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Colloids and Surfaces A: Physicochem. Eng.

Aspects 469 (2015) 307314

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Colloids and Surfaces A: Physicochemical and


Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Uptake uoride from water by caclined Mg-Al-CO3 hydrotalcite:


Mg/Al ratio effect on its structure, electrical afnity and adsorptive
property
Dongjin Wan a,b , Yongde Liu b , Shuhu Xiao a, , Jing Chen b , Jian Zhang b
a
b

State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou, Henan 450001, China

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

Higher Mg/Al ratio exhibited larger

interlayer spacing and lower electrical afnity which had reverse effect
on adsorption.
Pseudo-second order and Langmuir
model tted kinetics and isotherm
satisfactorily.
From both kinetics and equilibrium
study, the maximum adsorption rate
and capacity was achieved when
Mg/Al = 4.
The adsorption process was spontaneous and endothermic.
The detrimental effect of coexisting
anion
increased
as:
Cl < SO4 2 < PO4 3 .

a r t i c l e

i n f o

Article history:
Received 9 September 2014
Received in revised form 9 January 2015
Accepted 11 January 2015
Available online 29 January 2015
Keywords:
Hydrotalcite
Fluoride
Mg/Al ratio
Adsorption
Interlayer spacing
Zeta-potential

a b s t r a c t
Previous studies have found that calcined Mg-Al-CO3 hydrotalcites exhibit high uoride removal capacity.
The effect of Mg/Al ratio on its structure, electrical afnity and adsorptive property, however, remained
elusive, and their elucidation could enhance the functional optimization of the material. This study
presents signicant effect of Mg/Al ratio in calcined hydrotalcite (CHTx, x was the ratio: 2:1, 3:1, 4:1
and 5:1) on uoride adsorption. The materials were characterized by X-ray diffraction (XRD), N2 adsorption/desorption analysis using BET method, scanning electron microscopy (SEM), Zeta-potential and
Fourier transform infrared spectroscopy (FTIR) to conrm the adsorption mechanism. In this unique
study, we found that different Mg/Al ratios resulted in different interlayer spacing and electrical properties, inuencing the substances adsorptive properties. As the Mg/Al ratio increased, the interlayer spacing
increased and Zeta potential decreased, which had a reverse effect on adsorption. The CHT4 exhibits the
highest adsorption rate and capacity (Qmax = 119.04 mg/g at 298 K). The adsorption kinetics data best t a
Pseudo-second-order kinetic model. The Langmuir isotherm model t experiment data better than Freundlich model. The results of thermodynamic study highlighted the spontaneous and endothermic nature of
the adsorption process. The detrimental effect of co-existing anion increased as: Cl < SO42 < PO4 3 .
2015 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +86 10 84928381; fax: +86 10 84917906.


E-mail addresses: dongjinwan@yeah.net (D. Wan), xiaoshuhu@126.net (S. Xiao).
http://dx.doi.org/10.1016/j.colsurfa.2015.01.045
0927-7757/ 2015 Elsevier B.V. All rights reserved.

308

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

1. Introduction
Fluoride contamination in groundwater is a signicant problem
for many countries [1]. Fluoride is a naturally occuring substance,
and is released into groundwater through natural geological processes that dissolve uorine-rich rocks. However, ouride is also
produced through industrial activities, such as glass and ceramic
production and semiconductor manufacturing, also contributing
to uoride pollution [2,3]. Although small amounts of ouride in
drinking water is considered benecial in reducing dental cavities,
excess ouride intake can cause severe health problems, such as
osteoporosis, arthritis, brittle bones, cancer, infertility, and brain
damage [4,5]. Therefore, the World Health Organization (WHO) has
set a strict guideline of 1.5 mg/L for drinking water [6]. Unfortunately, it is estimated that over 200 million people worldwide rely
on drinking water with uoride concentration exceeding 1.5 mg/L
[7].
Primary conventional methods to remove uoride from water
include chemical-precipitation [8], membrane ltration such as
reverse osmosis [9], ion-exchange [10,11], electrodialysis [12], and
the adsorption method [7,13]. Among these methods, adsorption
is an effective and widely used physiochemical treatment process that yields promising removal results and is an attractive
method for uoride removal [7,13]. A variety of materials have been
studied as adsorbents to facilitate uride removal from aqueous
solutions, including alumina and aluminum-based sorbents [14],
calcium-based sorbents [15], carbon based adsorbents [16], and
hydrotalcites [17]. Among these, hydrotalcites and their calcined
products have attracted increasing attention because of their low
cost, high adsorption capacity, and unique structure [18].
The structure of hydrotalcites can be derived from the layered
mineral brucite Mg(OH)2 . Isomorphous substitution of divalent
cations (such as Mg2+ , Zn2+ ) by trivalent ones (such as Al3+ , Fe3+ )
generates positive charges on the brucite layers which are compensated by anions (e.g. CO3 2 ) located in the interlayer region. Besides,
water molecules are also found in the interlayer space. They
have the general formula: [M2+ (1 ) N3+ (OH)2 ] + [An ]/n mH2 O,
where M2+ is a divalent cation (Mg2+ , Zn2+ , Mn2+ , Co2+ , Ni2+ , Cd2+ ),
N3+ is a trivalent cation (Al3+ , Fe3+ , Cr3+ , Ga3+ ), An is a anion in
the interlayer and is dened as the N3+ /(M2+ + N3+ ) ratio. When
hydrotalcites are calcined, the interlayer water and anions, and the
hydroxyls are removed, and the layered structure is destroyed. The
resulting material is a mixture of metal oxides which can absorb
anions from aqueous solution to recover its original layered structure [1719].
Previous studies have found that calcined Mg-Al-CO3 hydrotalcites exhibit high uoride removal capacity, as the layered structure
facilitates adsorption processes [18,20]. Lv et al. [18] investigated
the uroide adsorption kinetics and equilibrium by calcined MgAl-CO3 hydrotalcite (Mg/Al = 2:1), the LangmuirFreundlich model
and modied multiplex model could be used to describe the
adsorption equilibrium and kinetics process satisfactorily. Wang
et al. compared the adsorptive property of Mg-Al-CO3 hydrotalcite
(Mg/Al = 3:1) with their calcined products, the calcined products
exhibited higher adsorption capacity than uncalcined material [20].
Research also demonstrates that parameters such as pH, temperature and co-existing ions are factors in ouride adsorption by
hydrotalcite-like componds [18,2022]. However, there are few
studies about the effect of M2+ /N3+ ratios on uoride adsorption.
The effect of Mg/Al ratio on its structure, electrical afnity and
adsorption property, however, remained elusive, and their elucidation could enhance the functional optimization of the material.
In a previous study, we found that the Mg/Al ratio greatly inuenced interlayer spacing and electrical properties, further affecting
adsorptive features during anion adsorption [23]. Based on this,
studying the Mg/Al ratio effect on uoride adsorption from aqueous

