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Adsorption of uoride from aqueous solution by graphene

Yanhui Li
a,b,
, Pan Zhang
a
, Qiuju Du
a
, Xianjia Peng
c
, Tonghao Liu
a
, Zonghua Wang
a
, Yanzhi Xia
a
,
Wei Zhang
d
, Kunlin Wang
d
, Hongwei Zhu
d
, Dehai Wu
d
a
Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road, Qingdao 266071, China
b
College of Electromechanical Engineering, Qingdao University, 308 Ningxia Road, Qingdao 266071, China
c
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
d
Key Laboratory for Advanced Manufacturing by Material Processing Technology, Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China
a r t i c l e i n f o
Article history:
Received 26 April 2011
Accepted 9 July 2011
Available online 23 July 2011
Keywords:
Graphene
Fluoride
Adsorption
Kinetics
Thermodynamics
a b s t r a c t
A batch adsorption system was applied to investigate the adsorption of uoride from aqueous solution by
graphene. The adsorption capacities and rates of uoride onto graphene at different initial pH, contact
time, and temperature were evaluated. The experimental results showed that graphene is an excellent
uoride adsorbent with an adsorption capacity of up to 17.65 mg/g at initial uoride concentration of
25 mg/L and temperature of 298 K. The isotherm analysis indicated that the adsorption data can be well
described by Langmuir isotherm model. Thermodynamic studies revealed that the adsorption reaction
was a spontaneous and endothermic process.
2011 Elsevier Inc. All rights reserved.
1. Introduction
Fluoride is a major naturally occurring contaminant in drinking
water in many regions of the world. Ingestion of uoride within
the permissible limit is benecial to human body for the calcica-
tion of dental enamel and maintenance of healthy bones. When
uoride is present in excess of 1.5 mg/L [1], it affects the metabo-
lism of elements such as Ca and P in human body [2] and causes
molting of teeth and lesion of endocrine glands, thyroid, liver,
and other organs [3,4]. The most common symptom of chronic
uoride exposures is skeletal uorosis, which can lead to the
permanent bone and joint deformations and dental uorosis. The
dental or skeletal uorosis is irreversible and no treatment exists.
The only remedy is prevention by keeping uoride ion intake
within safe limits. According to WHO, the permissible limit of
uoride in drinking water is 1.0 mg/L [5], and the superuous
uoride should be removed from drinking water. So, it is impera-
tive and signicant to explore the suitable technique to remove
excessive uorides from water.
Many methods have been developed for uoride removal from
water, such as precipitation [6], membrane processes, ion
exchange [7], and adsorption processes [3]. The main disadvantage
of precipitation is the generation of unwanted chemicals and waste
disposal issues [8]. The disadvantages of membrane processes are
low economic viability, high maintenance cost, fouling, scaling,
and membrane degradation. Adsorption is a widely accepted tech-
nology, because this is more effective in reducing uoride concen-
trations to permissible value than the precipitation methods [8].
Additionally, adsorption is considered a fast and inexpensive puri-
cation method [9]. Adsorption is a widely used method for deu-
oridation, which depends on ions (adsorbate) in uid diffusing to
the surface of a solid (adsorbent), where they bond with the solid
surface or are held there by weak intermolecular forces [10].
Among all of the deuoridation adsorbents, carbonaceous materi-
als such as activated carbon [11] and carbon nanotubes [12] are
the most commonly used adsorbents due to their large specic sur-
face area, large quantity of surface functional groups, and abundant
pore size distribution.
Graphene is a newly emerging member of carbon materials
with sp2-hybridized single-atom-layer structure. It is a typical
two-dimensional material of carbon atoms packed densely in a
honeycomb crystal lattice. It has drawn much scientic attention
since its discovery due to its unique electronic [1315] and
mechanical properties [15], specic magnetism [16], excellent
mobility of charge carriers [17], and high thermal conductivity
[18]. It exhibits great promise for potential applications in many
technological aspects such as eld-effect transistors [19], solar
cells [20], sensors [21], and adsorbent for heavy metal removal
[22]. However, up to now, no investigations have been carried on
utilizing graphene as adsorbent to remove uoride from aqueous
solution.
0021-9797/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.07.032

