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Chemical Engineering Journal 171 (2011) 167–174

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Chemical Engineering Journal

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The adsorption of Pb(II) on Mg2 Al layered double hydroxide

Donglin Zhao a,b , Guodong Sheng a , Jun Hu a , Changlun Chen a,∗ , Xiangke Wang a,∗
a
Key Laboratory of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031, PR China
b
School of Materials and Chemical Engineering, Anhui University of Architecture, Hefei 230601, PR China

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

Article history: The adsorption behavior of Pb(II) by Mg2 Al layered double hydroxide (Mg2 Al LDH) was studied as a func-
Received 11 December 2010 tion of contact time, pH, ionic strength, foreign ions, humic substances and temperature under ambient
Received in revised form 23 March 2011 conditions. The results showed that the kinetic adsorption could be described by a pseudo-second order
Accepted 23 March 2011
model very well. The adsorption of Pb(II) on Mg2 Al LDH was strongly dependent on pH and ionic strength.
The presence of HSs enhanced the adsorption of Pb(II) on Mg2 Al LDH at low pH, whereas reduced Pb(II)
Keywords:
adsorption at high pH. The Langmuir model fitted the adsorption isotherms of Pb(II) better than the
Pb(II)
Freundlich model at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic
Mg2 Al LDH
Adsorption
parameters (H◦ , S◦ and G◦ ) calculated from the temperature dependent adsorption isotherms indi-
cated that the adsorption process of Pb(II) on Mg2 Al LDH was endothermic and spontaneous. The results
show that Mg2 Al LDH is a promising material for the preconcentration and separation of pollutants from
large volumes of aqueous solutions.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction hydrotalcite-like compounds been used as adsorbents for heavy

Because of their special structure and unique applications, lay-
ered double hydroxides (LDHs), also known as hydrotalcite-like
compounds or anionic clays, are bidimensional solids with posi-
tive charge excess in their brucite (Mg(OH)2 )-like layers and have
received considerable attention. LDHs have the structural formula
x+
[M1−x II Mx III (OH)2 ] Ax/n n− · yH2 O, where MII and MIII denote diva-
lent (e.g., Ni, Zn, and Mg) and trivalent metals (e.g., Cr, Fe, and
Al), respectively; An− represents interlayer anions, such as NO3 − ,
SO4 2− , and CO3 2− , and x typically ranges from 0.17 to 0.33 [1]. This
charge excess is produced by isomorphic substitution of divalent
by trivalent cations and compensated by the introduction of anions
(together with water) in the interlayer space [2,3]. Since the inter-
layer anions are easily exchangeable, the anions in the interlayer
can be exchanged by other anions so that high anion exchange capa-
bility is the most remarkable characteristic of LDHs. Meanwhile, the
ease of preparation and widely variable ways in which their com-
ponents can be combined make LDHs useful for many applications
[2,4].
Recently, LDHs containing chelating agents such as ethylene-
diaminetetraacetate (EDTA) [5,6] and nitrilotriacetate (NTA) [7,8],
as well as the adsorption of heavy metal cations by these mate-
rials, were reported. These implied that LDHs could be used as
adsorbents for heavy metal cations. However, only recently have
∗ Corresponding authors. Tel.: +86 551 5592788; fax: +86 551 5591310.
E-mail addresses: clchen@ipp.ac.cn (C. Chen), xkwang@ipp.ac.cn (X. Wang).
metals [5,7,9–14]. The detailed reaction mechanisms of metal
cations in an aqueous solution with LDHs are therefore required
to exploit these materials in remediation applications.
The objectives of this work were: (1) to characterize the Mg2 Al
LDH sample by Fourier transform infrared (FT-IR) spectroscopy
for chemical functional groups and by X-ray powder diffraction
(XRD) for chemical composition; (2) to study the effects of dif-
ferent parameters on Pb(II) adsorption, such as contact time, pH,
ionic strength, coexisting electrolyte ions, humic substances (HSs)
and temperature; (3) to determine the thermodynamic parame-
ters of Pb(II) adsorption on Mg2 Al LDH; and (4) to presume the
adsorption mechanisms of Pb(II) on Mg2 Al LDH and to estimate
the possible application of Mg2 Al LDH in wastewater treatment.
Pb(II) is selected as a representative of bivalent metal ions because
of its ubiquitous present in wastewater.
2. Experimental
2.1. Materials
Mg2 Al LDH was prepared by co-precipitation according to Miy-
ata’s procedure [15]. MgCl2 ·6H2 O and AlCl3 ·6H2 O in the molar ratio
2:1 Mg/Al = 2.0 and 0.15 mol L−1 of total metals concentration were
dissolved in deionized water to prepare a mixed solution. The mix-
ture was adjusted to pH 10 by the addition of an ammonia solution
(6.0 wt%) and was stirred for 20 min. The mixture was aged for
60 min at room temperature, filtered and washed with distilled
water to remove the excess of ammonia. The filter cakes were