solution is a natural next step. The goals of this study were to: (1)
use a coprecipitation method to synthesize Mg-Al-CO3 hydrotalcites of different Mg/Al ratio; (2) investigate the uoride adsorption
process of calcined hydrotalcite with different Mg/Al ratios; and (3)
characterize hydrotalcites with different Mg/Al ratios and explore
the compositional effect on their structure and adsorptive properties.

2. Materials and methods


2.1. Adsorbents synthesis
Mg-Al-CO3 hydrotalcites (HTx, x was Mg/Al atomic ratio) was
synthesized using a conventional coprecipitation method. We rst
created a salt solution (200 mL) containing appropriate ratios of
MgCl2 6H2 O (1.2 mol/L) and AlCl3 6H2 O (1.2/x mol/L). The Mg/Al
atomic ratio (x) in the solution was selected as 2:1, 3:1, 4:1, and
5:1. We also created a second solution (200 mL) containing NaOH
and Na2 CO3 , at sufcient concentrations to precipitate the salt in
the rst solution. The two solutions were simultaneously added
drop by drop into a 200 mL sample of deionized water, which we
vigorously stirred. The temperature was xed at 313 K, and the pH
was maintained at 1011. The resulting slurry was allowed to rest
at 338 K for 12 h. The nal precipitate was centrifuged several times
with deionized water, until the superstratum water was free of Cl .
The precipitate was then dried at 378 K for 8 h to obtain the HTx
powder, and calcined hydrotalcites powder (CHTx, 100 meshes)
was obtained by calcining HTx in a mufe furnace at 773 K for 5 h.

2.2. Kinetics study


The adsorption rate is an important factor when studying adsorbents, and is best studied through kinetics experiments. For this
part of our study, the uoride solution was prepared by dissolving
NaF in deionized water and vigorously stirring. The initial concentration was xed at 200 mg/L; the solution volume was 500 mL; the
sorbent dosage was 1 g/L; and the temperature was controlled at
298 K. The CHTx adsorptive capacity toward uoride was calculated
as follows:
qt = (C0 Ct )

V
m

(1)

In this equation, qt is the adsorptive capacity of adsorbent at time


t (mg/g), V is the volume of solution (L), C0 and Ct (mg/L) are the
initial concentration of uoride and that at time t, and m is the mass
of adsorbent (g).

2.3. Equilibrium study


Equilibrium isotherms were obtained by subjecting a constant
mass (0.10 g) of CHTx to a range of different uoride concentration
solutions. The CHTx and uoride solutions were agitated in a series
of asks placed in a temperature controlled orbital shaker (stirring
speed of 150 rpm). We used equal solution volumes (100 mL), maintained at 298 K for a period of 24 h to achieve adsorb equilibrium.
The reaction mixture pH was not controlled, because we wanted to
avoid another anion impacting uoride uptake. After shaking the
asks for 24 h, the sample solution was removed from the reaction
mixture and passed through a 0.20 m membrane. The adsorption
capacity of CHTx toward uoride at equilibrium was denoted as qe
(mg/g).
In addition to these tests, we also tested the equilibrium at 288 K,
308 K, and 318 K to investigate temperature effect.

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

309

2.4. Effect of co-existing anions

4000
3500

We also explored the inhibiting effect of co-existing anions, such


as Cl , SO4 2 and PO4 3 in this study. A series of CHT4 and synthetic
solutions were agitated by shaking them for 24 h in conical asks
at 298 K to achieve adsorption equilibrium. The synthetic solution
contained equal concentrations of F with other competitive anions
(Cl , SO4 2 or PO4 3 ); the two anion concentrations ranged from
0.001 mol/L to 0.05 mol/L. The solution volume was 100 mL, and the
sorbent dosage was 1 g/L.

