Desalination 277 (2011) 121–127

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Removal of fluoride from drinking water by natural stilbite zeolite modified

with Fe(III)
Youbao Sun a,b, Qinghua Fang a, Junping Dong a,⁎, Xiaowei Cheng c, Jiaqiang Xu a
a
Department of Chemistry, Shanghai University, Shanghai, 200444, China
b
Shimadzu International Trading (Shanghai) Co. Ltd, Shanghai, 200052, China
c
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, China

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

Article history: Stilbite zeolite (STI), a natural zeolite with high crystallinity and an open pore system, was modified with
Received 23 November 2010 FeCl3 solution for the removal of fluoride from drinking water. The parent STI and modified STI (Fe(III)-STI)
Received in revised form 3 April 2011 were characterized by FTIR, scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray
Accepted 4 April 2011
photoelectron spectroscopy (XPS). Adsorption of fluoride on modified STI (Fe(III)-STI) was studied as a
Available online 6 May 2011
function of contact time, adsorbent dose, initial concentration, pH and coexisting ions. Fluoride concentration
Keywords:
can be reduced down to the lower level of 1 mg L−1 under the optimum condition (with solid/solution ratio of
Removal 1:100 and the contact time of 2 h and pH 6.94) when initial fluoride concentration of 10 mg L−1 is employed.
Fluoride The fluoride adsorption on Fe(III)-STI zeolite is well described by the Langmuir adsorption model, and the
Modified maximum fluoride adsorption capacity is 2.31 mg g−1. The kinetic result indicates that the adsorption of
Ferric fluoride on the modified natural zeolite follows pseudo-first-order model. The possible mechanism on
STI zeolite fluoride adsorption on Fe(III)-STI zeolite is also discussed.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Fluoride pollution of water occurs through two ways which are
natural reasons and human activities. Fluoride is frequently present in
minerals and it can be leached out due to erosion by rainwater, which
leads to contamination of ground and surface waters. On the other
hand, fluoride contamination occurs in a wide range of industrial
wastewater produced from aluminum and steel production, metal
finishing and electroplating, glass and semiconductor manufacturing,
ore beneficiation, and fertilizer operation [1].
As one of the trace elements, fluoride is essential to prevent dental
caries but an excess intake is detrimental to human health. Excess
ingestion of fluoride can cause dental/skeleton fluorisis [2]. It not only
affects teeth and skeleton but its accumulation over a long period of
time can lead to cancer, osteosclerosis (brittle bones and calcified
ligaments) and is also an indication of neurological impairment in
human beings[3]. According to World Health Organization (WHO)
norms, the acceptable fluoride concentration in drinking water is
generally in the range of 0.5–1.5 mg L−1[4]. Some methods such as
chemical precipitation [5,6], ion exchange [7], adsorption [8–10],
electrolysis [11,12], reverse osmosis [13] and nanofiltration [14] have
been investigated for defluoridation of water. Meenakshi [15] gave a
⁎ Corresponding author.
E-mail address: jpdong@shu.edu.cn (J. Dong).
full remark on the fluoride removal in drinking water. In this paper, a
broad overview of the available technologies for fluoride removal and
advantages and limitations of each one have been presented based on
literature survey and the experiments conducted in the laboratory. It
has been concluded that the selection of treatment process should be
site specific and each technology has some limitations and no one
process can serve the purpose in diverse conditions. Among these
methods, adsorption is the most suitable process for drinking water
treatment. Different adsorbents have been tested for fluoride removal,
including activated alumina [8], activated carbon [16,17], calcite [18],
clay [2] and red mud [19]. Recently, some work has been conducted in
developing new adsorbents loaded with metal ions for the purpose of
removal of fluoride. It has been reported that the adsorption capacity
of fluoride on aluminum-impregnated carbon is 3–5 times higher than
that of plain activated carbon [20]. The extent of removal of fluoride
ion by zirconium (IV)-impregnated collagen fiber is more than 97.4%
at pH 5.5 from an initial concentration of 5.00 mmol L−1[10]. In
addition, some adsorbents loaded with rare earth ion are attracting
more and more attention [21]. For example, lanthanum (III)-loaded
polymer matrices [22] and lanthanum oxide-coated silica gel [23] are
used for the removal of fluoride ion because of their good adsorptive
performance. But due to possible secondary water pollution intro-
duced by loaded metal ion and high cost, these techniques are not
applicable to provide fluoride free water on a large scale in developed
or under developing countries.
Natural zeolites are naturally occurring crystalline aluminosili-
cates. The fundamental building block of the zeolite is a tetrahedron