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.03.082
 Author's personal copy
168 D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174
further hydrothermally treated at 80 ◦ C for 24 h to improve their
crystallinity, forming Mg2 Al LDH sol samples. The sol was dried,
triturated and sieved to prepare for the adsorption experiments.
Humic acid (HA) and fulvic acid (FA) were extracted from the
soil of Hua-Jia county (Gansu province, China) near 35◦ N and 105◦ E
and has been characterized in detail [16,17]. Natural organic matter,
such as HA and FA, exists ubiquitously in natural aquatic environ-
ments. The presence of HA and FA may influence the adsorption
of heavy metal ions on solid in natural environment. Hence, the
HA and FA extracted from the soil were used as the representa-
tive of natural organic matter natural environment to determine
their effect on the adsorption behaviors of heavy metal ions at the
solid–water interface.
All other chemicals were purchased in analytical purity and used
without further purification and all solutions were prepared with
Milli-Q water under ambient conditions.
2.2. Experimental procedures
All the experiments were carried out using batch techniques in
polyethylene centrifuge tubes under ambient conditions. The stock
solutions of Mg2 Al LDH, NaClO4 , and Pb(II) were added to achieve
the desired concentrations of different components. The pH of each
test solution was adjusted to desired values by adding negligible
volumes of 0.01 or 0.1 M HClO4 or NaOH. After the suspensions were
shaken for 24 h, the solid and liquid phases were separated by cen-
trifugation at 9000 rpm for 30 min. The adsorption of Pb(II) on the
tube wall was negligible according to the test of Pb(II) adsorption
in the absence of Mg2 Al LDH.
The concentration of Pb(II) was analyzed by atomic absorption
spectrophotometry. The amounts of adsorbed Pb(II) were calcu-
lated from the difference between the initial (C0 ) and equilibrium
(Ce ) concentrations in the supernatant after centrifugation. The
adsorption percentage [adsorption (%) = (C0 − Ce )/C0 × 100] was
derived from the difference between C0 and Ce . All experimental
data were the average of triplicate determinations and the relative
errors were about 5%.
3. Results and discussion
3.1. Characterization
The surface functional groups were characterized by FT-IR. The
FT-IR of the sample is shown in Fig. 1, the spectrum was similar
to that reported by Cavani and Trifiro [2]. The spectrum exhib-
ited an intense broad band at 3451 cm−1 , which contributed to
Fig. 1. FT-IR spectrum of Mg2 Al LDH sample.
Fig. 2. XRD pattern of Mg2 Al LDH sample and adsorption products. (A) Mg2 Al LDH
and (B) Pb–Mg2 Al LDH.
the stretching vibration of structural O–H groups hydrogen bonded
with interlamellar water or O–H groups in adjacent layers. Another
band at 1623 cm−1 was due to the bending vibration of H–O–H
(ıH−O−H ) and it should be assigned to the adsorbed water molecule
in the interlayer. An intense absorption band at about 1363 cm−1
was assigned to the 3 mode asymmetric stretching of CO3 2− in the
interlayer, indicating that some CO3 2− ions existed in the gallery of
Mg2 Al LDH sample [13,18]. Also, the carbonate showed an absorp-
tion band at 676 cm−1 . The absorption at 573 cm−1 might be related
to the lattice vibrations, such as Mg–O–Al or O–Mg–O vibration
[12,19,20]. In particular, the sharp peak at 447 cm−1 was the def-
inite evidence of Mg2 Al LDH [21,22]. Elemental analysis gave the
atomic ratio [Mg]/[Al] of about 1.9 (Table S1), which was slightly
lower than the designed value (2.0).
Structural characterization of Mg2 Al LDH was carried out by
powder X-ray diffraction (XRD) in a Scintag XDS-2000 diffractome-
ter with Cu K␣ radiation ( = 1.5418 Å) operated at a voltage of
45 kV and current of 40 mA. The typical XRD pattern was shown
in Fig. 2A, the peaks at lower 2 values were sharp and symmetric
compared to those at higher 2 values, which were characteris-
tic of clay minerals having a layered structure [2,23,24]. All the
peaks were similar to hydrotalcite Mg6 Al2 CO3 (OH)16 ·4H2 O (JCPDS
card no. 22-700) [13,25] and secondary phases such as Al(OH)3 and
Mg(OH)2 were not observed in the XRD patterns, indicating that
Mg2 Al LDH sample had pure hydrotalcite crystal structure. Dur-
ing the preparation process of the hydrotalcite, there existed trace
amount of other material, which might result in the specified peaks
in the XRD pattern of the as-prepared hydrotalcite.
Elemental analysis (Table S1) gave information about the exis-
tence of chloride in interlayer space. From the XRD pattern (Fig. 2A),
using the (0 0 3) peak and Bragg equation, it was possible to calcu-
late the interlayer space (d-spacing) of the sample, and then gallery
height could be calculated through the interlayer space minus layer
thickness. For Mg2 Al LDH sample, the d-spacing and gallery height
were about 0.79 and 0.31 nm, respectively [13]. We could therefore
give information there exist two anions (carbonate and chloride) in
the LDH structure [2].
It can be obviously seen that the equilibrium pH values are about
9 (Fig. S1). Also, it can be clearly observed that the equilibrium
concentrations of Mg (Fig. S2A) and Al (Fig. S2B) of the super-
natant values dissolved from solid during the adsorption process
decreased with increasing pH.
For the adsorption products of Pb–Mg2 Al LDH (Fig. 2B), the
intensities of samples were decreased compared with the samples
before adsorption. For Pb–Mg2 Al LDH, a new phase can be detected