3000

(a)

2500

Intensity

003

2000
006

1500
012

015

1000

018

110 113

500
0

HT5
HT4

2.5. Analytical methods

HT3

Following the preparation discussed above, samples were


ltered using a 0.20 m membrane before analysis. The uoride concentration was analyzed using a uorine reagent
spectrophotometry method at 620 nm using a TU-1900 Persee
Spectrophotometer (Persee, China). The X-ray diffraction analysis was completed using X pert Pro MPD with Cu-Ka radiation
from 5 to 80 (2) (Panalytical, Netherlands). The surface area,
average pore volume, and pore diameter of the samples were
obtained using an ASAP 2020 apparatus (Micromeritics Co., USA),
using the BET method. The scanning electron microscopy (SEM)
images were obtained using a Hitachi S-3000N microscope. Fourier
transform infrared spectra (FTIR) were recorded with KBr-pressed
disks ranging from 400 to 4000 cm1 using an IR Prestige-21
Fourier Transform Infrared Spectrometer (Shimadzu, Japan). The
Zeta-potential was measured using a Malvern Zetasizer 2000
(0.001 mol/L NaCl, 298 K).

HT2
0

10

20

30

40

50

60

70

80

2 Theta (degree)
4000
3500

Intensity

3000

(b)

2500
2000
1500
1000
500
0

CHT5
CHT4
CHT3
CHT2

3. Results and discussion


0

10

20

30

40

50

60

70

80

2 Theta (degree)

3.1. Characterization

4000
3500
3000

(c)

2500
2000
1500

Intensity

3.1.1. XRD analysis


The X-ray diffraction analysis was used to explore sample structure. Fig. 1 shows the XRD patterns of HTx, CHTx, and CHTx-A
(after adsorption). Before being calcined, the HTx showed a well
crystallized hydrotalcite-like structure, with sharp and symmetric
reections (planes of 0 0 3, 0 0 6, 1 1 0, and 1 1 3), as well as wide and
asymmetric reections (planes of 0 1 2, 0 1 5, and 0 1 8). All of these
reections were characteristic planes of hydrotalcite-like compounds, indicating that our preparation was successful [19]. The
cell parameters were calculated as a = 2 d1 1 0 and c = 3 d0 0 3,
respectively [24]. The d0 0 3 values corresponded to the basal spacing of two consecutive brucite-like hydroxide layers in the HTx.
Therefore, the interlayer free spacing could be calculated by subtracting the brucite sheet thickness (0.480 nm as reported [24])
from the basal spacing d0 0 3.
The structural data calculated on the bases of XRD analyses are
presented in Table 1. The table shows that the increase in Mg/Al
ratio compared to the parent hydrotalcite is accompanied by the
increase in c parameter and, consequently, the interlayer spacing. This phenomenon indicates weaker electrostatic interactions

1000
500
0

CHT5-A
CHT4-A
CHT3-A
CHT2-A
0

10

20

30

40

50

2 Theta (degree)

60

70

80

Fig. 1. The XRD patterns of HTx, CHTx and CHTx-A (after adsorption).

Table 1
Structural data calculated on the basis of XRD analyses.
Sample

2 of d 0 0 3 ( )

2 of d 1 1 0 ( )

a (nm)

c (nm)

Interlayer spacing (nm)

HT2
HT3
HT4
HT5
CHT2-A
CHT3-A
CHT4-A
CHT5-A

11.74
11.33
11.16
11.12
11.65
11.48
11.47
11.35

60.88
60.42
60.04
60.09
60.70
60.69
60.65
60.20

0.304
0.300
0.302
0.302
0.299
0.299
0.300
0.302

2.274
2.318
2.367
2.415
2.281
2.316
2.387
2.424

0.278
0.293
0.309
0.326
0.280
0.292
0.316
0.328

310

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314
40

HT4
CHT2
CHT3
CHT4
CHT5

Zeta Potential (mV)

30

CHT4

T% 100
80

CHT4-A

60

20

-1

1641 cm

-1

1388 cm

-1

3541 cm
40

10

20
100

80

CHT4
-1

1643 cm

60

3480 cm

-10

-20

-1

1370 cm

-1

40
20
2

10

12

14

100

pH
80
Fig. 2. The Zeta potential of CHTx as a function of solution pH (0.001 mol/L NaCl,
298 K).

60

HT4
-1

1650 cm 1393 cm-1

-1

3532 cm

40

between layer and interlayer anions, due to the lower amount of


Al3+ in the brucite-type sheet when Mg/Al ratio increases from 2:1
to 5:1 [25].
When the material was calcined at 773 K for 4 h, the layered
hydrotalcite-like structure disappeared (Fig. 1b), leading to the formation of mixed oxide Mg(Al)O (attribute to peaks at 43 and 62 ).
We subsequently observed the layered structure reconstruction
when placing the CHTx in uoride solution (Fig. 1c). After adsorption of uoride, the layered structure of HTx was reformed; the
uoride in the water was adsorbed onto the positive layer and
formed the new negative layer. The cell parameters of CHTx-A, calculated on the basis of the XRD analyses, are listed in Table 1. This
table shows that, compared with HTx, there is no signicant change
in the interlayer space after adsorption.
3.1.2. BET and Zeta potential analysis
The adsorbents physical properties are very important and signicantly inuence adsorption capacity. The BET analysis results
are summarized in Table 2. All samples exhibited a similar surface
area (152.75170.28 m2 /g) and mesopore structure, with an average pore diameter of 13.8416.04 nm. The adsorptiondesorption
isotherm of CHTx could be classied as type-IV. The hysteresis loop
started at a relatively high pressure, indicating the mesoporous
nature of the sample (Fig. S1).
Zeta potential is an important parameter for adsorption process. When the material was calcined, the layered hydrotalcite-like
structure disappeared, leading to the formation of mixed oxide
Mg(Al)O. Zeta-potential of CHTx was derived from the redundant
positive charge on the mixed oxide surface. Fig. 2 presents the
results of Zeta-potential as a function of solution pH. It could be
concluded that the isoelectric points of CHTx were about pH 11.
Hence, all the CHTx had residual positive charge in suspension in
a wide pH range (pH < 11). Besides, the Zeta-potentials of these
samples follow the order: CHT5 < CHT4 < CHT3 < CHT2. This phenomenon could be explained by the electric charge density of the
Table 2
Physical characterization of BET analysis.
Sample