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.04.013
122 Y. Sun et al. / Desalination 277 (2011) 121–127
composed of four oxygen atoms surrounding a relatively small
silicon or aluminum atom. Since aluminum has one less positive
charge than silicon, the framework usually has a net negative
charge and is balanced by the exchangeable cation (K+, Na+, Mg2+,
and Ca2+). Therefore ion exchange capability of natural zeolite
makes it favorable for wastewater treatment to remove unwanted
ions. Besides, the cheap natural zeolite is attractive. The modifica-
tions of zeolite are usually required in order to promote properties
of zeolite in catalysis and adsorption. Three methods are proposed
for modifications of zeolite including skeleton element modifica-
tion, non-skeleton element modification and surface modification
[24–26]. Non-skeleton element modification is most widely utilized
and the modifications of zeolite are carried out by treatment in
inorganic acids or salts of metal using ion exchange or impregnation
methods. Clinoptilolite is one of the commonly known natural
zeolites and widely utilized in pollute control [27,28]. Olguı'n et al.
[29] reported a natural modified zeolite (clinoptilolite from Mexico)
treated with NaCl, CaCl 2 , La(NO 3)3 , and Eu(NO3 )3 for water
defluoridation. Adsorption studies reveal that the efficiency of
defluoridation on HEUCLI-La is higher than HEUCLI-Na, HEUCLI-Ca
and HEUCLI-Eu.
The STI zeolite is abundant in nature in China and has a typical
chemical formula of Na4Ca8[Al20Si52O144]·56H2O, in which Ca2+ ion is
the exchangeable cation. Its quality was confirmed with high
crystallinity and absence of other impurity of minerals. Long's group
has carried out some studies on structure, modification, adsorption,
and catalysis of the natural STI zeolite [30,31].
In the present study, natural STI zeolite was modified by Fe(III) ion
to obtain a fluoride adsorbent, and its adsorption behavior in
removing fluoride from drinking water was investigated.
2. Materials and methods
2.1. Materials
The natural zeolite sample of STI was collected from the northern
part of China. The natural zeolite sample of STI was crushed up and
sieved to the particle size fraction 10–20 μm. The parent sample of STI
was treated three times in 1 mol L−1 NH4Cl solution at 95 °C for 2 h
with a solid/solution ratio of 1:10 under stirring. After washing,
filtering and drying procedures, ion exchanged sample of NH4-STI was
obtained. The NH4-STI sample was calcined from room temperature to
550 °C at a rate of 10 K min− 1 under N2 flow to obtain a sample of
H-STI. The H-STI sample was treated three times in 0.1 mol L− 1 FeCl3
solution at 70–80 °C for 2 h with a solid/solution ratio of 1:10 under
stirring. Finally the sample of Fe(III)-STI was obtained by washing,
filtering and drying procedures.
2.2. Batch adsorption studies
Stock solution (100 mg L−1) was prepared by dissolving 0.221 g
anhydrous sodium fluoride to 1 L of deionized water. This was further
diluted to the desired concentration for practical use. The known
weight of the adsorbent was added to 100 mL of the desired fluoride
solution in a plastic bottle and then stirred thoroughly at room
temperature. After continuous stirring in magnetic stirrer for a fixed
time interval, the samples were filtered and the fluoride concentration
in the residual solution was analyzed by a fluoride ion selective
electrode (PF-1C, Model 201, China). Before determination, total ionic
strength adjusting buffer (TISAB) was added to solution in order to
maintain ionic strength and the pH, and eliminate the interference
effect of complexing ions. Similar procedures were followed to
investigate the effect of contact time, adsorbent dose, initial concen-
tration, pH and coexisting ions.
2.3. Regeneration
The exhausted Fe(III)-STI was regenerated using 1 mol L−1 HCl
solution as eluent [27,28]. Then the sample was treated three times in
0.1 mol L− 1 FeCl3 solution at 70–80 °C for 2 h with a solid/solution
ratio of 1:10 under stirring. Subsequently sample was washed,
filtered, and dried to get the regenerated sample. Similar regenerated
procedures were carried out in three consecutive adsorption–
desorption experiments.
2.4. Adsorbent characterization
The surface morphology of the modified natural STI zeolite was
observed using scanning electron microscope (SEM, Philips XL30)
with an energy dispersive X-ray (EDX). X-ray diffraction (XRD)
analysis was carried out on a Rigaku D-MAX/IIA X-ray diffractometer
in the 2θ range of 5–35° at a rate of 4° min− 1 with Cu Kα radiation.
FTIR spectra were obtained by using an Avatar 370 spectrophotometer
from Nicolet, the preparation of the samples consisted in dispersing
and gently grinding the powder in KBr. X-ray photoelectron
spectroscopy (XPS) data were collected on a RBD upgraded PHI-
5000C ESCA system (Perkin Elmer) with Al Kα radiation. The residual
fluoride concentration was analyzed by fluoride ion selective
electrode (PF-1C, Model 201, China). The content of Fe3+ impregnated
on STI zeolite was determined by inductively coupled plasma-atomic
emission spectroscopy (ICP-AES, Model ICPE9000 Shimadzu Japan).
3. Results and discussion
3.1. Adsorbent characterization
3.1.1. X-ray diffraction
Fig. 1 shows the XRD patterns of the parent STI sample and the
modified samples before and after fluoride adsorption: (a) parent STI;
(b) Fe (III)-STI; (c) Fe (III)Fn-STI (Fe (III)-STI after fluoride adsorption).
All samples are pure phase without other mineral impurity. Compared
to the parent STI, the modified samples retain the high crystallinity.
The number and position of diffraction peaks do not change, indicating
that no crystalline transformation occurs during treatment. Addition-
ally, d-spacing of the (0 2 0) plane increases after fluoride adsorption,
implying the cell expansion of STI zeolite after fluoride adsorption. The
decrease of the intensity could be the result of the higher absorption
coefficient of iron compounds for the X-ray radiation and the lower
zeolite content in the samples by the addition of iron salts [32].
30000
25000
c
20000
Intensity (a.u.)
15000
b
(020)
10000
5000
0
a
5 10 15 20 25 30 35
2-Theta (degree)
Fig. 1. XRD patterns of the parent STI sample and the modified samples before and after
fluoride adsorption: (a) parent STI; (b) Fe(III)-STI; (c) Fe(III)Fn-STI after fluoride
adsorption.
 Y. Sun et al. / Desalination 277 (2011) 121–127 123

