised by powder G2/FEI instrument at an accelerating voltage of 120 kV.
XRD, FTIR, TEM and TGA-DTA. The effects of var- The simultaneous thermogravimetric-differential ther-
ious parameters such as solution pH, contact time and mal analysis (TGA-DTA) curves were recorded on a
dye concentration on the removal of methyl orange by SETARAM LabsysTM Evo model instrument under
these precursors were studied in detail. The adsorp- argon atmosphere in the temperature range of 30700 C
tion kinetic data were tested by pseudo-first-order and and with a heating rate of 10 C/min.
pseudo-second-order kinetic models. The equilibrium
data were analysed using the Langmuir, Freundlich and 2.4. Adsorption experiments
DubininRadushkevich isotherm models.
Stock solutions of 1 g/L of MO were prepared by
2. Experimental dissolving the appropriate amount of the dye in dis-
tilled water, and the concentrations that were used were
2.1. Materials obtained by dilution. The adsorption experiments were
performed in a series of 250-mL beakers containing the
All of the chemicals used in this study were of analyti- desired weight (20 mg) of each LDH and 250 mL of
cal grade. Zn(NO3 )2 6H2 O, Al(NO3 )3 9H2 O, Na2 CO3 , the methyl orange solution at the desired concentration.
Na2 SO4 , NaCl, NaNO3 and methyl orange were pur- These experiments were carried out at a constant agita-
chased from SigmaAldrich (Germany). NaOH was tion speed of 500 rpm by varying the pH of the solution
purchased from Merck (Germany) and HNO3 from from 2 to 12, the contact time from 5 to 360 min and
Scharlau (Spain). The chemical structure and some other the initial dye concentration from 20 to 1000 mg/L. The
specific characteristics of methyl orange are summarised solution pH was adjusted to a given value with the addi-
in Table 1. tion of HCl (1 N) or NaOH (1 N), and it was measured
using a SensION+ PH31 pH meter.
2.2. Synthesis of ZnAl layered double hydroxides After each adsorption experiment was completed,
the solid phase was separated from the liquid phase
ZnAl layered double hydroxides intercalated with by centrifugation at 3000 rpm for 15 min. The resid-
CO3 2 , NO3 , Cl , or SO4 2 were synthesised via a co- ual concentrations were determined from UVVis
precipitation method at a constant solution pH of 10. An characteristics at a maximum absorption wavelength of
F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100 93

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- (101), (015), (018), (110) and (113) planes at higher 2
tometer. values can be observed from the figure. The (003) peak
The adsorbed amounts at equilibrium (qe ) and at any indicates the basal reflection of an interlayer anion in
time (qt ) were calculated using the following equation: LDH materials. The first peak of the doublet close to a
(C0 Ce,t ) V 2 of approximately 60 is due to the orientation from
qe,t = , (1) the (110) planes, and its spacing corresponds to the lat-
tice parameter a, which coincides with the closest MM
where qe,t (mg/g) is the adsorbed quantity at equilib- distance in the brucite-like layers. The unit cell param-
rium (qe ) or at any time (qt ), C0 (mg/L) is the initial dye eters a and c can be calculated from the positions of
concentration, Ce,t (mg/L) is the dye concentration at these reflections: a = 2d110 and c = 3d003 . The obtained
equilibrium (Ce ) or at any time (Ct ), V (L) is the volume parameters are presented in Table 2. These lattice param-
of the solution, and m (g) is the mass of the LDH sample eters agree well with those reported for hydrotalcite-like
(g). compounds [34]. The interlamellar distances (d003 ) of
the samples were found to be 7.57, 8.84, 8.86 and 11.16
3. Results and discussion for Zn-Al-CO3 , Zn-Al-NO3 , Zn-Al-Cl and Zn-Al-SO4 ,
respectively. The difference in the values of the inter-
3.1. Characterisation lamellar distances is evidence of the size and charge
of the corresponding anions intercalated between the
3.1.1. XRD analysis layers.
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 3.1.2. FTIR
hexagonal lattice with rhombohedral 3R symmetry [24]. The FTIR spectra of the LDHs shown in
The basal peaks for the (003) and (006) planes at 2 val- Fig. 2 reveal bands characteristic of hydrotalcite-like
ues between 7 and 26 and the non-basal peaks for the 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 989 cm1 can be attributed to the weak bending modes
of the hydroxyl groups and H2 O molecules. The weak (2 ) and the symmetric stretching mode (1 ), respec-
band at 1630 cm1 can be assigned to the H2 O bending tively, for the sulphate anion present in the LDH
vibration of the interlayer water. The bands recorded [35].