BET (m2 /g)

Mesopore
volume (mL/g)

Average pore
diameter (nm)

CHT2
CHT3
CHT4
CHT5

157.07
152.75
169.63
170.28

0.58
0.60
0.55
0.69

14.29
13.84
15.83
16.04

20
0
4000

3600

3200

2800

2400

2000

1600

1200

800

400

-1

Wave number (cm )


Fig. 3. FTIR spectra of HT4, CHT4 and CHT4-A.

sample. That is, higher Mg/Al ratio results in lower Al3+ content,
which could result in lower Zeta-potential of the sample. When uoride in solution was adsorbed onto the positive layers by electric
force, the lower Zeta-potential was unfavorable for adsorption.

3.1.3. FT-IR analysis


Fig. 3 represents the FTIR spectra of HT4, CHT4, and CHT4-A. The
rst broad peak, around 3532 cm1 , can be classied as the stretching of OH groups. This stretching was caused by the interlayer water
molecules and hydroxyls groups attaching to Mg and Al in the
brucite-layers. The band at 1650 cm1 is attributed to the bending
vibration of the interlayer water. The adsorption bands observed
at 1393 cm1 are due to a carbonate group [26]. Finally, the bands
ranging from 400 to 800 cm1 can be attributed to the characteristic stretching bands of magnesium and aluminum oxides. When
HT4 was calcined, the band of OH (3480 cm1 and 1643 cm1 )
and carbonate (1370 cm1 ) was weakened in the CHT4 spectra.
After adsorption of uoride, the bands observed at 3541 cm1 and
1641 cm1 become stronger, the band at 1370 cm1 shifts to higher
frequency 1388 cm1 , corresponding to the reconstruction of the
oxide material in the presence of uoride.

3.1.4. SEM analysis


Fig. S2 is a high vacuum SEM image of gold-coated HT4, CHT4,
CHT4-A. Before being calcined, the HT4 clearly shows a layered
hydrotalcite sheet. The image demonstrates that the crystal sheet
is very thin. When the material was calcined, the layered structure disappeared, and the compact structure of material was
observed (CHT4). After adsorption of uoride, the compacted structure became loose again. The layered structure of CHT4-A could not
be observed as clearly as HT4, indicating that the layered structure
was partly recovered. This result is consistent with the XRD analysis, in which the characteristic reection intensity of CHTx-A was
much lower than HTx.

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

311

90
120

80
100

70

80

qe (mg/g)

qt (mg/g)

60
50
40

CHT2
CHT3
CHT4
CHT5
First order model
Pseudo-second order model
Intraparticle diffusion model

30
20
10

60
CHT2
CHT3
CHT4
CHT5
Langmuir model
Freundlich model

40
20
0
0

0
0

50

100

150

200

250

Time (min)
Fig. 4. Kinetics of uoride adsorbed by CHTx at 298 K. (C0 = 200 mg/L, adsorbent
dosage 1 g/L, V = 500 mL, initial pH 7.20 0.10).

3.2. Sorption kinetics


Fig. 4 shows the kinetics curves of uoride adsorption onto
caclined Mg/Al-CO3 hydrotalcites with different Mg/Al ratios at
298 K. The initial uoride concentration was 200 mg/L and the
adsorbent dosage was 1 g/L. Fluoride uptake increased rapidly in
the initial 120 min for the four adsorbents; the curves started
to atten after that due to a much slower adsorption rate.
Both the adsorption rate and adsorbent capacity proceeded
along the following sequence during the adsorption process:
CHT4 > CHT5 > CHT3 > CHT2. The results indicate that the CHTx
experienced a greater adsorption rate as the Mg/Al ratio increased
from 2:1 to 4:1. Furthermore, when the Mg/Al ratio increased
from 4:1 to 5:1, the adsorbent did not exhibit higher adsorptive ability. The CHT4 showed the highest adsorptive capacity (qt
achieved 84.31 mg/g) and achieved a removal efciency of 42.2%
over 240 min of adsorption. To further our understanding of kinetic
characteristics, we used three common adsorption kinetic models
to t the experimental data. These models included (Eqs. (24))
[18,23,26,27]:
ln(qe qt ) = ln(qe ) k1 t
t
1
t
=
+
qt
qe
k2 q2e
qt = k3 t 0.5

First-order kinetics model

Pseudo-second-order kinetics model

(2)
(3)
(4)

Intraparticle diffusion model

200

400

In these equations, t is the contact time of adsorption experiment (min); k1 (min1 ), k2 (g/mg min) and k3 (mg/g min0.5 ) is the
rate constant of each kinetics model.
Table 3 lists the results seen from tting the experimental
data against the three models. Of the three models, the Pseudosecond-order model showed a better mathematical t, based on the

600

800

Ce (mg/L)

300

1000

Fig. 5. Isotherms of uoride adsorbed by CHTx at 298 K. (Adsorbent dosage 1 g/L,


V = 100 mL, adsorption time was 24 h, initial pH 7.20 0.10, and the pH was
11.20 0.10 at equilibrium without buffer and acid/alkaline solutions adjustment).