Corresponding author at: Laboratory of Fiber Materials and Modern Textile, The
Growing Base for State Key Laboratory, Qingdao University, 308 Ningxia Road,
Qingdao 266071, China. Fax: +86 532 85951842.
E-mail address: liyanhui@tsinghua.org.cn (Y. Li).
Journal of Colloid and Interface Science 363 (2011) 348354
Contents lists available at ScienceDirect
Journal of Colloid and Interface Science
www. el sevi er . com/ l ocat e/ j ci s
In this study, the uoride adsorption properties of graphene
were studied through investigating experimental parameters such
as pH, contact time, and temperature. Adsorption isotherm, kinetic
and thermodynamic parameters have been estimated from
experimental results.
2. Experimental
2.1. Sample preparation
Graphene was prepared by a facile liquid phase exfoliation of
worm-like graphite as described elsewhere [23]. In brief, natural
graphite akes were dispersed into a mixture (20:1 by volume)
of concentrated sulfuric acid (98 wt%) and hydrogen peroxide
(30 wt%). After stirred for 1 h and washed with deionized water,
the mixture was dried at 100 C for 24 h to obtain graphite interca-
lation compounds. The graphite intercalation compounds were
heated at 900 C for 10 s, the decomposition of the intercalating
acid leads to a dramatic increase in the dimension perpendicular
to the graphite sheets (worm-like graphite). The worm-like graph-
ite was subjected to a nal exfoliation to obtain monolayer or a few
layers of graphene sheets by ultrasonication and centrifugation of a
1-methyl-2-pyrrolidinone (NMP) suspension (0.1 mg/mL) of the
sample. The top half of the dispersion was heated at 200 C to
remove NMP for further use.
2.2. Characterization of graphene
The morphology and structure of graphene was characterized
by SEM (JEOL JSM-6390LV) and TEM (JEM-2100F). Raman
spectroscopy was performed with a Renishaw RM2000 Raman
microscope. The BrunauerEmmettTeller (BET) surface area
and porous properties of graphene were determined from the
N
2
adsorption at 196 C using a Micrometric ASAP 2000 system.
FTIR spectrum of graphene was recorded with a FTIR Spectrome-
ter (Nicolet 5700) over the wave number range from 4000 to
400 cm
1
. Pressed disks were prepared by grinding the powdered
graphene with KBr in an agate mortar. Zeta potential of graphene
was measured by a Malvern zetameter (Zetasizer 2000). The pH
values of graphene solution were adjusted from 4.0 to 9.0 by
adding 0.1 M hydrochloric acid or sodium hydroxide solution to
the glass beaker at 298 K.
2.3. Batch adsorption experiments
Batch adsorption experiments were conducted to determine the
uoride adsorption equilibrium and kinetic properties of graphene.
Fluoride stock solution (1000 mg/L) was prepared by dissolving
NaF (AIBI, Shanghai, China) in deionized water and further diluted
to the required concentrations before used.
The effect of initial and nal pH on uoride adsorption by
graphene was conducted in a pH range of 3.610.2. The pH of
the solution was adjusted to a desired value using appropriate
concentrations of HNO
3
or NaOH solutions. For every experiment,
100 mL of the solution with uoride concentration of 15 mg/L
was mixed with 0.05 g of graphene in a 250 mL glass conical ask.
The ask was sealed tightly and placed on a SHZ-82A thermostatic
water-bath shaker and shaken for 6 h. The suspension was ltered
through a 0.45 lm membrane lter. The ltrate was measured by a
uoride ion spectrophotometer (IC-Dionex 500, USA). The amount
of uoride adsorbed at equilibrium was calculated using the
following equation:
q
e

C
0
C
e
m

V 1
where C
0
and C
e
are initial and equilibrium concentrations of uo-
ride (mg/L), respectively, m is the mass of graphene (g) and V is vol-
ume of the solution (L).
Adsorption kinetic study was carried out by adding 1.0 g of
graphene into a glass beaker containing 2000 mL solution with dif-
ferent uoride concentrations (5, 15 and 25 mg/L) to determine the
minimum time required for adsorption to reach equilibrium at pH
7.0 and at temperature of 298 K. At selected time intervals, 5 mL
samples were extracted from the beaker using a 10 mL syringe
and analyzed by the ion spectrophotometer. The amount of
adsorption at time t, q
t
(mg/g) was calculated by:
q
t

