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g r a p h i c a l a b s t r a c t
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i n f o
Article history:
Received 21 April 2015
Received in revised form 4 June 2015
Accepted 7 June 2015
Available online 12 June 2015
Keywords:
Chitosan and graphene oxide composite
adsorbent
pH-tunable surface charge
Removal of multiple pollutants
Adsorption mechanism
a b s t r a c t
A versatile composite adsorbent combination of chitosan and graphene oxide (CSGO) has been prepared
by self-assembly method. This well-obtained adsorbent has amphoteric characteristics that show
pH-tunable surface charge and morphology. These vital features result in its exible and tunable
adsorption performance. CSGO is highly efcient in removing multiple types of pollutants from water,
including various dyes and metal ions with different charge properties: cationic [methylene blue (MB)
and Cu(II)] and anionic species [methyl orange (MO) and Cr(VI)]. Multiple mechanisms, including
electrostatic interaction, pp stacking, and chelating effects, are involved in the adsorption of the four
pollutants for their different structural characteristics and charge properties. Both pollutants can be
efciently removed at suitable pH conditions in MB/Cu(II) and MO/Cr(VI) binary systems. Moreover,
CSGO shows strongly preferential adsorption of MB over Cu(II) at lower pH levels, whereas very slight
selectivity of MO over Cr(VI). According to the adsorption kinetics results, the equilibrium time of CSGO
for adsorption of each pollutant is less than 10.0 min, which is sufciently fast and satisfactory for practical use. After saturated adsorption, CSGO can be efciently regenerated and reused with little uptake
loss. Therefore, CSGO is a versatile adsorbent that efciently removes various pollutants from water.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Water pollution has become serious with the rapid development of modern industries [1]. High water quality has been
demanded with increasingly strict environmental quality standards [2]. Various techniques of water treatment have been used,
1398
1399
pollutants before and after adsorption were determined using different methods: MB and MO were analyzed on a unico 7200 Vis
spectrometer, and the analyzing wavelengths were 662 nm and
464 nm for MB and MO respectively. A thermo M6 atomic absorption spectrometer (AAS) was used to determine the concentrations
of Cu(II) and Cr(VI). Proper dilution and pH adjustment were made
to meet the analytical conditions.
Adsorption capacity (q, mmol/g) of CSGO for each pollutant
was calculated from the change of pollutant concentration in the
adsorption process on the basis of the following equation:
C 0 C e V
m
where C0 and Ce (mmol/L) are the initial and equilibrium concentrations of the pollutants respectively; V (L) is the total volume of the
solution; m (g) is the mass of CSGO.
2.4.1.2. Adsorption equilibrium study. The adsorption equilibrium
study was conducted at 298 K and pH 5.0. The concentrations of
each series of pollutant solutions ranged from 0.05 mmol/L to
1.6 mmol/L. 15.0 mg of CSGO was dispersed and stirred in
30 mL of a certain pollutant solution. After saturated adsorption,
similar analysis methods as described in Section 2.4.1.1 have been
used to determine the initial and nal concentrations of pollutants
using Vis or AAS spectrometer. The uptakes were calculated on the
basis of Eq. (1).
2.4.1.3. Adsorption kinetics study. Adsorption kinetic experiments
were also conducted at 298 K and pH 5.0. 300.0 mg of CSGO
was added to 600 mL of a certain pollutant solution, and the mixture was continuously stirred. The initial concentration was
approximately 1.0 mmol/L for each pollutant. About 1.0 mL of solution was obtained at desired time intervals to analyze the current
concentration of pollutant. Meanwhile, the same volume of pure
water was added into the bulk solution to keep the volume constant. The pollutant uptake at time ti, q(ti) (mmol/g) was calculated
using the following equation:
qt i
C 0 C ti V 0
m
Pi1
2
C ti1 V s
where C0 and C ti (mmol/L) are the initial concentration and pollutant concentration at time ti, respectively. V0 and Vs (L) are the volume of the mixed solution and that of the sample solution taken out
each time for concentration analysis, respectively. In this equation,
Vs is equal to 0.001 L. Finally, m (g) represents the mass of the
adsorbent.