high correlation coefcient (R2 ). The Pseudo-second-order model


assumes that the chemisorption of the adsorbate on the adsorbent
is the rate-limiting step [18].
3.3. Sorption equilibrium
3.3.1. Adsorption equilibrium of CHTx
Equilibrium studies were conducted to determine the maximum
uoride adsorption capacity of CHTx. Fig. 5 shows the equilibrium isotherm of CHTx. It indicates that the adsorption capacity of
CHTx increased steadily with the increase of equilibrium concentration. Over the range of tested concentrations, the CHTx adsorption
capacity followed this sequence: CHT2 < CHT3 < CHT5 < CHT4. The
CHT4 exhibits the highest adsorption capacity at both low equilibrium concentrations (qe achieved 53.5 mg/g when Ce was 6.9 mg/L)
and high equilibrium concentrations (qe achieved 108.7 mg/g when
Ce was 291.3 mg/L). When the equilibrium concentration of uoride
exceeded 300 mg/L, the CHTx adsorption isotherm curves became
at.
Two common equilibrium models were used to try to t the
experimental data:
Langmuir model

qe =

Freundlich model

Q0 Ce KL
(1 + Ce KL )

(5)

qe = KF Cen

(6)

In these equations, Ce is the uoride concentration in the


solution at equilibrium (mg/L), Q0 is the monolayer capacity of
the adsorbent (mg/g), KL is related to the energy of adsorption
(L/mg), and KF (mg/g) (L/mg)n and n are the Freundlich temperature
dependent constants.
Table 4 shows the results from the tting exercise, and indicates
that the Langmuir model describes the sorption equilibrium more
effectively than the Freundlich model with higher coefcients (R2 ).

Table 3
Experimental data and parameters for the three kinetics models at 298 K.
Adsorbent

qe exp
mg/g

First-order

qe cal (mg/g)
CHT2
CHT3
CHT4
CHT5

55.91
64.16
84.31
75.61

52.74
56.59
65.76
60.95

Pseudo-second order
k1 102
min1

V0 102
mg/g min

R2

1.59
1.76
1.78
1.68

83.86
99.60
117.05
102.40

0.9916
0.9935
0.9856
0.9906

qe cal (mg/g)
67.57
74.07
90.09
84.03

Intra particle
diffusion model

k2 104
g/mg min

v0 102

2.80
3.57
5.34
4.03

127.84
195.86
433.40
284.56

R2

k3

R2

0.9966
0.9979
0.9993
0.9999

3.88
4.59
6.17
5.45

0.8938
0.8006
0.5499
0.7106

mg/g min

312

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

Table 4
Adsorption isotherm parameters.
Adsorbent

Freundlich: qe = KF Cen

Langmuir: qe = Q0 Ce KL /1 + Ce KL
Q0
(mg N/g)

KL
(L/mg)

KF
(mg/g) (L/mg)n

R2

T = 298 K
CHT2
CHT3
CHT4
CHT5

87.71
97.09
119.04
109.89

0.025
0.041
0.050
0.047

0.9986
0.9995
0.9990
0.9976

10.46
16.54
28.20
21.82

0.341
0.290
0.240
0.265

0.8221
0.8106
0.8547
0.8344

T = 288 K
CHT4

102.04

0.022

0.9993

50.17

0.182

0.8873

T = 308 K
CHT4

142.86

0.055

0.9989

39.56

0.199

0.9375

T = 318 K
CHT4

158.73

0.065

0.9992

17.16

0.271

0.9198

3.3.2. Effect of temperature on CHT4 adsorption equilibrium


Many researchers have reported that temperature greatly
affects CHTx anion adsorption, such as Cl [24] and Cr (VI) [30].
In this study, CHT4 adsorption isotherms under different temperatures (288 K, 298 K, 308 K, and 318 K) were explored, the results
are shown in Fig. 6. We conclude from these results that the uoride uptake was enhanced with the increase of the adsorption
temperature. In addition, the adsorption data were tested using the
Langmuir model and Freundlich model. The tting results are listed in
Table 4. It was discovered that the adsorption isotherm for uoride
t well with Langmuir model. The maximum adsorption capacities
Q0 obtained by the Langmuir model linear regression were 102.04,
119.04, 142.86, and 158.73 mg/g at 288 K, 298 K, 308 K, and 318 K,
respectively. Generally, adsorption decreases with higher temperature due to the exothermic nature of the physical adsorption
process. Our results for uoride adsorbed by CHTx suggest that the
adsorption process involves an endothermic chemical interaction.
The standard free energy (G0 ) was calculated by the following
equation:
G0 = RT

(7)

In this equation, R is the ideal gas constant (8.314 J/mol K), T is


Kelvin temperature (K), and KL is the Langmuir constant (L/mol). The
values of standard enthalpy change (H0 ) and the standard entropy

160
140
120

qe (mg/g)