at 460, 550, and 790 cm1 are ascribed to the Al-O
condensed groups, the Zn/Al-OH translation and the 3.1.3. TEM observation
Al-OH deformation, respectively. For the Zn-Al-CO3 Fig. 3 presents TEM images of different LDH
sample, the band around 1365 cm1 can be attributed samples. As shown, the Zn-Al-CO3 and Zn-Al-SO4
to the anti-symmetric stretching mode (3 ) of carbon- samples consisted of hexagonal platelets having some
ate, and bands observed around 870 and 680 cm1 small cracks at the edge of the hexagonal sheets and
are attributed to the weak non-planar bending mode part of the sheets presenting a vertical crossing at
(2 ) and the angular bending mode (4 ) of carbonate, the hexagonal sides. The particle size varied from 20
respectively. The FTIR spectra of Zn-Al-NO3 reveal a to 150 nm. The spherical particles can be observed
strong peak around 1380 cm1 attributed to the anti- in Zn-Al-NO3. The TEM micrograph of the Zn-Al-
symmetric stretching mode (3 ) of the nitrate anion Cl sample indicates the formation of agglomerates.
present in the LDH [35]. The bands observed around This difference in the size and morphology could be
839 and 670 cm1 can be attributed to the weak out- attributed to the nature and amount of the interlayer
of-plane symmetric deformation mode (2 ) and the anions.
anti-symmetric deformation mode (4 ) of nitrate, respec-
tively. The distortion of Cl in the interlayer of Zn-Al-Cl 3.1.4. TGA-DTA analysis
is reflected in the IR spectra with both 3 and 4 bands The thermogravimetric analysis of the synthesised
split at 11001145 cm1 and 626635 cm1 , respec- LDHs is shown in Fig. 4. All of the TGA-DTA pat-
tively. For Zn-Al-SO4 , the band observed at 1112 cm1 terns are characterised by a weight loss between 10
can be attributed to the stretching mode (3 ) of sul- and 14% due to the loss of the interlayer water in
phate, and the weak bands observed around 619 and 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

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

qe (mg/g)

100 60 Zn-Al-Cl

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 3.3. Kinetics
250 C. These steps can be interpreted as resulting from
the loss of adsorbed and interlayer water followed by The variation with contact time in the amounts of
water loosely coordinated to the interlayer carbonate. MO adsorbed is shown in Fig. 6. The figure indicates
The interlayer carbonate is released as CO2 at approx- that the adsorbed amounts increased rapidly in the first
imately 350 C. The total mass loss was 20.86%. For hour. Then, it slowed until equilibrium was established
Zn-Al-NO3 , there are mass losses at 150, 250, 350 and after 4 h for Mg-Al-CO3 and Mg-Al-Cl and 5 h for Mg-
450 C. The mass losses at 150 and 250 are accom- Al-NO3 and Mg-Al-SO4 . The figure also indicates that
panied by a change in the heat flow; it should result the adsorption affinity increased in the following order:
from the removal of the adsorbed surface water and the Zn-Al-CO3 , Zn-Al-NO3 , Zn-Al-Cl and Zn-Al-SO4 . This
interlayer water. The second distinct mass loss region result correlates with the differences in the structural
of 350460 C resulted from two processes, namely properties of each LDH, essentially the interlayer spac-
the dehydroxylation of the Zn-Al-LDH layers and the ing, as confirmed by XRD analysis.
decomposition of the interlayer NO3 anions. The total To characterise the kinetics involved in the process of
mass loss was 21.5%. TGA-DTA analysis for Zn-Al-Cl adsorption, pseudo-first-order and pseudo-second-order
shows a similar dehydration behaviour to that of Zn- kinetic models were proposed, and the kinetics data were
Al-NO3 , but Cl was lost in the temperature range of analysed based on the regression coefficient (r2 ) and the
400500 C. The total mass loss at 700 C was 18.84%. amount of dye adsorbed per unit weight of the adsorbent.
The decomposition of Zn-Al-SO4 occurred in the fol- The first-order rate expression of Lagergren based on
lowing steps: the first mass loss at 150 C corresponded the solid capacity is generally expressed as follows [37]:
to the evaporation of surface-adsorbed water followed
by evaporation of the interlayer water at 250 C; a third q = qe (1 ek1 t ), (2)
loss of mass occurring at 350 C is attributed to the
where qe and q (both in mg/g) are, respectively, the
dehydroxylation of the brucite-like octahedral layers.