2.4.2. Adsorption study in MB/Cu(II) and MO/Cr(VI) binary systems
Adsorption experiments in coexistent systems were conducted
at 298 K. Pollutants with opposite charges are prone to react with
each other and form precipitates; thus, the pollutants in each coexistent system, i.e. MB/Cu(II) and MO/Cr(VI), have the same charge.
The concentration of each pollutant in the binary system is the
same at 1.0 mmol/L to investigate the competitive adsorption
between two pollutants on CSGO, since the adsorption of pollutants could not be saturated yet in the lower concentrations and
both of pollutants could be simultaneous removal completely on
the basis of previously preliminary tests. Then, the effects of initial
solution pH were studied, and the measured conditions were similar to those in single pollutant system as described in
Section 2.4.1.1 except that two pollutants coexisted in the solution.
2.4.3. Recycling and reuse
Recovering and recycling experiments were conducted at room
temperature. Different desorption agents were used for different
pollutants, 0.01 mol/L HCl for Cu(II) and 0.01 mol/L NaOH for MB,
1400
D%
CiV i
100%
q0
R%
qi
100%
q0
From FTIR spectra in Fig. 2a, apart from the similar characteristic bands at around 3100 cm1 to 3500 cm1 because of OH and
NH stretching vibrations and at 1054 cm1 due to CO stretching
vibration in COH, [38] CSGO-A and CSGO-B still show several
different characteristic peaks although they comprise two similar
components. The characteristic peak at 1722 cm1 corresponding
to C@O stretching vibration of COOH in GO [38] appears in
CSGO-A but disappears in CSGO-B, whereas the peak at
1647 cm1 ascribed to NH bending vibration of NH2 in CS
[21] seems transfer to 1597 cm1 in CSGO-A and 1580 cm1 in
CSGO-B. These differences are mainly because CSGO had different pre-treatment. The carboxyl groups in CSGO-A pre-treated by
acid are protonated, so the characteristic peak of COOH appears at
1722 cm1 which is similar to pure GO situation prepared from
strong acid according to modied Hummer method [35].
However, the carboxyl groups in CSGO-B pre-treated by alkaline
are fully de-protonated, its characteristic peak, i.e. COO, transfers to low wavenumber and overlaps with that of NH2 at
1580 cm1 [39]. Furthermore, new peaks, 1367 cm1 in CSGO-A
and 1339 cm1 in CSGO-B, has been observed. These peaks are
ascribed to some bonding interactions between amino groups on
CS and oxygen-containing acidic ones on GO [34], which may also
result in the red shift of NH bands of NH2 in both forms of
CSGO. Therefore, CSGO is not simply accumulated by CS and
GO but assembled together.
Moreover, Fig. 2b shows N1s XPS spectra of CS and two forms of
CSGO. Only one characteristic peak at the binding energy (BE) of
about 399 eV in CS and CSGO-B attributed to NH2 is found.
However, an additional peak near 401 eV in CSGO-A appears also.
This new peak corresponds to NH+3 because of the protonation of
the amino groups in acidic condition, which effects may also cause
different degrees of the red shift of NH bands of NH2 between
CSGO-A and CSGO-B in their FTIR spectra illuminated in Fig. 2a.
The zeta potentials of CS, GO, and CSGO have been analyzed
(Fig. 2c). CS has a positive surface charge at pH lower than 9.5
where D% and R% are the desorption and recovery efciency respectively. Ci (mmol/L), Vi (L), and qi (mmol/g) are efuent concentration, efuent volume and pollutant uptakes of CSGO at cycle i
(15), respectively. q0 (mmol/g) is pollutant uptakes of CSGO at
rst adsorption.
(a)
(b)
CS-GO-B
CS-GO-A
CS
1580
1722
1339
-NH2
CS-GO-B
-NH3+
1597 1367
CS-GO-A
1647
GO
1722
CS
410
405
Wavenumber (cm-1)
potential (mv)
60
40
400
395
390
B. E. (eV)
(c)
CS-GO
CS
GO
CS-GO-A
20
0
-20
CS-GO-B
-40
-60
1
pH
9 10 11 12
Fig. 2. Characterizations of CSGO: (a) FTIR spectra, (b) N1s XPS spectra, and (c) zeta potential, where CSGO-A and CSGO-B represent acid and alkaline pre-treated CSGO
respectively.