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D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174
Fig. 3. Time dependent of Pb(II) adsorption on Mg2 Al LDH. pH = 5.70 ± 0.01,
I = 0.01 mol L−1 NaClO4 , C(Pb)initial = 15.0 mg L−1 , m/V = 0.2 g L−1 , and T = 303.15 K.
as lead oxide chloride hydrate [26] or carbonate chloride [12] and all
the character peaks of the Mg2 Al LDH sample were also observed,
however, the intensities of the XRD peaks decreased, indicating that
the Pb(II) adsorption did not obviously affect the layered crystal
structure of the Mg2 Al LDH [12]. The decrease of the XRD peak
intensities (Fig. 2B) maybe arises from the slight decomposition of
LDH sample, which was evidenced by analyzing the supernatant
after adsorption (Fig. S2). The results showed that Pb(II) adsorp-
tion on Mg2 Al LDH took place partly though precipitation reaction
[13,27].
3.2. Time dependent adsorption
Fig. 3 indicated the adsorption of Pb(II) on Mg2 Al LDH as a
function of contact time. The adsorption of Pb(II) onto Mg2 Al LDH
increased sharply within the first 30 min, then it rises slowly and
reaches equilibrium in 4.0 h. According to the above results, the
shaking time was fixed at 24 h in the following experiments to
ensure that the adsorption reaction can achieve complete equilib-
rium. The fast Pb(II) removal rate in the beginning is attributed
to the rapid diffusion of Pb(II) from the solution to the external
surfaces of Mg2 Al LDH. The subsequent slow adsorption process
is attributed to the longer diffusion range of Pb(II) into the inner-
sphere of Mg2 Al LDH or the ion-exchange in the inner surface of
Mg2 Al LDH. Such slow diffusion will lead to a slow increase in the
adsorption curve at later stages [28]. Moreover, the initial rapid
adsorption may be because of an increased number of available
sites at the initial stage. The increase in concentration gradient
tends to increase in Pb(II) adsorption rate at the initial stages. As
time proceeds, the concentration gradients became reduced owing
to the accumulation of Pb(II) adsorbed on the surface sites, lead-
ing to the decrease in adsorption rate at the later stages. Here, the
pseudo-first-order and pseudo-second-order kinetic models have
been employed to fit the experimental data. The pseudo-first-order
kinetic model [29] describes the adsorption of liquid/solid system
based on solid capacity. The model can be written as:
dqt
= k1 (qe − qt )
dt
where qe and qt is the capacity of metal ions adsorbed (mg g−1 )
at equilibrium and time t (h), respectively and k1 is the pseudo-
first-order rate constant (h−1 ). After integration between boundary
conditions (t = 0 to t and qe = 0 to qe ), Eq. (1) can be rewritten as:
k1
log(qe − qt ) = log qe − t (2)
2.303
169
Fig. 4. Effect of ionic strength on Pb(II) adsorption on Mg2 Al LDH as a function of
initial pH. m/V = 0.2 g L−1 , C(Pb)initial = 15.0 mg L−1 , and T = 303.15 K.
Thus the values of qe and k1 can be determined experimentally
by plotting log(qe − qt ) versus t and extracting information from
the least squares analysis of slope and intercept and substituting
into Eq. (2). The values of qe and k1 calculated from the linear form
analysis (Fig. S3A) are 57.51 mg g−1 and 2.60 h−1 , respectively.
The pseudo-second-order adsorption kinetic model is expressed
as following formulation [30]:
dqt
= k2 (qe − qt )2 (3)
dt
where k2 (g mg−1 h−1 ) is the pseudo-second-order rate constant
for the adsorption, and is a complex function of the initial con-
centration of solute. Eq. (3) can be rearranged to give the linear
expression:
t 1 1
= 2
+ t (4)
qt k2 qe qe
Thus the values of k2 and qe can be calculated from the intercept
and the slope of the linear relationship, Eq. (4), between t/qt and t.
The kinetic model parameters are obtained from fitting results
and presented in Table 1. From the fit curve shown in Fig. 3 and the
relative coefficient, it can be seen that the pseudo-second-order
kinetic model fit the adsorption of Pb(II) on Mg2 Al LDH better than
the pseudo-first-order model.
3.3. Effect of pH and ionic strength
Fig. 4 shows that the adsorption of Pb(II) on Mg2 Al LDH is obvi-
ously influenced by pH values. The adsorption curve of Pb(II) on
Mg2 Al LDH can be divided into three regions. The adsorption of
Pb(II) in 0.01 M NaClO4 solution increases gradually from 14% to
91% when pH increases from 3.5 to 7 (region I). In region II, from
pH 7 to 10, the adsorption of Pb(II) on Mg2 Al LDH maintains at
the maximum value of 91%. Above pH 10, the removal of Pb(II)
gradually decreases with increasing pH (region III). The results are
similar to the adsorption of Pb(II) on MX-80 bentonite [31–33] and
Na-rectorite [16]. The adsorption edges spread over three pH units
indicates the formation of multifarious surface complexes and rep-
resents different adsorption mechanisms [34]. The increase of Pb(II)
(1)
adsorption on Mg2 Al LDH with increasing pH may be attributed to
the surface properties of Mg2 Al LDH in terms of surface charge and
dissociation of functional groups. The surface of Mg2 Al LDH con-
tains a large number of binding sites and may become positively
charged at low pH due to the protonation reaction on the surfaces
(i.e., SOH + H+ ⇔ SOH2 + ). At pH < 10.7, the surfaces were positively
charged, and at pH > 10.7 the surfaces were negatively charged. The
zero point of change (pHzpc ) is about 10.7 (Fig. S4). The electrostatic
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170 D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174