3.1.2. Fourier transform infrared spectroscopy (FTIR)

IR spectra of all samples in Fig. 2 are in agreement with the STI
zeolite characteristic vibrations [30,33]. The vibration of the symmet-
rical stretch at 779 cm− 1 of the Fe (III)Fn-STI is found to split into two
peaks at 795 and 779 cm− 1 respectively, due to fluoride adsorption.

3.1.3. Morphology
The morphology and surface element distribution of fluoride
adsorbed Fe(III)Fn-STI are examined by SEM combined with an EDX.
The morphology of Fe(III)Fn-STI is unchanged after fluoride adsorp-
tion (Fig. 3a and b). The presence of Fe and F signals in EDX (Fig. 3c)
spectra reveals that Fe3+ is successfully impregnated on the natural
STI zeolite and fluoride is adsorbed on Fe(III)-STI. The quantitative
analysis from EDX shows that the atomic ratio of Fe to F is close to 5:1.

3.1.4. X-ray photoelectron spectroscopy (XPS)

XPS is used to examine the local oxidation states and chemical
bonding environment of the material. XPS narrow region scans of Fe
2p and F 1s in Fe (III)Fn-STI sample are shown in Fig. 4. The bands at
716.6 and 730.8 eV (Fig. 4a) are respectively attributed to Fe2P3/2 and
Fe2P1/2, which is characteristic of Fe (III) [34]. The binding energy at
698 eV (Fig. 4b) is assigned to the F 1s [35]. These results reveal that
both Fe3+ and F− are present on the surface of Fe(III)-STI zeolite. Also
the quantitative analysis from XPS shows that the atomic ratio of Fe to
F is close to 8:1.

3.2. Batch adsorption study

3.2.1. Effect of contact time

The removal of fluoride from drinking water with time is shown in
Fig. 5. It is observed that fluoride uptake increases with contact time
and reaches equilibrium within 2 h. At this time the maximum
efficiency of fluoride removal is about 92%, so 2 h is fixed as the period
of contact time for further studies.