C
0
C
t
m

V 2
where C
t
(mg/L) is the concentration of uoride ions at indicated
time.
To evaluate the thermodynamic properties, 0.05 g graphene
was added into 100 mL solutions with pH of 7.0 and initial uoride
concentrations ranging from 5 to 30 mg/L at a step of 5 mg/L. These
samples were shaken continuously for 2 h at 273, 298, and 323 K,
respectively.
3. Results and discussion
3.1. Characterizations of graphene
The surface morphology of graphene was characterized by SEM
and TEM. As shown in Fig. 1a, graphene lm has irregular form, and
its lateral dimensions range from several micrometers to ten or
more micrometers. The surface of graphene has lots of leaf-like
veins that come from the crumpling and scrolling of graphene
sheets. TEM image (Fig. 1b) shows that graphene lm is transpar-
ent, which is usually rippled and entangled due to partial overlap-
ping of graphene sheets. BET analysis shows that the specic
surface area of graphene is only 3.08 m
2
/g; the relatively low spe-
cic surface area of graphene may be due to the severe aggregation
of graphene layers. The average pore size (4 V/A by BET) of graph-
ene is 2.98 nm, suggesting that the graphene sheets overlap and
aggregate into a mesoporous material.
Raman spectroscopy is a fast, nondestructive, and unambiguous
technique to study carbonaceous materials. The Raman spectrum
of graphene is very sensitive to the number of atomic layers and
the presence of disorder or defects, which allows for accurate
graphene characterization [24]. Fig. 2 shows Raman spectrum of
the graphene measured at 514 nm excitation. The G peak at
1583 cm
1
represents the E
2g
in-plane vibrational modes [24].
The single and sharp 2D peak appears at 2688 cm
1
. The higher
intensity of the 2D peak than the G peak indicates that the sample
prepared by this method is graphene.
The FT-IR spectrum of graphene was characterized and shown
in Fig. 3. The band at wavenumber of 3420 cm
1
is indicative of
the appearance of the stretching of AOH. The bands at
2920 cm
1
and 2360 cm
1
are associated with the stretching of
CH2 and CH3 groups from the organic solvent of NMP. The band
at 1640 cm
-1
can be ascribed to stretching mode of amide type
C@O bond introduced by oxidation treatment of graphite by sulfu-
ric acid and hydrogen peroxide. The bands at 1430 and 1110 cm
1
can be ascribed to the appearance of CH2 and CAN groups, which
are possibly introduced on the surface of graphene by NMP
treatment.
Zeta potential is a physical parameter used to quantify the elec-
trical potential of the solid particle surface. By measuring the zeta
potential as function of pH, the acidity or basicity of graphene sur-
face and the isoelectric point (IEP) where the zeta potential equals
zero can be determined. The IEP of graphene is 4.7 (Fig. 4). This
Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354 349
indicates that at pH < IEP, the graphene has positive surface charge
and can act as anion exchanger, while at pH > IEP, the surface
charge of graphene is negative, which benets for adsorbing
cations.
3.2. Adsorption studies
3.2.1. Effect of pH
Solution pH is one of the most important parameters to deter-
mine the adsorption property of an adsorbent due to its effect not
only on surface charge of the adsorbent but also on the degree of
ionization and speciation of adsorbate [25]. Fig. 5 shows the
variation of adsorption capacity of uoride adsorbed by graphene
at various initial and nal pH values. Fluoride adsorption by
graphene is sensitive to pH variations. The adsorption capacity
increases with pH
initial
in acidic range and reaches the maximum
value of 11.4 mg/g at pH
initial
7.0. The lower adsorption capacity
at pH 3.6 may be due to the formation of hydrouoric acid
[26,27]. Further increasing pH
initial
shows a decreasing trend,
and the adsorption capacity has a sudden decrease when the
pH
initial
is over 7.5. The decrease of the adsorption capacity in
alkaline pH may be attributed to the repulsion between nega-
tively charged surface of graphene and uoride ion and the
competition for surface adsorption sites between the negative
hydroxyl ions and uoride ions [26,27].
Fig. 1. (a) SEM and (b) TEM images of graphene.
1000 1500 2000 2500 3000
1000
1200
1400
1600
1800
2000
I
n
t
e
n
s
i
t
y

(

a
.

u
.
)
Raman shift (cm
-1
)
G
2D
Fig. 2. Raman spectra of graphene.
1000 2000 3000 4000
0.0
0.1
0.2
0.3
2920
1640
1430
1110
2360
A
b
s
o
r
b
a
n
c
e
Wavenumber (cm
-1
)
3420
Fig. 3. FTIR spectrum of graphene.
- 40
- 30
- 20
- 10
0
10
20
4 6 8
pH
Z
e
t
a

p
o
t
e
n
t
i
a
l

(
m
V
)
Fig. 4. Zeta potential curve versus pH of graphene.
3 4 5 6 7 8 9 10
2
4
6
8
10
12
q
e