Table 1
The kinetics models for the adsorption of Pb(II) on Mg2 Al LDH.

Temp. (K) qe,exp (mg g−1 ) Pseudo first-order kinetic model Pseudo second-order kinetic model
−1 −1 −1 −1
k1 (h ) qe,mod (mg g ) R2
k2 (g mg h ) qe,mod (mg g−1 ) R2

303.15 59.86 2.60 57.51 0.945 0.17 60.98 0.998

repulsion occurred between metal ions and the edge groups with complex adsorption of Pb2+ on Mg2 Al LDH samples can be described
positive charge (SOH2 + ) on Mg2 Al LDH surface results in the low as follows [12]:
adsorption efficiency of Pb(II). At high pH values, the surface of
Mg2 Al LDH becomes negatively charged due to the deprotonation Sur–OH + Pb2+ → Sur–O–Pb+ + H+ chemicalbindingadsorption
process (i.e., SOH ⇔ SO− + H+ ) and electrostatic repulsion decreases
with raising pH because of the reduction of positive charge density Sur–O− + Pb2+ → Sur–O−···Pb2+ electrostaticbindingadsorption
on the adsorption edges, which enhances the adsorption of the pos-
itively charged Pb(II) ions through electrostatic force of attraction. Outer-sphere surface complexes are expected to be more
The characteristic of Pb(II) complex that predominates at a spe- impressionable to ionic strength variations than inner-sphere com-
cific solution pH may also play an important role in the removal plexes as the background electrolyte ions are placed in the same
efficiency of Mg2 Al LDH towards Pb(II). According to the hydroly- plane for outer-sphere surface complexes [39]. By the above
sis constants of Pb(II) (log K1 = 6.48, log K2 = 11.16, log K3 = 14.16, analysis, one can deduce that outer-sphere surface complexation
Kn = [Pb(OH)2−n + n 2+ contributes to Pb(II) adsorption on Mg2 Al LDH at pH < 7, while
n ] · [H ] /[Pb ]) [35], Pb(II) ions present in the
forms of Pb , Pb(OH) , Pb(OH)2 0 , Pb(OH)3 − and Pb3 (OH)4 2− at var-
2+ + inner-sphere surface complexation is the adsorption mechanism
ious pH values. At pH < 7, the predominant Pb(II) species is Pb2+ of Pb(II) on Mg2 Al LDH at pH > 7 [40]. For Pb–Mg2 Al LDH (Fig. 2B),
and the removal of Pb(II) is mainly accomplished by adsorption the results showed that Pb(II) adsorption on Mg2 Al LDH took place
reaction. The adsorption of Pb(II) that takes place at pH < 7 (region partly though precipitation reaction. Therefore, it was apparent
I) can be attributed to the ion exchange between Pb2+ and H+ on from this study that Mg2 Al LDH removed Pb(II) metal cations from
the surface ion exchange sites. In the range of pH 7–10 (region II), aqueous solution mainly by surface complex adsorption and pre-
the removal of Pb(II) gets to maximum and maintains high level. cipitation [14].
The predominant species at pH 7–10 are Pb(OH)+ and Pb(OH)2 0 In our earlier study [41], the main mechanisms of Pb(II) removal
and thus the removal of Pb(II) is possibly accomplished by simul- by other materials such as diatomite, ␤-MnO2 and cyclodextrin
taneous precipitation of Pb(OH)2 0 and adsorption of Pb(OH)+ . At grafted onto multiwall carbon nanotube/iron oxides were surface
the pH range of 10–12 (region III), the main species are Pb(OH)2 0 complexation. However, Pb(II) removal by Mg2 Al LDH was mainly
and Pb(OH)3 − , hence, the decrease of Pb(II) adsorption on Mg2 Al dominated by surface complexation and precipitation, especially at
LDH can be partly attributed to the competition between OH− and high pH values.
Pb(OH)3 − . At higher pH values, the negative charged Pb(OH)3 − is
difficult to be adsorbed on the negatively charged surface of Mg2 Al 3.4. Effect of solid content
LDH due to electrostatic repulsion. It is necessary to make certain
whether the formation of Pb(OH)2 (s) precipitation contributes to Fig. 5 shows the dependence of Pb(II) adsorption on Mg2 Al LDH
the adsorption of Pb(II) on Mg2 Al LDH. at different solid contents. The adsorption of Pb(II) increases rapidly
From Fig. 4, the adsorption of Pb(II) on Mg2 Al LDH increases with increasing Mg2 Al LDH contents. With increasing solid con-
with decreasing ionic strength at pH < 7. This phenomenon may be tents, the number of functional groups at the Mg2 Al LDH surfaces
contributed to the facts: (1) the ionic strength of solution affects increases, hence, more exchangeable surface sites are available to
the activity coefficient of Pb(II) ions, which limits their transfer to form complexes with Pb(II) at solid surfaces. The adsorption capac-
Mg2 Al LDH surfaces [36,37]; one possible interpretation was that ity of Pb(II) on Mg2 Al LDH decreases gradually with the increase of
at lower concentrations of Pb(II) ions, Pb(II) ions were completely solid content. The solid surface is composed of sites with a spectrum
solvated in water and were combined with water molecules. At of binding energies. At low adsorbent content, all kinds of sur-
the lower ionic strength, Pb(II) ions combined with more water face sites are entirely exposed for adsorption and the surface gets
molecules (Fig. S5A), and at the higher ionic strength, Pb(II) ions to saturation faster, resulting in a higher adsorption capacity. But
combined with less water molecules (Fig. S5B). This can affect
the activity coefficient of Pb(II) ions in solution; (2) Pb(II) ions
form electrical double layer complexes with Mg2 Al LDH, which
is in favour of the adsorption when the concentration of the
competing salt is decreased. This may show that the adsorption
interaction between the functional groups of Mg2 Al LDH and Pb(II)
ions is mainly an ionic interaction in nature, which is in agree-
ment with the ion exchange mechanism; (3) ionic strength effects
can impact particle aggregation by affecting electrostatic inter-
actions. From Fig. S6, with increasing ionic strength, the particle