1401
Moreover, CSGO shows different pH dependencies in adsorption of anionic and cationic pollutants during the respective measured pH range. The removal efciencies of CSGO for anionic
ones are strongly inhibited at higher pH levels as shown in
Fig. 4a, but those for cationic ones are evidently suppressed at
lower pH conditions based on Fig. 4b. Different pH dependencies
of pollutant removal efciency are mainly attributed to the various
charge properties of different pollutants and amphoteric features
of CSGO. CSGO at pH below its isoelectric point of 4.5 has positive surface charge which would be attractive to anionic pollutants
but repulsive to cationic ones. Moreover, the opposite situations
are applicable in the composite adsorbent at pH above 4.5.
Besides the effects of the surface charge properties, the compact
morphology of CSGO at alkaline conditions based on Fig. 3 may
result in reduction of active adsorption sites on chitosan and
decrease of the anionic pollutants uptakes at higher pH levels.
Interestingly, the aforementioned pH dependencies of pollutant
removal efciency for the two anionic ones are also quite different
from each other as shown in Fig. 4a. Cr(VI) uptake continuously
decreases with the increase of pH, whereas MO uptake retains a
higher level and does not decrease at a wide pH range from 5.0
to 9.0. The unusual pH dependence in MO adsorption by CSGO
is due to the fact that certain hydrophobic effect such as pp stacking [1318,40] also plays an important role in adsorption process
besides the electrostatic interactions [41].
In contrast to anionic pollutants, both cationic ones, MB and
Cu(II), show similar trends in their pH dependencies of adsorption
efciency by CSGO (Fig. 4b). The MB and Cu(II) uptakes increase
linearly until the pH is near CSGOs isoelectric point of 4.5 then
both reach the plateau. However, at strong acidic level of approximately pH 2.0, Cu(II) uptake decreases to near zero, whereas MB
retains a certain amount of adsorption. This result is because
Cu(II) and MB follow different adsorption mechanisms. In this case,
chelating and electrostatic interactions are both involved in Cu(II)
adsorption [39]. However, the aforementioned two effects could be
evidently affected by pH. With the decrease of pH, the surface
charge of CSGO turns positive resulting in electrostatic repulsion
between the adsorbent and adsorbate. The simultaneously increasing amount of proton in water would strongly compete the active
adsorption sites on CSGO with Cu(II). As for MB, pp stacking
interactions are pH independent [1318,40,41] causing MB adsorption on GO content of CSGO even at lower pH levels, although
electrostatic interactions are diminished at the same time.
However, as for pure GO, its zeta potentials remain negative
according to Fig. 2c even at acidic conditions resulting in almost
pH-independence of its MB uptakes.
Overall, CSGO exhibits higher adsorption capacities for cationic pollutants than anionic ones from Fig. 4. This result can be
1402
1.0
(a)
q (mmol/g)
0.8
(H3C)2N
N N
SO 3Na
MO
0.6
0.4
MO on CS-GO
Cr(VI) on CS-GO
0.2
MO on GO
Cr(VI) on GO
0.0
1
10 11
pH
2.0
(b)
1.6
q (mmol/g)
1.2
N
Cl
MB
0.8
MB on CS-GO
Cu(II) on CS-GO
MB on GO
Cu(II) on GO
0.4
0.0
1
10 11
pH
11
(c)
pH (equilibrium)
10
MO
Cr(VI)
MB
Cu(II)
9
8
7
6
5
4
3
2
1
10 11
pH (initial)
Fig. 4. Effect of initial solution pH on adsorption of various pollutants by CSGO
and GO at 298 K: (a) anionic and (b) cationic ones. (c) Final pHs after reaching
adsorption equilibrium by CSGO at different initial solution pHs.
composite adsorbent through chelating effect, whereas pp stacking effect [1318,40] plays an important role in the adsorption of
MB and MO. The diverse adsorption mechanisms indicate that
CSGO is a broad-spectrum adsorbent and is capable of efciently
removing various pollutants.