The R2 for Langmuir model t was >0.99, indicating that the uoride adsorption toward CHTx was consistent with the hypothesis
of monolayer adsorption. The mechanism used to remove anions
from the solution could be reframed as the reconstruction of the
calcined material [18]. That is, after being calcined, the HTx layer
structure was destroyed; and the interlayer water, the interlayer
carbonates, and the hydroxyls were removed. The resulting material was a mixture of metal oxides Mg (Al) O, which then picked up
uoride from the solution in an effort to recover its layered structure. During the adsorption process, uoride was adsorbed onto
CHTx positive surface, thereby forming the new negative layer. The
adsorbed layer was a monolayer, hence, the adsorption isotherm
attributed to the Langmuir model.
The maximum monolayer adsorption capacity (Q0 ) of CHTx, calculated using the Langmuir model, achieved 87.71, 97.09, 119.04,
and 109.89 mg/g or CHT2, CHT3, CHT4, and CHT5, respectively. All
the materials exhibited excellent sorption abilities. When Mg/Al
ratios increased from 2:1 to 4:1, the CHTx absorption capacity
increased accordingly. When the Mg/Al ratio further increased from
4:1 to 5:1, the CHTx adsorption capacity did not increase further.
Previous research indicated that the Langmuir constant KL could
reect the adsorption ability; that is, a larger KL value indicated
greater adsorption afnity [28]. In this study, KL values increased
steadily when Mg/Al ratios increased from 2:1 to 4:1, and when
Mg/Al ratios further increased from 4:1 to 5:1, the increase in KL
values was not observed. The effect of the Mg/Al ratio on adsorption
is related to its structure and will be further discussed in Section 3.4.
To avoid contaminating co-existing anions, the buffer and
acid/alkaline solutions were not used to adjust pH in the adsorption
tests, while the initial and equilibrium pH values were monitored.
The initial pH of the NaF solution was 7.20 0.10, and the pH
was 11.20 0.10 at the studys equilibrium point. The increase
of pH for the adsorption process is mainly due to the release of
OH during the structural regeneration process of hydrotalcite
[23].
Fig. S2 shows the effect of initial pH on adsorption capacity
and nal pH. Solutions of 0.05 M HCl or NaOH were added to
the NaF solution to adjust initial pH, which varied from 3.11 to
10.87. The CHT4 exhibit high adsorption capacity when the initial
pH varied from 4.71 to 10.87. When the initial pH was 3.11, we
observed a signicant decline in CHT4 adsorption capacity, possibly due to CHT4 dissolution. This result is consistent with Ferreira
et al.s study [29], which reported that given the high pH buffering capacities of hydrotalcites, the solution pH at the equilibrium
increased when initial pH was low. In addition, because of the
buffering effect, hydrotalcites exhibited consistently high adsorptive capacity, irrespective of initial pH (which varied from 4 to 10)
[29].

100

288 K
298 K
308 K
318 K
Langmuir model
Freundlich model

80
60
40
20
0

200

400

600

800

1000

Ce (mg/L)
Fig. 6. Isotherms of uoride adsorbed by CHT4 at different temperatures (adsorbent
dosage 1 g/L, V = 100 mL, adsorption time was 24 h, initial pH of the solution was
7.20, and the pH was 11.20 0.10 at equilibrium without buffer and acid/alkaline
solutions adjustment).

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

anions, especially PO4 3 are present. When equal concentrations


of Cl , SO4 2 and PO4 3 exist, the maximum adsorption capacity of uoride decreased from its level of 6.26 to 4.87, 4.16, and
3.15 mmol/g, respectively. CHTxs ability to pick up uoride from
the solution mainly depends on the electrical afnity of its positive
surface [19]. Multivalent anions are adsorbed more readily onto
the positive surface than monovalent anions. As such, the effect
of co-existing anions decreased on uoride uptake followed the
following sequence: PO4 3 > SO4 2 > Cl .

10
9
8
7

qe (mmol/g)

313

6
5
4
3
2

3.4. Mechanism

Operation line: qe=(C0-Ce)V/m

The hydrotalcite structure could be derived from the layered


mineral brucite Mg(OH)2 , where Mg2+ is located in the center of an
edge-sharing octahedral surrounded with hydroxyls. When Mg2+
was isomorphously substituted by Al3+ , positive charges were generated on the layers, which could be compensated by anions (CO3 2
in this study) in the interlayer region. This formed a sandwich-like
structure [19], with water molecules found in the interlayer space.
In this study, the XRD analysis indicated that the structure size
of HTx compounds is affected by Mg/Al ratios (Fig. 1a and Table 1).
When the Mg/Al ratio increased from 2:1 to 5:1, the interlayer spacing of HTx increased from 0.278 nm to 0.326 nm. When HTx was
calcined, the interlayer water, interlayer anions, and the hydroxyls were removed (Fig. 1b). The resulting material is a mixture
of Mg(Al)O, which takes up uoride from the solution to recover
its layered structure. The layered structure reconstruction could be
observed in Fig. 1c. After adsorption of uoride, the CHTx-A exhibited similar reection patterns compared with HTx, indicating that
the uoride in the water was adsorbed onto the positive layer and
formed the new negative layer.
We can conclude, therefore, that the Mg/Al ratio has a double effect on the adsorption process. On one hand, higher Mg/Al
ratio leads to a larger interlayer spacing of HTx, benetting uoride adsorption. On the other hand, as reported elsewhere [31], the
higher Mg/Al ratio (which means lower Al3+ concentrations) is consistent with weaker hydrogen bonding to the interlayer anions and
water, with decreasing charges on the brucite-type layer, which is
conrmed by Zeta-potential analysis in this study (Fig. 2).
Based on the adsorption kinetics and equilibrium results, when
the Mg/Al ratio increased from 2:1 to 4:1, the positive inuence
of interlayer spacing was dominant. When Mg/Al ratio further
increased from 4:1 to 5:1, the negative impact of electrical afnity was more of a factor. The maximum adsorption capacity was
achieved when the Mg/Al ratio was 4:1 (Fig. 8).