(
m
g
/
g
)
P
H
pH
initial
pH
final
Fig. 5. Effect of initial and nal pH on uoride adsorption by graphene.
350 Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354
Anions have been proposed to be adsorbed on adsorbents
through specic and/or nonspecic adsorption [28,29]. The specic
adsorption involves ligand exchange reactions, where the anions
displace OH groups from the surface [28]. The nonspecic adsorp-
tion involves the coulombic forces and mainly depends on the IEP
of the adsorbent [29]. The nonspecic adsorption indicates that the
uoride adsorption capacity of an adsorbent decreases at pH PIEP
due to neutrally or negatively charged surface of the adsorbent
[30]. However, our experimental result shows that the best uo-
ride adsorption occurs at pH 7.0, which is much higher than IEP
of graphene (IEP of graphene = 4.7). This means that the adsorption
takes place even though the surface is electrically negative. The
phenomenon suggests that adsorption of uoride by graphene is
mainly a specic process. Thus, at pH = 7.0, uoride ions are pre-
dominantly adsorbed by the following surface-exchange reactions
[31]:
GrapheneOH

2
surf F

GrapheneF surf H
2
O 3
GrapheneOH surf F

GrapheneF surf OH

4
The nal pH has an obvious increase after uoride adsorption at
acidic pH range (Fig. 5), indicating that the adsorption mechanism
for the graphene is ion exchange between uoride ions in solution
and hydroxyl ions in the adsorbent [32].
3.2.2. Adsorption kinetics
The effect of contact time on uoride adsorbed by graphene was
studied and shown in Fig. 6. It can be seen that adsorption is fast
due to the availability of plenty of active sites on the adsorbent
surface at initial stage. The fast adsorption may be due to the
special one-atom-thick layered structure of graphene, and as it gets
in touch with uoride ions in the aqueous solution, the adsorption
occurs immediately due to the higher driving force to make fast
uoride transfer to the active sites on the surface of graphene
[33]. With further increasing time, the diminishing availability of
the remaining active sites and the decrease in the driving force
make it take long time to reach equilibrium. Thus, the adsorption
rate becomes slower. Equilibrium time increases with increasing
initial uoride concentration. It only takes about 20 min to reach
adsorption equilibrium for initial uoride concentration of 5 mg/
g, while it needs 60 min for initial uoride concentration of
25 mg/g.
In order to investigate the mechanism of adsorption and poten-
tial rate controlling steps such as chemical reaction, diffusion
control, and mass transport processes, three kinetic models,
namely pseudo-rst-order, pseudo-second-order, and intra-parti-
cle diffusion models, were analyzed.
The pseudo-rst-order equation is expressed as follows [34]:
logq
e
q
t
log q
e

k
1
2:303
t 5
where k
l
is the Lagergren rate constant of adsorption (1/min). The
plot of log(q
e
q
t
) against t gives a linear relationship from which
k
1
and q
e
are determined from the slope and intercept of plot,
respectively.
The pseudo-second-order model can be represented by the fol-
lowing linear form [35]:
t
q
t

1
k
2
q
2
e

t
q
e
6
where k
2
is the pseudo-second-order rate constant of adsorption
(g/mg min). The values of q
e
and k
2
are determined from the slope
and intercept of the plot of t/q
t
against t.
The validity of each kinetic model was checked by the tted
straight lines and depicted in Fig. 7. The corresponding kinetic
parameters and the determination coefcients are summarized in
Table 1. The values of the determination coefcient obtained from
the linear plot of pseudo-rst-order (Fig. 7a) model are very small
(R
2
< 0.9744), suggesting that the applicability of this model to the
adsorption processes of uoride adsorption by graphene is unfeasi-
ble. The higher determination coefcients (R
2
> 0.9924) are
obtained for pseudo-second-order model (Fig. 7b), indicating that
the experimental data are well described by pseudo-second-order
model, and the nature of adsorption is a chemical-controlling
process [36]. The rate constant (k
2
) of the pseudo-second-order
equation decreases with increasing initial uoride concentration,
indicating that uoride adsorption may be more favorable at low
solute concentration.
0 20 40 60 80 100
0
5
10
15
20
5 mg/g
15 mg/g
25 mg/g
q
e