amounts of dye adsorbed at equilibrium and at any time
The fourth step at 600 C was likely due to the elim-
t, and k1 (1/min) is the adsorption rate constant.
ination of the intercalated SO4 2 in the ZnAl LDH
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-
3.2. Effect of solution pH on the adsorption of MO
tion follows a second-order chemisorption mechanism.
The pseudo-second-order model can be expressed as:
Generally, pH is considered to be an important param-
eter controlling the adsorption at the water-adsorbent k2 qe 2 t
interface. Adsorption experiments were carried out q= , (3)
1 + k2 q e t
under the same experimental conditions by varying the
solution pH from 2 to 12. The obtained results are illus- where k2 (g/mg min) is the rate constant of the pseudo-
trated in Fig. 5. From the figure, it can be observed that second-order adsorption.
the amounts of MO adsorbed at equilibrium (qe ) were Parameters of the pseudo-first-order and pseudo-
higher under acidic conditions. The maximum adsorp- second-order models were estimated with the aid of a
tion was observed at a pH of approximately 4.5 and non-linear regression. The obtained data and the corre-
steadily decreased as the solution pH increased. The lation coefficients, r2 , are given in Table 3. The table
equilibrium was difficult to establish in alkaline con- shows that the correlation coefficient for the pseudo-
ditions because of the competition between the excess second-order kinetic model is closer to unity than that of
OH in the solution and the anionic molecules of MO. the pseudo-first-order models. From these results, it was
However, under acidic conditions, the equilibrium was concluded that the pseudo-second-order model was bet-
easy to establish because the rate of adsorption strongly ter than the Lagergren first-order model for the systems
depends on the chemical adsorption effect. The disso- investigated in this work. Because ion adsorption fol-
ciation constant (pKa ) of the MO is 3.46; therefore, the lows pseudo-second-order kinetics, this suggested that
monovalent anions of MO were predominantly present the boundary layer resistance was not the rate-limiting
at these equilibrium pHs. Furthermore, the structure of step [36]. The rate of MO adsorption may be con-
the LDH materials was destroyed when the pH was trolled largely by a chemisorption process in conjunction
below 4 [36]. In this case, the adsorption of MO strongly with the chemical characteristics of the LDHs and MO
decreased. 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- model [43]. The DubininRadushkevich isotherm has
ble hydroxides [39]. been written by the following equations:
qe = qm exp(B2 ) (6)
3.4. Adsorption isotherms  
= RT ln 1 +
The isotherms of the adsorption of methyl orange by Ce
LDHs are shown in Fig. 7. They all display the typical where B is a constant related to the adsorption energy,
L shape according to Giless classification [40]. MO qmax is the theoretical saturation capacity, and is the
is highly concentration dependent. The increase in the Polanyi potential.
adsorption capacity with the dye concentration in the A non-linear regression is used to determine the best-
solution is probably due to a high driving force for the fitting isotherm, and the applicability of the isotherm
mass transfer. In fact, a high concentration in the solution equations is compared by comparing the correlation
implicates a large number of dye molecules fixed at the coefficients, r2 . Table 4 shows the obtained results. The
surface of the adsorbent. The Langmuir, Freundlich and table indicates that the Langmuir equation gives the
Dubinin Redushkevich isotherm models were applied for best satisfactory fitting to the adsorption isotherms of
the analysis of the obtained equilibrium sorption data. the MO adsorption onto the LDH samples with higher
The Langmuir adsorption model is based on the correlation coefficients than the others, indicating the
assumption that the maximum adsorption corresponds homogeneous nature of all the surfaces and the for-
to a saturated monolayer of solute molecules on the mation of a monolayer of methyl orange molecules
adsorbent surface. Therefore, The Langmuir isotherm on the surface of the adsorbents. The Langmuir maxi-
assumes that sorption comes from the monolayer cov- mum adsorption capacities were 2758, 2455, 2270 and
erage of the adsorbate over a homogenous adsorbent 1684 mg/g for Zn-Al-SO4 , Zn-Al-Cl, Zn-Al-NO3 and
surface [41]. This model supposes that sorption occurs Zn-Al-CO3 , respectively.