C0 (mmol/L)

0
0

10

20

30

40

50

Ce (mmol/L)
Fig. 7. Isotherms of uoride adsorbed by CHT4 when competitive anion exists with
equal substance concentrations at 298 K (the two anion initial concentration was
presented as C0 of corresponding operation line, adsorbent dosage 1 g/L, V = 100 mL,
adsorption time was 24 h; initial pH of the solution was 7.20 0.10, and the pH was
11.20 0.10 at equilibrium without buffer and acid/alkaline solutions adjustment).

change (S0 ) were calculated from the slope and intercept of the
Vant Hoff plot using regression:
ln KL =

S 0
H 0
+
RT
R

(8)

Table 5 presents the thermodynamic parameter values of CHTx


as they adsorb uoride. It can be seen that the adsorption of uoride ions by CHT4 is a spontaneous process, since the G0 values
are negative. Given that the value of H0 is positive, we conclude
that the adsorption process of uoride ions by CHT4 is endothermic
in nature, and the positive values of S0 reveal the increasing randomness at the solid solution interface of the adsorption process.
3.3.3. Effect of co-existing anions on CHT4 adsorption equilibrium
A variety of other anions are commonly present in uoridecontaminated water, including Cl , SO4 2 , and PO4 3 . These may
compete with uoride for adsorption by CHTx. As such, in this study,
we explored the isotherms of uoride adsorbed by CHT4 alongside equal concentrations of other competitive anions (Cl , SO4 2
or PO4 3 ). The experimental results are presented in Fig. 7; the
adsorption data were also tted against the Langmuir model and
Freundlich model and the tting results were listed in Table 6. In
this case, the Langmuir model tted experimental data best.
As Fig. 7 shows, when compared with the blank experiment,
the uoride adsorption capacity decreases signicantly when other

4. Conclusions

Table 5
Thermodynamic parameters for uoride ions adsorbed by CHT4.
Temperature (K)

ln KL

G0 (kJ/mol)

H0 (kJ/mol)

S0 (J/mol K)

288 K
298 K
308 K
318 K

6.03
6.86
6.95
7.12

14.45
16.98
17.80
18.82

25.788

141.27

Higher Mg/Al atomic ratios in Mg-Al-CO3 hydrotalcite led to


greater interlayer spacing and lower electrical afnities, adversely
affecting the adsorption of ouride ions. When Mg/Al atomic
ratios increased from 2:1 to 4:1, the hydrotalcites adsorption
properties were mainly affected by interlayer spacing. When
Mg/Al atomic ratio further increased from 4:1 to 5:1, the negative impact of electrical afnity played more of a role. Based on

Table 6
Adsorption isotherm parameters for uoride ions adsorbed by CHT4 when competitive anion exists with equal substance concentration at 298 K.
Co-existing anions

Blank
Cl
SO4 2
PO4 3

Freundlich: qe = KF Cen

Langmuir: qe = Q0 Ce KL /1 + Ce KL
2

Q0
(mmol/g)

KL
(L/mmol)

KF
(mmol/g) (L/mmol)n

R2

6.26
4.87
4.16
3.15

0.727
0.485
0.234
0.138

0.9979
0.9972
0.9936
0.9800

2.997
2.258
1.402
0.833

0.196
0.209
0.279
0.324

0.8701
0.7003
0.8310
0.8230

314

D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314

0.325
0.300
0.275
0.250
20

15

10

5
130
120

(mg/g)

Qmax of CHTx

Zeta potential
of CHTx(mV)

Interlayer spacing
of HTx (nm)

0.350

Interlayer spacing dominant

110
100

Electrical affinity dominant

90
80

Mg/Al ratio
Fig. 8. Interlayer spacing, Zeta potential (at pH 10.0 0.1) and Qmax (298 K) of each
material.

both the kinetics and equilibrium components of the study, the


adsorption rate and capacity of the materials follows the order:
CHT2 < CHT3 < CHT5 < CHT4. This study provides a reasonable way
to understand the role of Mg/Al ratio in hydrotalcite adsorption
process and its mechanism.
The pseudo-second-order kinetics model and the Langmuir model
could be used to effectively describe adsorption kinetics and
isotherms. The results of thermodynamic study highlighted the
spontaneous and endothermic nature of the adsorption process.
Multivalent anions are adsorbed more readily than monovalent
anions; as such, the effect of co-existing anions decreased in the
following order: PO4 3 > SO4 2 > Cl .
Acknowledgments
This work was supported by National Science Foundation of
China (NSFC Grant NO.51208179, NO.21277134 and NO.21107103)
and Plan for Scientic Innovation Talent of Henan University of
Technology (NO.2014CXRC04).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2015.01.045.
References
[1] M. Amini, K. Mueller, K.C. Abbaspour, T. Rosenberg, M. Afyuni, K.N.
Mller, M. Sarr, C.A. Johnson, Statistical modeling of global geogenic uoride contamination in groundwaters, Environ. Sci. Technol. 42 (2008)
36623668.
[2] N.B. Reddy, K.S.S. Prasad, Pyroclastic uoride in ground waters in some parts
of Tadpatri Taluk, Anantapur district, Andhra Pradesh, Indian J. Environ. Health
45 (2003) 285288.
[3] F. Shen, X.M. Chen, P. Gao, G.H. Chen, Electrochemical removal of uoride ions
from industrial wastewater, Chem. Eng. Sci. 58 (2003) 987993.