aggregations were enhanced due to the reduction of electrostatic
repulsion, and thereby improves particle aggregation of Mg2 Al LDH,
which reduces the amount of available binding sites and thereby
decreases the adsorption of Pb(II) on Mg2 Al LDH [38].
The surface of Mg2 Al LDH has some hydroxyl groups as func-
tional groups that can react with Pb2+ by chemical binding to
form inner-sphere complexes. Meanwhile there are some depro-
tonated hydroxyl groups (Sur–O− ) which may form outer-sphere Fig. 5. Adsorption of Pb(II) on Mg2 Al LDH as a function of solid content.
complexes with Pb2+ through electrostatic binding reaction. The pH = 5.70 ± 0.01, C(Pb)initial = 15.0 mg L−1 , I = 0.01 mol L−1 NaClO4 , and T = 303.15 K.
 Author's personal copy
D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174
Fig. 6. Influence of foreign ions and pH on the adsorption of Pb(II) on Mg2 Al LDH.
m/V = 0.2 g L−1 , C(Pb)initial = 15.0 mg L−1 , and T = 303.15 K.
at higher particle concentrations the availability of higher energy
sites decreases with a larger fraction of lower energy sites becom-
ing occupied, leading to a lower adsorption capacity [42]. Besides,
higher adsorbent amount enhances the probability of collision
between solid particles and therefore creates particle aggregation,
causing a decrease in the total surface area and an increase in dif-
fusion path length, both of which contribute to the decrease in the
adsorption capacity of Pb(II) on Mg2 Al LDH. Another possible inter-
pretation is that the increase ratio of net adsorption quantity of
Pb(II) on Mg2 Al LDH surface is lower than that of the solid con-
tent, correspondingly decreasing the adsorption capacity of Pb(II)
on Mg2 Al LDH.
3.5. Effect of coexisting electrolyte ions
The metal ions in the environment are often found to be in
a matrix containing various inorganic ions. Cations in the multi-
component system may compete for the binding sites of solid
particles because of the difference in their affinities on adsorbent.
Besides, some anions can form soluble or insoluble complexes with
the metal ions, displacing with difficulty in the presence of adsor-
bent [43]. For these reasons, it is of great importance to investigate
the influence of coexisting electrolyte ions on Pb(II) adsorption on
Mg2 Al LDH. Fig. 6 shows the adsorption of Pb(II) from aqueous
solution to Mg2 Al LDH was affected by different electrolyte ions,
viz., Na+ , K+ , Li+ , ClO4 − , NO3 − and Cl− , respectively. From Fig. 6A,
the adsorption of Pb(II) on Mg2 Al LDH is strongly influences by
the electrolyte cations. The adsorption of Pb(II) on Mg2 Al LDH at
171
Fig. 7. Effect of FA/HA on the adsorption of Pb(II) on Mg2 Al LDH as a function of initial
pH. m/V = 0.2 g L−1 , C(Pb)initial = 15.0 mg L−1 , I = 0.01 mol L−1 NaClO4 , and T = 303.15 K.
pH 3.5–7 are in the following sequence: K+ < Na+ < Li+ , indicating
that the cations can influence the adsorption of Pb(II) on Mg2 Al
LDH surfaces. Cations in solution will compete for interaction with
the surface of Mg2 Al LDH, and Pb(II) ions have higher charge and
have higher affinity to the surface than the alkali metals. As support
for this competition principle, the order of Pb(II) uptake under the
same pH value was found to be lowest for potassium and highest
for lithium, which is the order of their radii of hydration: K+ = 2.32,
´ The adsorption of Pb(II) on Mg Al LDH
Na+ = 2.76 and Li+ = 3.4 Å. 2
can be considered as a competition of Pb(II) with Li+ (or Na+ , K+ )
at the Mg2 Al LDH surfaces. The radius of Li+ is larger than those of
the other two cations and therefore the influence of Li+ on Pb(II)
adsorption is smaller than those of Na+ and K+ . Similar results were
found in the previous studies [32,44–46].
From Fig. 6B, the order of decrease in the adsorption of Pb(II)
is the highest in NaClO4 solution and the lowest in NaCl solution
at pH < 7. This phenomenon could be attributed to the following
reasons: (1) idiocratic adsorption of Cl− to Mg2 Al LDH surface is a
little easier than NO3 − and ClO4 − , and Cl− adsorption on the sur-
face of Mg2 Al LDH changes the surface properties of Mg2 Al LDH
and decreases the availability of binding sites for Pb(II); (2) Cl−
and NO3 − can form soluble complexes with Pb(II) ion in solution
(e.g. PbClx (2−x)− , Pb(NO3 )x (2−x)− ), while ClO4 − does not form soluble
complexes with Pb(II) in solution. Pb(II) has the highest affinity to
Cl− but the lowest affinity to ClO4 − ; (3) the inorganic acid radicals
radium sequence is Cl− < NO3 − < ClO4 − , the smaller radium inor-
ganic acid radicals can take up more ionic exchange sites and lead
to the decline of Pb(II) adsorption on Mg2 Al LDH [32,39].
3.6. Effects of HSs
HSs contain both hydrophobic and hydrophilic moieties as well
as many chemical functions such as carboxylic, phenolic, carbonyl,
and hydroxyl groups connected with the aliphatic or aromatic car-
bons in the macromolecules. At very low pH values, HSs will be
protonated (i.e., SOH + Hs + ⇔ SOH2 + ) and become more positively
charged, and at high pH values, HSs become negatively charged
due to the deprotonation process (i.e., SOH ⇔ SO− + H+ ). The zeta
potentials of FA/HA at various pH conditions have been extensively
studied in previous reports [47,48]. The point of zero  potential
of HA/FA is about pH 2.0 [47]. Fig. 7 shows the pH dependence
of Pb(II) adsorption on Mg2 Al LDH in the absence and presence
of FA and HA. The presence of FA/HA enhances the adsorption
of Pb(II) on Mg2 Al LDH at pH < 7, while reduces Pb(II) adsorption
at pH > 7. At low pH values, the negatively charged FA/HA can
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172 D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174