on specific homogeneous sites within the adsorbent and The adsorption capacities decreased in the follow-
that all of the sorption sites are energetically identical. ing order: Zn-Al-SO4 > Zn-Al-Cl > Zn-Al-NO3 > Zn-
The Langmuir isotherm can be written in the following Al-CO3 . This behaviour can be attributed to the peculiar
form: structural properties of each LDH. As confirmed by
XRD, the interlayer spacing decreased in the same order.
qm KL Ce
qe = , (4) The main mechanism for the MO adsorption on the
1 + KL C e LDHs could be the ion exchange between the MO anions
where qm (mg/g) is the maximum amount of dye and previously intercalated anions, although the surface
adsorbed per unit mass of adsorbent, and KL (L/mg) is adsorption is also presumed to be involved [44].
the Langmuir constant related to the rate of adsorption.
Ce is the equilibrium concentration. 4. Conclusion
The Freundlich isotherm is an empirical model of a
heterogeneous surface with a non-uniform distribution ZnAl layered double hydroxides intercalated with
of heat sorption and affinities by means of multilayer CO3 2 , NO3 , Cl or SO4 2 were successfully pre-
adsorption [42]. pared via a co-precipitation method. The presence
The form of the Freundlich equation can be stated as of the anions in the hydrotalcite structure was con-
follows: firmed by infrared spectroscopy. The XRD analyses
showed that the interlayer spacing followed this order:
qe = KF Ce1/n , (5) Zn-Al-SO4 > Zn-Al-Cl > Zn-Al-NO3 > Zn-Al-CO3 . All
TGA-DTA curves are characterised by a weight loss
where KF (mg11/n /g/Ln ) and n are Freundlich constants, between 10 and 14% due to a loss of interlayer water
n indicates whether the adsorption process is favourable, in the temperature range of 50250 C. The maximum
and KF is related to the adsorption capacity of the adsor- adsorption capacity of MO was obtained in an acidic
bent. pH medium. The equilibrium adsorption was increased
The DubininRadushkevich isotherm model does not by increasing the initial dye concentration in the
assume a homogenous surface or a constant sorption solution. Adsorption kinetics data fitted well to a pseudo-
potential, as other models do. It can be noted that this second-order kinetic model. The adsorption equilibrium
isotherm model is more general than the Langmuir data fitted best to the Langmuir isotherm model. The
F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100 99

adsorption affinity correlated with the structural prop- [14] N. Barka, A. Assabbane, Y. At Ichou, A. Nounah, Decontamina-
erties, essentially the interlayer spacing, in each LDH. tion of textile wastewater by powdered activated carbon, J. Appl.
The precursors exhibited exceptional adsorption capaci- Sci. 6 (3) (2006) 692695.
[15] M.A. Ahmad, N.A. Ahmad Puad, O.S. Bello, Kinetic, equi-
ties indicating that these materials could be a potentially librium and thermodynamic studies of synthetic dye removal
efficient broad-spectrum adsorbent for dye removal from using pomegranate peel activated carbon prepared by microwave-
wastewater. With respect to the selection of sorbents, induced KOH activation, Water Resour. Ind. 6 (2014) 1835.
these results are of practical interest for the optimisation [16] R. Elmoubarki, F.Z. Mahjoubi, H. Tounsadi, J. Moustadraf, M.
of aquatic environment remediation technologies. Abdennouri, A. Zouhri, A. ElAlbani, N. Barka, Adsorption of
textile dyes on raw and decanted Moroccan clays: kinetics, equi-
librium and thermodynamics, Water Resour. Ind. 9 (2015) 1629.