[4] M. Mahramanlioglu, I. Kizilcikli, I.O. Bicer, Adsorption of uoride from aqueous solution by acid treated spent bleaching earth, J. Fluorine Chem. 115 (2002)
4147.
[5] N.J. Chinoy, Effects of uoride on physiology of animals and human beings,
Indian J. Environ. Toxicol. 1 (1991) 1732.
[6] W.H.O. Guidelines for Drinking Water Quality, Geneva, 2004.
[7] A. Bhatnagar, E. Kumar, M. Sillanp, Fluoride removal from water by adsorption
a review, Chem. Eng. J. 171 (2011) 811840.
[8] N.C. Lu, J.C. Liu, Removal of phosphate and uoride from wastewater by a hybrid
precipitation- microltration process, Sep. Purif. Technol. 74 (2010) 329335.
[9] P. Sehn, Fluoride removal with extra low energy reverse osmosis membranes:
three years of large scale eld experience in Finland, Desalination 223 (2008)
7384.
[10] F. Luo, K. Inoue, The removal of uoride ion by using metal (III)-loaded amberlite resins, Solvent Extr. Ion Exch. 22 (2004) 305322.
[11] I.B. Solangi, S. Memon, M.I. Bhanger, Removal of uoride from aqueous environment by modied Amberlite resin, J. Hazard. Mater. 171 (2009) 815819.
[12] K. Nalan, A. zgr, S. Saba, Y. mran, Y. Mithat, Separation of uoride from
aqueous solution by electrodialysis: effect of process parameters and other
ionic species, J. Hazard. Mater. 153 (2008) 107113.
[13] S. Ayoob, A.K. Gupta, V.T. Bhat, A conceptual overview on sustainable technologies for deuoridation of drinking water and removal mechanisms, Crit. Rev.
Environ. Sci. Technol. 38 (2008) 401470.
[14] S. Ghorai, K.K. Pant, Investigations on the column performance of uoride
adsorption by activated alumina in a xed-bed, Chem. Eng. J. 98 (2004)
165173.
[15] B.D. Turner, P. Binning, S.L.S. Stipp, Fluoride removal by calcite: evidence for
uorite precipitation and surface adsorption, Environ. Sci. Technol. 39 (2005)
95619568.
[16] Y. Ma, S.-G. Wang, M. Fan, W.-X. Gong, B.-Y. Gao, Characteristics and deuoridation performance of granular activated carbons coated with manganese
oxides, J. Hazard. Mater. 168 (2009) 11401146.
[17] L. Lv, J. He, M. Wei, X. Duan, Kinetic studies on uoride removal by calcined
layered double hydroxides, Ind. Eng. Chem. Res. 45 (2006) 86238628.
[18] L. Lv, J. He, M. Wei, D.G. Evans, Z. Zhou, Treatment of high uoride concentration water by MgAl-CO3 layered double hydroxides: kinetic and equilibrium
studies, Water Res. 41 (2007) 15341542.
[19] F. Cavani, F. Triro, A. Vaccari, Hydrotalcite-type anionic clays: preparation,
properties and applications, Catal. Today 11 (1991) 173301.
[20] H. Wang, J. Chen, Y. Cai, J. Ji, L. Liu, H.H. Teng, Deuoridation of drinking water
by Mg/Al hydrotalcite-like compounds and their calcined products, Appl. Clay
Sci. 35 (2007) 5966.
[21] W. Ma, N. Zhao, G. Yang, L. Tian, R. Wang, Removal of uoride ions from aqueous
solution by the calcinations product of Mg-Al-Fe hydrotalcite-like compound,
Desalination 268 (2011) 2026.
[22] T. Lv, W. Ma, G. Xin, R. Wang, J. Xu, D. Liu, F. Liu, D. Pan, Physicochemical characterization and sorption behavior of Mg-Ca-Al(NO3 ) hydrotalcite-like
compounds toward removal of uoride from proten solutions, J. Hazard. Mater.
237238 (2012) 121132.
[23] D. Wan, H. Liu, R. Liu, J. Qu, S. Li, J. Zhang, Adsorption of nitrate and nitrite from
aqueous solution onto calcined (Mg-Al) hydrotalcite of different Mg/Al ratio,
Chem. Eng. J. 195196 (2012) 241247.
[24] N. Das, R. Das, Insertion of chromium (III) ascorbate complex into layered double hydroxide through reduction of intercalated chromate by ascorbic acid,
Appl. Clay Sci. 42 (2008) 9094.
[25] G. Kanchan, K. Sridhar, K. Hiroaki, Uptake of arsenite by synthetic layered double hydroxides, Water Res. 43 (2009) 38843890.
[26] L. Lv, J. He, M. Wei, D.G. Evans, X. Duan, Uptake of chloride ion from aqueous solution by calcined layered double hydroxides: equilibrium and kinetic
studies, Water Res. 40 (2006) 735743.
[27] H.-J. Hong, J.-S. Yang, B.-K. Kim, J.-W. Yang, Arsenic removal behavior by Fe-Al
binary oxide: thermodynamic and kinetic study, Sep. Sci. Technol. 46 (2011)
25312538.
[28] J. Das, B.S. Patra, N. Baliarsingh, K.M. Parida, Calcined MgFeCO3 LDH as
an adsorbent for the removal of selenite, J. Colloid Interface Sci. 316 (2007)
216223.
[29] P.F. Odair, G.M. Sandra, D. Nelson, C. Lorena, L.A. Oswaldo, Evaluation of boron
removal from water by hydrotalcite-like compounds, Chemosphere 62 (2006)
8088.
[30] L. Xiao, W. Ma, M. Han, Z. Cheng, The inuence of ferric iron in calcined nanoMg/Al hydrotalcite on adsorption of Cr (VI) from aqueous solution, J. Hazard.
Mater. 186 (2011) 690698.
[31] J.S. Paul, G.N. Ulla, G. Zhehong, P.G. Clare, Mg/Al ordering in layered double
hydroxides revealed by multinuclear NMR spectroscopy, Science 321 (2008)
113117.