3.2.2. Effect of adsorbent dose

The effect of adsorbent doses is investigated as shown in Fig. 6. As
the dosage of adsorbent is increased from 2 to 10 g L−1, there is an
obvious ascend in the percentage of fluoride removal. This indicates
that the number of active adsorption sites at higher dosage is much
enough to accommodate fluoride ions. However, there is only a slight

a
775
b 696
Transmittance (%)

1641
552
Fig. 3. SEM images of the (a) parent sample and (b) fluoride-adsorbed Fe(III)Fn-STI and
c 1645 779
693
439
(c) EDX of fluoride-adsorbed Fe(III)Fn-STI.

562
1037 694
1647 795 779
563 446 improvement in the fluoride removal when the dosage of adsorbent is
above 10 g L−1. This suggests that adsorption reaction is likely to
1071
reach to a dynamic equilibrium. In order to achieve the minimum
456 dosage for maximum fluoride removal, 10 g L−1 is chosen as the
optimum dosage.
1079
3.2.3. Effect of initial concentration
2000 1600 1200 800 400
The specific amount adsorbed is calculated from the following
Wavenumber (cm-1)
equation.
Fig. 2. FTIR spectra of the parent STI sample and the modified samples before and after  
Co −Ce
fluoride adsorption: (a) parent STI; (b) Fe(III)-STI; (c) Fe(III)Fn-STI after fluoride qe = ·V ð1Þ
adsorption. W
124 Y. Sun et al. / Desalination 277 (2011) 121–127

80000 100
a
Fe2p1/2 90
75000 Fe2p3/2

Fluoride removal (%)

70000 80
Intensity (CPS)

65000 70

60
60000

50
55000

40
50000
0 2 4 6 8 10 12 14 16 18 20 22
45000 Adsorbent dose (mg L-1)
750 740 730 720 710 700
Binding energy (ev) Fig. 6. Effect of adsorbent dose (particle size 10–20 μm, fluoride initial concentration
5.0 mg L−1, contact time 2 h and pH 6.7 ± 0.3).

168000 b
The effect of initial concentration on fluoride removal is shown in
Fig. 7. It is noticed that the adsorption capacity reaches stable at high
166000 F1S initial concentration. This plateau represents saturation of the active
adsorption sites available at the high initial concentration.
Additionally, the equilibrium concentration of fluoride increases
Intensity (CPS)

164000 with increasing in initial fluoride concentration. When the initial

fluoride concentration is below 10 mg L−1, the equilibrium concen-
tration of fluoride can be reduced down to the level of 1 mg L−1 under
162000 the current experimental conditions, which approaches to the Chinese
Drinking Water Standards of fluoride concentration (1 mg L−1).

160000 3.2.4. Effect of pH

The removal of fluoride ions from aqueous solution is highly
dependent on the pH. Fluoride removal is studied over the pH range of
158000
3 to 11 as shown in Fig. 8.
It is evident from Fig. 8 that the adsorption capacity of fluoride
705 700 695 690 685 680 increases with increasing the pH. The adsorption capacity reaches to a
Binding energy (ev) maximum of 0.54 mg g−1 at pH 6.94 and then slightly decreases to
0.45 mg g−1 at pH 8.05. After that, the adsorption capacity dramat-
Fig. 4. XPS narrow region scans of Fe 2p (a) and F 1s (b) in Fe (III)Fn-STI sample.
ically decreases and the adsorbent exhibits negligible adsorption
0.11 mg g−1 at pH 11.2. The quick reduction of the amount of fluoride
where qe is the adsorption capacity (mg g− 1) at the equilibrium; Co adsorbed in alkaline pH range should be attributed to competitive
and Ce are the initial and equilibrium concentrations of fluoride
(mg L− 1) respectively; V is the volume of the aqueous solution (L) 12 3
and W is the mass (g) of adsorbent used in the experiments.
10
95

90 8 2
Ce (mg L-1)

qe (mg g-1)
Fluoride removal (%)

85
6
80
4 1
75 Ce (mg/L)
qe (mg/g)
70 2

65
0 0
60 0 5 10 15 20 25 30 35 40 45
0 20 40 60 80 100 120 140 160 180 200 Initial concentration (mg L-1)
Time (min)
Fig. 7. Effect of initial concentration (particle size 10–20 μm, initial fluoride concentration
Fig. 5. Effect of contact time (particle size 10–20 μm, adsorbent dose 10 g L−1, fluoride in the range of 5.0–40 mg L− 1, contact time 2 h, adsorbent dose 10 g L− 1 and pH 6.7 ±
concentration of 5.0 mg L−1 and pH 6.7 ± 0.3). 0.3).
 Y. Sun et al. / Desalination 277 (2011) 121–127 125