Table 2
The parameters for the Langmuir and Freundlich fitting of Pb(II) adsorption on Mg2 Al
LDH.

Correlation parameters T = 303.15 K T = 323.15 K T = 343.15 K

Langmuir
qmax (mg g−1 ) 66.16 69.23 75.18
b (L mg−1 ) 0.23 0.29 0.47
RL 0.159–0.465 0.130–0.408 0.085–0.299
R2 0.975 0.969 0.991
Freundlich
kF (mg1−n Ln g−1 ) 19.76 23.31 30.91
n 0.591 0.562 0.498
R2 0.948 0.917 0.934

where b is Langmuir constant (L mg−1 ). The value of RL indicates the

Fig. 8. Adsorption isotherm, and Langmuir and Freundlich model fitting for
Pb(II) adsorption on Mg2 Al LDH at three different temperatures. pH = 5.70 ± 0.01,
m/V = 0.2 g L−1 , initial Pb(II) concentration = 5–23 mg L−1 , I = 0.01 mol L−1 NaClO4 .
Symbols denote experimental data, solid lines represent the model fitting of Lang-
muir equation, dash lines represent the model fitting of Freundlich equation.
adsorption process to be irreversible (RL = 0), favorable (0 < RL < 1),
linear (RL = 1) or unfavorable (RL > 1) [51].
The Freundlich isotherm model allows for several kinds of
adsorption sites on the solid surface and represents properly the
adsorption data at low and intermediate concentrations on hetero-
geneous surfaces [46]. The equation is represented by the following
equation:

