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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
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.
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.
V
m
(1)
D. Wan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 469 (2015) 307314
309
4000
3500
3000
(a)
2500
Intensity
003
2000
006
1500
012
015
1000
018
110 113
500
0
HT5
HT4
HT3
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
10
20
30
40
50
60
70
80
2 Theta (degree)
3.1. Characterization
4000
3500
3000
(c)
2500
2000
1500
Intensity
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)
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
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
-1
3532 cm
40
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
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.
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).
(2)
(3)
(4)
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
qe =
Freundlich model
Q0 Ce KL
(1 + Ce KL )
(5)
qe = KF Cen
(6)
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
(7)
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
10
9
8
7
qe (mmol/g)
313
6
5
4
3
2
3.4. Mechanism
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)
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
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
110
100
90
80
Mg/Al ratio
Fig. 8. Interlayer spacing, Zeta potential (at pH 10.0 0.1) and Qmax (298 K) of each
material.
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