the regenerated sample indicate that Fe(III)-STI zeolite has no obvious

0.6
reduction in adsorption capacity after three cycles (total 5% reduction
Adsorption capacity ( mg g-1)

in adsorption capacity). The secondary contamination in defluori-

0.5 dated solution is monitored using ICP-AES through three regenerated
cycles. The results show that the concentration of Fe3+ leaching into
0.4 defluoridated water is about 0.05 mg L− 1, which is below the Chinese
Drinking Water Standards (0.3 mg L− 1).
0.3
3.4. Adsorption isotherms
0.2
Fig. 10 exhibits that the adsorption capacity increases with
increasing equilibrium concentration of fluoride. The maximum
0.1 adsorption capacity on Fe(III)-STI zeolite is 2.31 mg g−1.
The distribution of fluoride between the liquid and solid phases
2 4 6 8 10 12
can be expressed by the Langmuir and Freundlich equations in the
pH
adsorption process. The expression of the Langmuir model is given
Fig. 8. Effect of pH on fluoride removal (particle size 10–20 μm, initial fluoride below:
concentration 5.0 mg L− 1, contact time 2 h and adsorbent dose 10 g L− 1).

adsorption between hydroxyl ions and fluoride ions on active sites of 1 1 1 1

Langmuir model: = × + ð2Þ
Fe(III). Moreover, the relatively lower adsorption capacity of fluoride qe qo :b Ce q0
in the acidic pH range may be due to the leakage of active sites Fe ion
in lower acidity. It is worthy of mention here that the optimum pH is
where Ce is the equilibrium concentration (mg L− 1), qe is the
6.94 for fluoride removal, which implies the application of developed
adsorption capacity (mg g− 1), qo is the theoretical maximum
method in drinking water.
adsorption capacity, and b (L mg− 1) is a Langmuir constant related
to the enthalpy of adsorption. qo and b are determined from the slope
3.2.5. Effect of coexisting ions
and intercept of the plot, respectively.
A variety of other anions are generally present in drinking water,
The Freundlich isotherm model is expressed as follows:
and may compete with fluoride ion for adsorption on the Fe(III)-STI
zeolite. In order to investigate the effect of interfering ions on fluoride
removal, the experiments were carried out in the presence of 5 mg L−1 1
of fluoride ion and various concentrations of coexisting ions (chloride, log qe = log KF + log Ce : ð3Þ
n
sulfate, nitrate, carbonate and bicarbonate) ranging from 100–
500 mg L−1 respectively. It is found (Fig. 9) that the percentage of
fluoride removal is almost unchanged when the coexisting ion KF and 1/n are empirical constants, indicative of the adsorption
concentration is below 300 mg L−1, and then decreases dramatically capacity and adsorption intensity, respectively.
when the coexisting ion concentration is over 500 mg L−1. This high Parameters of the Langmuir and Freundlich isotherms fitting for
selectivity and affinity for fluoride make Fe(III)-STI zeolite as a suitable fluoride adsorption data are listed in Table 1. It can be found that the
adsorbent for water treatment application. linear equation of Langmuir model shows higher correlation (R2 =0.996)
than Freundlich model (R2 = 0.926). Therefore Langmuir model is
3.3. Desorption and regeneration selected as the best-fit model for adsorption of fluoride on Fe (III)-STI
zeolite. Satisfactory fitting of the Langmuir model to the adsorption
Any adsorbent is economically viable if the adsorbent can be isotherm suggests that the adsorption of fluoride involves the monolayer
regenerated and reused in many cycles of operation. The regeneration coverage on the surface of the Fe(III)-STI zeolite.
experiments were performed using 1 mol L−1 HCl solution as eluent.
After desorption, adsorbent was regenerated using 0.1 mol L− 1 FeCl3 2.5
solution as described in experimental Section 2.3. Adsorption tests on

100
2.0

80
Fluoride removal (%)

qe (mg g -1)

1.5
60

40 1.0

20
0.5

0
Blank 100 mgL-1 200 mgL-1 300 mgL-1 400 mgL-1 500 mgL-1
0 2 4 6 8 10 12
Ce (mg L-1)
Fig. 9. Effect of coexisting ions with different concentrations on fluoride removal
(particle size 10–20 μm, initial fluoride concentration 5.0 mg L− 1, contact time 2 h, Fig. 10. Adsorption isotherm on Fe(III)-STI zeolite (particle size 10–20 μm and pH 6.7 ±
adsorbent dose 10 g L− 1 and pH 6.7 ± 0.3). 0.3).
126 Y. Sun et al. / Desalination 277 (2011) 121–127