be easily adsorbed on positively charged Mg2 Al LDH, the strong
complexation ability of surface adsorbed FA/HA with Pb(II) should
enhance the adsorption of Pb(II). The complexation between Pb(II)
and FA/HA is more stronger than that between Pb(II) and Mg2 Al
LDH. However, with increasing pH, the negatively charged FA/HA
is difficult to be adsorbed on negatively charged Mg2 Al LDH due
to electrostatic repulsion. At high pH, the competition between the
soluble FA/HA and Mg2 Al LDH with Pb(II) increases the formation
of strong FA/HA–Pb complexes in solution, thereby competitively
diminishing the extent of Pb(II) adsorption on FA/HA–Mg2 Al LDH
hybrids [49]. It is generally regarded that the presence of FA/HA
promotes the adsorption of metal ions at low pH, whereas declines
the adsorption of metal ions at high pH [50].
3.7. Adsorption isotherms and thermodynamics
The adsorption isotherms for Pb(II) on Mg2 Al LDH at 303.15,
323.15 and 343.15 K are shown in Fig. 8. The adsorption isotherm
is the highest at T = 343.15 K and is the lowest at T = 303.15 K. The
result indicates that high temperature is advantageous for Pb(II)
adsorption on Mg2 Al LDH. The Langmuir and Freundlich isotherm
models are used to simulate the adsorption isotherms. The Lang-
muir model assumes that adsorption occurs in a monolayer with
all adsorption sites identical and energetically equivalent [49]. Its
form can be described by the following equation:
bqmax Ce
qe =
1 + bCe
Eq. (5) can be expressed in linear form:
1 1 1 1
= + · (6)
qe qmax bqmax Ce
where Ce is the equilibrium concentration of metal ions remained
in the solution (mg L−1 ); qe is the amount of metal ions adsorbed
on per weight unit of solid after equilibrium (mg g−1 ); qmax , the
maximum adsorption capacity, is the amount of adsorbate at com-
plete monolayer coverage (mg g−1 ), and b (L mg−1 ) is a constant
that relates to the heat of adsorption. Furthermore, a dimension-
less constant called separation factor (RL , also called equilibrium
parameter) is commonly used to predict whether an adsorption
system is favorable or unfavorable:
RL =
1
1 + bC0
qe = kF Cen (8)
Eq. (8) can be expressed in linear form:
log qe = log kF + n log Ce (9)
where kF (mg1−n g−1 Ln ) represents the adsorption capacity when
metal ion equilibrium concentration equals to 1, and n represents
the degree of dependence of adsorption with equilibrium concen-
tration. The relative values calculated from the two models are
listed in Table 2.
From Fig. 8 and R2 values, the Langmuir model fits the experi-
mental data better than the Freundlich model, indicating that the
binding energy on the whole surface of Mg2 Al LDH is uniform. In
other words, the whole surface has identical adsorption activity
and therefore the adsorbed Pb(II) ions do not interact or com-
pete with each other, and they are adsorbed by forming an almost
complete monolayer coverage of the Mg2 Al LDH particles. This phe-
nomenon also shows that chemosorption is the principal uptake
mechanism in adsorption process [52]. Moreover, Mg2 Al LDH has a
finite specific surface and adsorption capacity, thus the adsorption
could be better described by the Langmuir model better than by
the Freundlich model. The values of qmax obtained from the Lang-
muir model for Pb(II) adsorption on Mg2 Al LDH are the highest
at T = 343.15 K and the lowest at T = 303.15 K, indicating that the
adsorption is improved with increasing temperature. The fact that
all the RL values for the adsorption of Pb(II) on Mg2 Al LDH at the
three temperatures are in the ranges of 0.085–0.465 implies that
(5)
the adsorption process is favorable.
The thermodynamic parameters (H◦ , S◦ , and G◦ ) for Pb(II)
adsorption on Mg2 Al LDH can be determined from the tempera-
ture dependence. Free energy change (G◦ ) is calculated from the
relationship:
G◦ = −RT ln K ◦ (10)
where K◦ is the adsorption equilibrium constant. Values of ln K◦
obtained by plotting ln Kd versus qe for adsorption of Pb(II)
on Mg2 Al LDH and extrapolating qe to zero [53,54] are 10.12
(T = 303.15 K), 10.36 (T = 323.15 K) and 10.98 (T = 343.15 K), respec-
tively. Standard entropy change (S◦ ) is calculated using the
equation:
 
∂G◦
(7) = −S ◦ (11)
∂T
P
 Author's personal copy

D. Zhao et al. / Chemical Engineering Journal 171 (2011) 167–174 173

Table 3 Table 4
Values of thermodynamic parameters for the adsorption of Pb(II) adsorption on Comparison of Pb(II) adsorption capacities of Mg2 Al LDH with other adsorbents.
Mg2 Al LDH.
Adsorbents Solution chemistry qmax (mg g−1 ) Reference
T (K) G◦ (kJ mol−1 ) S◦ (J mol−1 K−1 ) H◦ (kJ mol−1 ) conditions