(
m
g
/
g
)
Time (min)
Fig. 6. Time effect on uoride adsorption by graphene.
0 10 20 30 40 50 60
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
l
o
g

(
q
e
-
q
t
)
Time (min)
5 mg/L
15 mg/L
25 mg/L
a
0 20 40 60 80 100 120
0
5
10
15
20
25
30
35
t
/
q
t
5 mg/L
15 mg/L
25 mg/L
Time (min)
b
Fig. 7. Adsorption kinetics of uoride adsorption by graphene: (a) pseudo-rst-
order and (b) pseudo-second-order.
Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354 351
3.2.3. Effect of temperature
Fig. 8 shows that adsorption increases with increasing temper-
ature. The adsorption capacity increases from 12.29 to 19.59 mg/g
at uoride equilibrium concentration of 15 mg/L, as the tempera-
ture rises from 273 to 323 K. The observation shows that the inter-
action between adsorbate and adsorbent is endothermic in nature.
3.2.4. Adsorption isotherms
Adsorption isotherms can be generated based on numerous the-
oretical models, where Langmuir and Freundlich models are the
most frequently used.
The Langmuir model supposes that uptake of metal ions occurs
on a homogenous surface by monolayer adsorption without any
interaction between adsorbed ions, with homogeneous binding
sites, equivalent sorption energies, and no interaction between
adsorbed species. Its mathematical form is written as [37]:
C
e
q
e

C
e
q
max

1
q
max
k
L
7
where q
max
is the maximum adsorption capacity corresponding to
complete monolayer coverage (mg/g) and k
L
is a constant indirectly
related to adsorption capacity and energy of adsorption (L/mg),
which characterizes the afnity of the adsorbate with the adsor-
bent. A straight line is obtained when C
e
/q
e
was plotted against C
e
and q
max
, and k
L
could be calculated from the slopes and intercepts
(Table 2).
The Freundlich equation [38] is an empirical equation based on
adsorption on a heterogeneous surface. The equation is commonly
represented by:
lnq
e
lnk
F

1
n
lnc
e
8
where k
F
and n are the Freundlich constants characteristics of the
system, indicating the adsorption capacity and the adsorption
intensity, respectively. From the slope and intercept of the straight
portion of the linear plot obtained by plotting ln q
e
against ln C
e
,
the values of Freundlich parameters were calculated and listed in Ta-
ble 2.
Table 2 shows that the Langmuir isotherm model has higher
determination coefcients R
2
(>0.9813). It indicates that the
Langmuir model ts the experimental data well, and the adsorp-
tion of uoride by graphene takes place in a monolayer adsorption
manner. The calculated monolayer saturated adsorption capacity
reaches 35.59 mg/g at pH = 7.0 and at 298 K, which is higher than
that of the previously reported adsorbents (Table 3). Therefore,
graphene is an effective uoride removal material in wastewater
treatment. Although the determination coefcients R
2
(0.9528,
0.9566, and 0.9815) of the Freundlich equation are lower than
those of the Langmuir equation (Table 2), the Freundlich equation
can be used to roughly evaluate the adsorption capacity and
afnity of graphene for uoride ions. The higher values of k
F
indicate that graphene has a higher adsorption capacity and
afnity for uoride ions. The n values are between 1 and 10, indi-
cating that the adsorption is favorable at these studied conditions
[42].
3.2.5. Adsorption thermodynamic study
Thermodynamic parameters can be calculated from the
variation of the thermodynamic equilibrium constant K
0
, with
the change in temperature [43]. For adsorption reactions, K
0
is
dened as follows:
K
0

a
s
a
e

v
s
v
e
C
s
C
e
9
where a
s
is the activity of adsorbed uoride, a
e
is the activity of uo-
ride in solution at equilibrium, C
s
is the amount of uoride adsorbed
by per mass of graphene (mmol/g), v
s
is the activity coefcient of
the adsorbed uoride, and v
e
is the activity coefcient of uoride
in solution. As uoride concentration in the solution decreases
and approaches zero, K
0
can be obtained by plotting ln(C
s
/C
e
) versus
C
s
and extrapolating C
s
to zero [43]. A linear regression analysis
nds that the straight line ts the data well, and the values of K
0
are obtained from the straight line intercept with the vertical axis.
The calculated values of K
0
at temperatures of 273, 298, and 323 K
are 1.70, 1.67, and 2.05, respectively.
The average standard enthalpy change (DH
0
) is obtained from
Vant Hoof equation:
lnK
0
T
3
lnK
0
T
1