[17] F.-C. Tsai, N. Ma, T.-C. Chiang, L.-C. Tsai, J.-J. Shi, Y. Xia,
References T. Jiang, S.-K. Su, F.-S. Chuang, Adsorptive removal of methyl
orange from aqueous solution with crosslinking chitosan micro-
[1] K. Itoh, Y. Kitade, C. Yatote, A pathway for biodegradation of an spheres, J. Water Process Eng. 1 (2014) 27.
anthraquinone dye, C.I. Disperse Red 15, by a yeast strain Pichia [18] M. Zarezadeh-Mehrizi, A. Badiei, Highly efficient removal of
anomala, Bull. Environ. Contam. Toxicol. 56 (1996) 413418. basic blue 41 with nanoporous silica, Water Resour. Ind. 5 (2014)
[2] H.M. Pinherio, E. Touraud, O. Tomas, Aromatic amines from 4957.
azo dye reduction: status review with emphasis on direct UV [19] M. Dogan, M.H. Karaoglu, M. Alkan, Adsorption kinetics of
spectrophotometric detection in textile industry wastewater, Dyes maxilon yellow 4GL and maxilon red GRL dyes on kaolinite,
Pigments 61 (2004) 121139. J. Hazard. Mater. 165 (2009) 11421151.
[3] N. Barka, S. Qourzal, A. Assabbane, A. Nounah, Y. Ait-Ichou, [20] M. Dogan, M. Alkan, Adsorption kinetics of methyl violet onto
Triphenylmethane dye, patent blue V, photocatalytic degradation perlite, Chemosphere 50 (2003) 517528.
on supported TiO2 : kinetics, mineralization and reaction pathway, [21] Y. Ozdemir, M. Dogan, M. Alkan, Adsorption of cationic dyes
Chem. Eng. Commun. 198 (2011) 12331243. from aqueous solutions by sepiolite, Microporous Mesoporous
[4] T. Suzuki, S. Timofei, L. Kurunczi, U. Dietze, G. Schuurmann, Mater. (2006) 419427.
Correlation of aerobic biodegradability of sulfonated azo dyes [22] A.H. Gemeay, A.S. El-Sherbiny, A.B. Zaki, Adsorption and
with the chemical structure, Chemosphere 45 (2001) 19. kinetic studies of the intercalation of some organic compounds
[5] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation onto Na+ -montmorillonite, J. Colloid Interface Sci. 245 (2002)
of dyes in textile effluent: a critical review on current treatment 116125.
technologies with a proposed alternative, Bioresour. Technol. 77 [23] N. Barka, K. Ouzaouit, M. Abdennouri, M. El Makhfouk, Dried
(2001) 247255. prickly pear cactus (Opuntia cus indica) cladodes as a low-
[6] J. Shore, Advances in direct dyes, Indian J. Fibre Text. Res. 21 cost and eco-friendly biosorbent for dyes removal from aqueous
(1996) 129. solutions, J. Taiwan Inst. Chem. Eng. 44 (2013) 5260.
[7] A.B.D. Santos, F.J. Cervantes, J.B.V. Lier, Review paper on [24] F. Cavani, F. Trifirb, A. Vaccari, Hydrotalcite-type anionic clays:
current technologies for decolorisation of textile wastewaters: preparation properties and applications, Catal. Today 11 (1991)
perspectives for anaerobic biotechnology, Bioresour. Technol. 98 173301.
(2007) 23692385. [25] V. Rives, Layered Double Hydroxides: Present and Future, Nova
[8] A. Abaamrane, S. Qourzal, N. Barka, S. Mancour-Billah, A. Science Publishers, Inc., New York, 2001.
Assabbane, Y. Ait-Ichou, Optimal decolorization efficiency of [26] F. Li, X. Duan, Applications of layered double hydroxides, Struct.
indigo carmine by TiO2 /UV photocatalytic process coupled with Bond. 119 (1) (2005) 193223.
response surface methodology, Orient. J. Chem. 28 (3) (2012) [27] D.G. Evans, X. Duan, Preparation of layered double hydroxides
10911098. and their applications as additives in polymers, as precursors to
[9] M.V. Sureshkumar, C. Namasivayam, Adsorption behavior of magnetic materials and in biology and medicine, Chem. Commun.
Direct Red 12B and Rhodamine B from water onto surfactant- 5 (2006) 485496.
modified coconut coir pith, Colloids Surf. A: Physicochem. Eng. [28] S. Mandal, S. Mayadevi, Adsorption of fluoride ions by ZnAl
Aspects 317 (2008) 277283. layered double hydroxides, Appl. Clay Sci. 40 (2008) 5462.