303.15 −25.49 146.01 18.77 Oxidized MWCNTs pH = 5.9, T = 293 K 2.05 [57]
323.15 −27.84 146.01 19.34 Oak bark char pH = 5.0, T = 298 K 13.05 [58]
343.15 −31.33 146.01 18.79 Cicer arientinum pH = 4.0, T = 303 K 27.77 [59]
biomass
Syzygium cumini L pH = 6.0, T = 303 K 32.53 [60]
H2 O2 -oxidized pH = 5.0, T = 303 K 37.92 [61]
The average standard enthalpy change (H◦ ) is then calculated activated carbon
from the expression: Montmorillonite– pH = 4.0, T = 300 K 51.80 [62]
illite type of clay
H ◦ = G◦ + TS ◦ (12) Mg2 Al LDH pH = 5.7, T = 303 K 66.16 Present study
Modified quebrach pH = 5.0, T = 296 K 86.20 [63]
o tannin resin
The values obtained from Eqs. (10)–(12) are tabulated in Table 3.
A positive value of the standard enthalpy change shows that the
adsorption is endothermic. One possible explanation to this posi-
attractive adsorbent for the cost-effective disposal of Pb-bearing
tive entropy is that Pb(II) is solved well in water, and the hydration
wastewater.
sheath of Pb(II) has to be destroyed before its adsorption on Mg2 Al
LDH. This dehydration process needs energy, and it is favored at
high temperature. The removal of water from ions is essentially 4. Conclusion
an endothermic process, and it appears that the endothermicity of
the desolvation process exceeds that of the enthalpy of adsorption From the results of Pb(II) adsorption on Mg2 Al LDH under
by a considerable extent. As is expected for a spontaneous process our experimental conditions, the following conclusions can be
under the experimental conditions, it is clear that the free energy obtained:
changes (G◦ ) of Pb(II) adsorption on Mg2 Al LDH is more nega-
tive at higher temperature, which indicates that the spontaneity (1) The adsorption of Pb(II) on Mg2 Al LDH is quick and the kinetic
of the adsorption process increases with the rise in temperature. adsorption is fitted by the pseudo-second-order model very
At high temperature, cations are readily desolvated and hence its well.
adsorption becomes more favorable. The positive value of entropy (2) Cations and anions influence the adsorption of Pb(II) on Mg2 Al
change (S◦ ) implies some structural changes in sorbate and sor- LDH obviously at pH < 7, and no obvious influence is found at
bent during the adsorption process, which leads to an increase in pH > 7.
the disorderness of the solid-solution system [17]. Pb(II) ions in (3) The presence of HA/FA enhances the adsorption of Pb(II) on
solution are surrounded by a tightly bound hydration layer where Mg2 Al LDH at low pH, whereas reduces Pb(II) adsorption at high
water molecules are more highly ordered. When Pb(II) ions come pH.
into close interaction with the hydration surface of adsorbent, the (4) The thermodynamic analysis derived from temperature depen-
ordered water molecules in the two hydration layers are compelled dent adsorption isotherms indicates that the adsorption
and disturbed, thus increasing the entropy of water molecules. reaction of Pb(II) on Mg2 Al LDH is endothermic and sponta-
The thermodynamic analysis derived from temperature dependent neous.
adsorption isotherms shows that the adsorption process of Pb(II) (5) Mg2 Al LDH has good potentialities for cost-effective removal of
on Mg2 Al LDH is spontaneous and endothermic. However, Wong Pb(II) from Pb(II)-contaminated wastewaters.
et al. [55] investigated the removal of Pb(II) and Cu(II) by tartaric
acid modified rice husk from aqueous solutions and found that the Acknowledgements
adsorption process was spontaneous and exothermic. The results
derived from this work and the above-mentioned references sug- Financial supports from the National Natural Science Foun-
gest that the thermodynamic parameters are related not only on dation of China (21071147; 20971126), Special Foundation for
the nature of adsorbate, but also on the nature of solid particles High-level Waste Disposal (2007-840) and the Knowledge Inno-
[56]. vation Program of CAS are acknowledged.

3.8. Comparison of Pb(II) adsorption capacity of Mg2 Al LDH with
other adsorbents
In order to assess the potential improvements to Pb(II) removal
offered by Mg2 Al LDH over other adsorbent systems, qmax , a
Langmuir parameter that has been used in most of the earlier
investigations for defining Pb(II) adsorption capacity of different
materials, can be applied to compare the efficacy of Mg2 Al LDH with
those of other adsorbents reported in the literatures [57–63] (see
Table 4). Although a direct comparison of Mg2 Al LDH with other
adsorbents is difficult owing to the different experimental condi-
tions applied, it has been found that Pb(II) adsorption capacity of
Mg2 Al LDH is higher than that of activated carbon, oxidized MWC-
NTs and some biosorbents, comparable with montmorillonite–illite
type of clay, but lower than that of modified quebracho tannin
resin. However, the ease of preparation and widely variable ways
in which their components can be combined make Mg2 Al LDH an
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.cej.2011.03.082.
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