DH
0
R
1
T
3

1
T
1

10
where T
3
and T
1
are two different temperatures. The calculated va-
lue of DH
0
is 1064.54 cal/mol.
The adsorption standard free energy changes (DG
0
) can be cal-
culated according to:
DG
0
RT lnK
0
11
where R is the universal gas constant (1.987 cal/K mol) and T is the
temperature in Kelvin. The standard entropy change (DS
0
) can be
obtained by:
DS
0

DG
0
DH
0
T
12
Table 1
Parameters of two kinds of kinetic models.
Kinetic model Parameters Values
5
(mg/L)
15
(mg/L)
25
(mg/L)
Pseudo-rst-order q
e
(mg/g) 5.02 13.45 19.15
k
1
(1/min) 0.23 0.07 0.06
R
2
0.9619 0.9180 0.9744
Pseudo-second-order q
e
(mg/g) 4.05 14.31 22.68
K
2
(g/mg min) 10
3
50.82 3.99 2.49
R
2
0.9972 0.9924 0.9953
0 10 20 30 40
5
10
15
20
25
30
q
e

(
m
g
/
g
)
C
e
(mg/L)
273 K
298 K
323 K
Fig. 8. Temperature effect on uoride adsorption by graphene.
Table 2
Parameters of Freundlich and Langmuir adsorption isotherm models for uoride
adsorbed by graphene.
T (K) Freundlich Langmuir
n k
F
R
2
q
max
k
L
R
2
273 1.85 2.57 0.9528 22.42 0.0783 0.9910
298 1.53 2.49 0.9566 35.59 0.0528 0.9813
323 1.45 2.75 0.9815 48.31 0.0429 0.9815
352 Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354
The thermodynamic parameters are listed in Table 4. The
calculated values of DG
0
at temperatures of 273, 298, and 323 K
are 287.50, 303.76, and 460.71 cal/mol, respectively. The
calculated values of DS
0
at temperatures of 273, 298, and 323 K
are 3.46, 3.22, and 3.46 cal/mol K, respectively. Positive values of
DH
0
suggest that the interaction of uoride adsorbed by graphene
is endothermic process, which is supported by the increasing
adsorption of uoride with the increase in temperature. The
negative values of DG
0
reveal the fact that adsorption process
was spontaneous. The positive values of DS
0
indicate increased
randomness at the adsorbent/solution interface during the adsorp-
tion of uoride onto graphene [44].
3.3. Potential applications and limitations
Actually, the adsorbents are usually used at a uoride concen-
tration below 5 mg/L. Therefore, the mass of the adsorbent, which
reduces the uoride concentration from 5 to 1 mg/L for an aqueous
solution of 1 m
3
, is compared according to the following mass bal-
ance equation [45]:
VC
0
mq
e
VC
e
13
where q
e
and C
e
must be in equilibrium, q
e
for graphene can be cal-
culated by substituting k
F
= 2.49 and n = 1.53 (Table 2, pH = 5.0) into
the Eq. (8), C
0
, C
e
, and V are 5, 1 mg/L, and 1 m
3
, respectively. The
mass required for graphene is 1.2 kg, which is 6.3 and 2.3 times less
than that of the AlC-300 carbon (7.5 kg) [45] and aligned carbon
nanotubes (2.7 kg) [12], respectively. Obviously, graphene is suit-
able for application as adsorbent to remove uoride from wastewa-
ter. However, there are numerous challenges still to be faced. The
rst is high cost of graphene. It is necessary to explore new prepa-
ration techniques to produce graphene in bulk so as to decrease the
cost of graphene greatly. Another is the toxicity of graphene. A pre-
liminary study on the toxicity of graphene oxide in a human lung