Table 1 4. Conclusions
Langmuir and Freundlich isotherm constants for the adsorption of fluoride on Fe(III)-
STI zeolite.
The natural STI zeolite modified with Fe(III) has a considerable
Langmuir constant Freundlich constant potential for the removal of excess fluoride from the drinking water.
b (L mg− 1) qo (mg g− 1) R2a n KF (mg g− 1) R2 Batch adsorption studies show that fluoride concentration can be
reduced down to the very low level of 1 mg L−1 under the optimum
0.543 2.31 0.996 0.282 0.988 0.926
conditions. XPS and EDX studies all reveal that Fe3+ is impregnated on
a
R2 representing correlation coefficient of linear equation.
the natural STI zeolite and the fluoride is adsorbed on the Fe(III)-STI
zeolite. Desorption and regeneration results show that the exhausted
3.5. Adsorption kinetics Fe(III)-STI zeolite can be regenerated using 1 mol L−1 HCl as eluent
and the regenerated samples still remain the good adsorptive
Adsorption of fluoride ion is rapid for the first 15 min and its rate performance. The fluoride adsorption on Fe(III)-STI is well described
gradually slows down as the equilibrium approaches. The rate by the Langmuir adsorption model, and the maximum adsorption
constant Kad for adsorption of fluoride is investigated by Lagergren capacity is 2.31 mg g−1. The kinetic result indicates that the
rate equation [36,37]. A larger adsorption rate constant Kad usually adsorption of fluoride on the modified natural zeolite follows
represents a quicker adsorption rate. Lagergren equation. Fluoride sorption on the Fe(III)-STI zeolite may
be a diffusion controlled process combined with chemisorption. The
Kad t natural STI zeolite is an environment-friendly adsorbent with lower
logðqe −qÞ = logqe − ð4Þ
2:303 chemical consumption and waste release and operating costs.

where qe and q (both in mg g− 1) are the amounts of fluoride adsorbed at

equilibrium and at time ‘t’, respectively. Straight line plot of log (qe − q)
versus ‘t’ at different times indicates the validity of Lagergren rate
equation.
In this case the plot of log (qe − q) versus ‘t’ is straight line with
R2 = 0.986, indicating that adsorption of fluoride follows first order
kinetics. The adsorption rate constant (Kad), calculated from the slope of
the plot is found to be 0.0085 min− 1 for initial fluoride concentration of
5.0 mg L− 1. This rate is not very quick compared with those values
reported in the literatures [38–40], indicating that the diffusion of
fluoride into the cavity of zeolite has a significant influence on
adsorption process. As we know, the framework of STI zeolite is
negatively charged, which impedes the penetration of fluoride ions with
high electronegativity into the cavity of zeolite.
3.6. Adsorption mechanism
In aqueous solution, the active sites of Fe3+ on the Fe(III)-STI
zeolite form into oxyhydroxides [41,42] which can be explained by
the following reactions (in acid media on acid-treated zeolite):
þ þ
Zeo−FeOH + H ⇌Zeo−FeOH2
þ −
Zeo−FeOH⇌H + Zeo−FeO :
Hence, anions such as F− can be adsorbed through direct ion
exchange according to the schemes:
− −
Zeo−FeOH + F ⇌Zeo−FeF + OH
þ −
Zeo−FeOH2 + F ⇌Zeo−FeF + H2 O:
Or they can undergo non-specific columbic interaction
þ − þ −
Zeo−FeOH2 + F ⇌Zeo−FeOH2 ::::F :
According to the above equations, an iron atom can bind a fluoride
atom during adsorption process. From EDX and XPS surface
quantitative analyses, the atomic ratio of Fe to F on zeolite surface is
close to 5–8:1, far beyond theoretical value of 1:1. This implies that
fluoride does not easily penetrate into the cavity of zeolite due to
repulsion of zeolite framework, and only 10–20% active sites of iron
located on the outer surface of zeolite are accessible to fluoride.
Overall, the mechanism of the fluoride sorption on the Fe(III)-STI
zeolite is a complex process, which may be a diffusion controlled
process combined with chemisorption.
Acknowledgments
This work was financially supported by Key Discipline of Shanghai
Education Committee (No. J50102). We also give many thanks to Pro.
Yingcai Long from Fudan University in Shanghai for his friendly help.
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