[10] E. Alventosa-deLara, S. Barredo-Damas, E. Zuriaga-Agust, M.I. [29] T. Ishikawa, K. Matsumoto, K. Kandori, T. Nakayama, Anion-
Alcaina-Miranda, M.I. Iborra-Clar, Ultrafiltration ceramic mem- exchange and thermal change of layered zinc hydroxides formed
brane performance during the treatment of model solutions in the presence of Al(III), Colloids Surf. A: Physicochem. Eng.
containing dye and salt, Sep. Purif. 129 (2014) 96105. Aspects 293 (2007) 135145.
[11] K. Ravikumar, S. Krishnan, S. Ramalingam, K. Balu, Optimiza- [30] J.W. Boclair, P.S. Braterma, Layered double hydroxide stability. 1.
tion of process variables by the application of response surface Relative stabilities of layered double hydroxides and their simple
methodology for dye removal using a novel adsorbent, Dyes Pig- counterparts, Chem. Mater. 11 (1999) 298302.
ments 72 (2007) 6674. [31] C.D. Hoyo, Layered double hydroxides and human health: an
[12] M. Ghaedi, A. Golestani Nasab, S. Khodadoust, R. Sahraei, A. overview, Appl. Clay Sci. 36 (2007) 103121.
Daneshfar, Characterization of zinc oxide nanorods loaded on [32] J. Das, D. Das, K.M. Parida, Preparation and characterization of
activated carbon as cheap and efficient adsorbent for removal of MgAl hydrotalcite-like compounds containing cerium, J. Col-
methylene blue, J. Ind. Eng. Chem. 21 (2015) 986993. loid Interface Sci. 30 (2006) 569574.
[13] M. Arami, N.Y. Limaee, N.M. Mahmoodia, Evaluation of the [33] S.V. Prasanna, P.V. Kamath, Chromate uptake characteristics of
adsorption kinetics and equilibrium for the potential removal of the pristine layered double hydroxides of Mg with Al, Solid State
acid dyes using a biosorbent, Chem. Eng. J. 139 (2008) 210. Sci. 10 (2008) 260266.
100 F.Z. Mahjoubi et al. / Journal of Taibah University for Science 11 (2017) 90100

[34] J.T. Kloprogge, D. Wharton, L. Hickey, R.L. Frost, Infrared and [40] C.H. Giles, T.H. Mac Ewan, S.N. Nakhwa, P. Smith, Studies on
Raman study of interlayer anions CO3 2 , NO3 , SO4 2 and adsorption XI. A system of classification of solution adsorption
ClO4 in Mg/Al-hydrotalcite, Am. Miner. 87 (2002) 623. isotherms and its use in diagnosis of adsorption mechanisms and
[35] I.D. Mall, V.C. Srivastava, N.K. Agarwal, Removal of Orange- in measurement of specific surface areas of solids, J. Chem. Soc.
G and Methyl Violet dyes by adsorption onto bagasse fly ash 111 (1960) 39733993.
kinetic study and equilibrium isotherm analyses, Dyes Pigments [41] I. Langmuir, The constitution and fundamental properties of
69 (2006) 210223. solids and liquids, J. Am. Chem. Soc. 38 (1916) 22212295.
[36] J. Das, B.S. Patra, N. Baliarsingh, K.M. Parida, Appl. Clay Sci. [42] H. Freundlich, W. Heller, The adsorption of cis- and trans-
32 (2006) 252. azobenzene, J. Am. Chem. Soc. 61 (1939) 22282230.
[37] S. Lagergren, About the theory of so-called adsorption of soluble [43] M.M. Dubinin, L.V. Radushkevich, The equation of the charac-
substance Seven Vetenskapsakad, Handband 24 (1898) 139. teristic curve of the activated charcoal, Proc. Acad. Sci. USSR
[38] Y.S. Ho, G. McKay, Pseudo-second order model for sorption Phys. Chem. Sect. 55 (1947) 331337.
processes, Process Biochem. 34 (1999) 451465. [44] E.L. Crepaldi, J. Tronto, L.P. Cardoso, J.B. Valim, Sorption of
[39] H. Zaghouane-Boudiaf, M. Boutahala, L. Arab, Removal of terephthalate anions by calcined and uncalcined hydrotalcite-like
methyl orange from aqueous solution by uncalcined and calcined compounds, Colloid Surf. A: Physicochem. Eng. Aspects 211
MgNiAl layered double hydroxides (LDHs), Chem. Eng. J. 187 (2002) 103114.
(2012) 142149.