carcinoma epithelial cell (A549) [46] showed that graphene oxide
hardly enters cells and has no obvious cytotoxicity. Systematic
studies on the toxicity of graphene need to be carried out further.
In short, the high adsorption efciency, large adsorption capacity,
and nontoxicity suggest that graphene is a promising uoride
adsorbent in environment protection.
4. Conclusions
The results obtained in this study show that graphene is an
effective adsorbent for removal of uoride from aqueous solution.
The experimental data were well tted with the Langmuir
isotherm equation. The monolayer adsorption capacity of uoride
by graphene was found to be 35.59 mg/g at pH = 7.0 and at
298 K. Kinetic data were well tted to a pseudo-second-order
kinetic model, suggesting that the adsorption was a chemical-
controlling process. Thermodynamic investigations indicated that
the adsorption reaction was a spontaneous, endothermic, and
irreversible process.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (50802045 and 20975056), Natural Science,
Program of NSFC-JSPS (21111140014), SRF for ROCS, SEM, the Mid-
dle-aged and Youth Scientist Incentive Foundation of Shandong
Province (BS09018), the Taishan Scholar Program of Shandong
Province, and Program for Changjiang Scholars and Innovative Re-
search Team in University (IRT0970), China.
References
[1] L.M. Camacho, A. Torres, D. Saha, S. Deng, J. Colloid Interface Sci. 349 (2010)
307313.
[2] Y. engeloglu, E. Kir, M. Erz, Sep. Purif. Technol. 28 (2002) 8186.
[3] H. Lounici, L. Addour, D. Belhocine, H. Grib, S. Nicolas, B. Bariou, Desalination
114 (1997) 241251.
[4] M. Hichour, F. Persin, J. Sandeaux, C. Gavach, Sep. Purif. Technol. 18 (2000)
111.
[5] S.S. Tripathy, J.L. Bersillon, K. Gopal, Sep. Purif. Technol. 50 (2006) 310317.
[6] S. Saha, Water Res. 27 (1993) 13471350.
[7] S.K. Adhikary, U.K. Tipnis, W.P. Harkare, K.P. Govindan, Desalination 71 (1989)
301312.
[8] S. Ayoob, A.K. Gupta, V.T.A. Bhat, Crit. Rev. Environ. Sci. Technol. 38 (2008)
401470.
[9] I. Ali, V.K. Gupta, Nat. Protoc. 1 (2007) 26612667.
[10] T.N. de Castro Dantas, A.A. Dantas, M.C.P. de, A. Moura, Water Res. 35 (2001)
22192224.
[11] A.A.M. Daifullah, S.M. Yakout, S.A. Elreefy, J. Hazard. Mater. 147 (2007)
633643.
[12] Y.H. Li, S. Wang, X. Zhang, J. Wei, C. Xu, Z. Luan, D. Wu, Mater. Res. Bull. 38
(2003) 469476.
[13] D. Eom, D. Prezzi, K.T. Rim, H. Zhou, M. Lefenfeld, S. Xiao, C. Nuckolls, M.S.
Hybertsen, T.F. Heinz, G.W. Flynn, Nano Lett. 9 (2009) 28442848.
[14] C. Mattevi, G. Eda, S. Agnoli, S. Miller, K.A. Mkhoyan, O. Celik, D. Mastrogio-
vanni, G. Granozzi, E. Garfunkel, M. Chhowalla, Adv. Funct. Mater. 19 (2009)
25772583.
[15] C. Lee, X. Wei, J.W. Kysar, J. Hone, Science 321 (2008) 385388.
[16] A.K. Singh, B.I. Yakobson, Nano Lett. 9 (2009) 15401543.
[17] S. Latil, L. Henrard, Phys. Rev. Lett. 97 (2006) 036803.
[18] A.A. Balandin, S. Ghosh, W. Bao, I. Calizo, D. Teweldebrhan, F. Miao, C.N. Lau,
Nano Lett. 8 (2008) 902907.
[19] Y.B. Tang, C.S. Lee, Z.H. Chen, G.D. Yuan, Z.H. Kang, L.B. Luo, H.S. Song, Y. Liu,
Z.B. He, W.J. Zhang, I. Bello, S.T. Lee, Nano Lett. 9 (2009) 13741377.
[20] X. Wang, L. Zhi, K. Mullen, Nano Lett. 8 (2008) 323327.
[21] P.K. Ang, W. Chen, A.T.S. Wee, K.P. Loh, J. Am. Chem. Soc. 130 (2008)
1439214393.
[22] X. Deng, L. L, H. Li, F. Luo, J. Hazard. Mater. 183 (2010) 923930.
Table 3
Comparison of adsorption capacity of uoride by different adsorbents.
Adsorbents Experimental conditions Ref.
Dosage (g/L) pH T (C) Concentration (mg/L) q
max
(mg/g)
Alum impregnated activated alumina 8.0 6.5 25 135 40.30 [5]
Activated carbon 1.5 2.0 25 520 23.30 [12]
Aligned carbon nanotubes 0.5 7.0 25 540 1.99 [13]
Magnetic chitosan particle 1.0 7.0 20 540 22.49 [39]
Plaster of Paris 20.0 6.72 30 210 0.37 [40]
Bleaching earth 1.25 3.5 25 545 5.39 [41]
Graphene 0.5 7.0 25 540 35.59 This study
Table 4
Thermodynamic parameters for uoride adsorbed by graphene.
Thermodynamic
constant
Temperature (K)
273 298 323
K
0
1.70 1.67 2.05
DG
0
(cal/mol) 287.50 303.76 460.71
DH
0
(cal/mol) 656.03 656.03 656.03
DS
0
(cal/mol K) 3.46 3.22 3.46
Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354 353
[23] W. Gu, W. Zhang, X. Li, H. Zhu, J. Wei, Z. Li, Q. Shu, C. Wang, K. Wang, W. Shen,
F. Kang, D. Wu, J. Mater. Chem. 19 (2009) 33673369.
[24] I. Calizoa, S. Ghosh, W. Bao, F. Miao, C.N. Lau, A.A. Balandin, Solid State
Commun. 149 (2009) 11321135.
[25] M. Jimnez-Reyes, M. Solache-Ros, J. Hazard. Mater. 180 (2010) 297302.
[26] S.P. Kamble, G. Deshpande, P.P. Barve, S. Rayalu, N.K. Labhsetwar, A. Malyshew,
B.D. Kulkarni, Desalination 264 (2010) 1523.
[27] Y. Zhou, C. Yu, Y. Shan, Sep. Purif. Technol. 36 (2004) 8994.
[28] J.L. Reyes Bahena, A. Robledo Cabrera, A. Lpez Valdivieso, R. Herrera Urbina,
Sep. Sci. Technol. 37 (2002) 19731987.
[29] P.D. Rude, R.C. Aller, Am. J. Sci. 293 (1993) 124.
[30] Y. Li, S. Wang, A. C, D. Zhao, X. Zhang, C. Xu, Z. Luan, D. Ruan, J. Liang, D. Wu, B.
Wei, Chem. Phys. Lett. 350 (2001) 412416.
[31] A. Lpez Valdivieso, J.L. Reyes Bahena, S. Song, R. Herrera Urbina, J. Colloid
Interface Sci. 298 (2006) 15.
[32] T. Hiemstra, W.H. van Riemsdijk, J. Colloid Interface Sci. 225 (2000) 94104.
[33] Y. Wu, S. Zhang, X. Guo, H. Huang, Bioresour. Technol. 99 (2008) 77097715.
[34] Y.S. Ho, G. McKay, Water Res. 34 (2000) 735742.
[35] Y.S. Ho, G. McKay, Process Biochem. 34 (1999) 451465.
[36] Z. Cheng, X. Liu, M. Han, W. Ma, J. Hazard. Mater. 182 (2010) 408415.
[37] I. Langmuir, J. Am. Chem. Soc. 38 (1916) 22212295.
[38] H.M.F. Freundlich, Z. Phys. Chem. 57 (1906) 385471.
[39] W. Ma, F.Q. Ya, M. Han, R. Wang, J. Hazard. Mater. 143 (2007) 296302.
[40] V. Gopal, K.P. Elango, J. Hazard. Mater. 141 (2007) 98105.
[41] M. Mahramanlioglu, I. Kizilcikli, I.O. Bicer, J. Fluorine Chem. 115 (2002).
[42] B.H. Hameed, J. Hazard. Mater. 154 (2008) 204212.
[43] R. Niwas, U. Gupta, A.A. Khan, K.G. Varshney, Colloids Surf. A 164 (2000)
115119.
[44] Y. Nuhoglu, E. Malkoc, Bioresour. Technol. 100 (2009) 23752380.
[45] R. Leyva Ramos, J. Ovalle-Turrubiartes, M.A. Sanchez Castillo, Carbon 37 (1999)
609.
[46] Y. Chang, S. Yang, J.H. Liu, E. Dong, Y. Wang, A. Cao, Y. Liu, H. Wang, Toxicol.
Lett. 200 (2011) 201210.
354 Y. Li et al. / Journal of Colloid and Interface Science 363 (2011) 348354