In addition, the adsorption processes may also affect the solution pH. The nal solution pHs after reaching adsorption equilibrium for removal of aforementioned four pollutants by CSGO
have been also determined and shown in Fig. 4c. From Fig. 4c,
the equilibrium pHs increase at initial solution pH around below
CSGOs isoelectric point of 4.5, but decrease at initial solution
pH above 4.5. It may be due to the amphoteric natures of the composite adsorbent.
3.2.2. Equilibrium adsorption experiments
The equilibrium adsorption isotherms of CSGO for removing
the four pollutants have been performed at 298 K and pH 5.0 which
are illustrated in Fig. 6. Those isotherms have similar appearance.
The adsorption capacities linearly increase with the initial concentrations of pollutants increasing at the beginning, then reach the
plateau at high concentrations, indicating that the active adsorption sites on the adsorbent surfaces are saturated and the pollutant
adsorptions achieve equilibrium.
To further investigate the adsorption behavior and mechanism
of the composite adsorbent, those isothermal data were subjected
to Langmuir [42] and Freundlich [43] models for quantitative analysis. Langmuir [42] and Freundlich [43] isothermal models are
based on the assumption of monolayer homogeneous and multilayer heterogeneous adsorptions respectively. Their equations are
shown below:
Ce
1
Ce
qe qm b qm
log qe
1
logC e log K f
n
where qe (mmol/g) is the amount of pollutant adsorbed at equilibrium; Ce (mmol/L) is the concentration at equilibrium; qm (mmol/g)
is the adsorption capacity when the adsorbent is fully covered; b
(L/mmol) is the Langmuir adsorption constant; Kf is the
Freundlich isothermal constant and n (dimensionless) is the heterogeneity factor.
The nal simulated parameters are all listed in Table 1.
According to the correlation coefcients (R2) of the linear form
for the two models, R2s of the Langmuir model for MB and Cr(VI)
1403
1.0
1.0
(a)
q(t) (mmol/g)
q (mmol/g)
0.8
0.6
0.4
MO
Cr (VI)
0.2
0.8
(a)
0.6
0.4
MO
Cr (VI)
0.2
0.0
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Ce (mmol/L)
15
20
1.6
q(t) (mmol/g)
1.5
1.0
MB
Cu (II)
0.5
(b)
1.4
1.2
1.0
0.8
0.6
MB
Cu (II)
0.4
0.2
0.0
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Ce (mmol/L)
Table 1
Simulated results of adsorption isotherms of CSGO for removal of various pollutants
at 298 K and pH 5.0.
qm,exp
(mmol/g)
0.8
0.55
1.6
1.34
Langmuir
10
15
20
25
30
t (min)
Fig. 6. Adsorption isotherms of CSGO for removal of various pollutants: (a) anionic
and (b) cationic ones at 298 K and pH 5.0.
MO
Cr(VI)
MB
Cu(II)
30
1.8
(b)
Pollutants
25
t (min)
2.0
q (mmol/g)
10
Freundlich
qm
(mmol/g)
b
(L/mmol)
R2
Kf
R2
0.75
0.63
1.59
1.24
108.5
10.51
198.5
61.73
0.8969
0.9965
0.998
0.9677
4.74
0.86
1.84
2.44
1.73
2.11
6.3
2.64
0.9935
0.9747
0.9627
0.9969
were much closer to 1.0 than those of the Freundlich model, but for
MO and Cu(II) it is the inverse. Besides the data tting results, on
the basis of the theoretic assumption of aforementioned two
isothermal models and adsorption characteristics of CSGO for
those pollutants as discussed in previous section and described
in Fig. 5, the adsorptions of MB and Cr(VI) occur only on a single
component of CSGO, MB mainly on GO but Cr(VI) on CS.
Whereas the adsorptions of MO and Cu(II) could take place on both
components of CSGO for diverse adsorption mechanisms.
Therefore, adsorption behaviors of the composite adsorbent for
MB and Cr(VI) show homogeneous features which isotherms obey
the Langmuir model, whereas those for MO and Cu(II) exhibit
heterogeneous features which isotherms follow the Freundlich
models.
3.2.3. Kinetic adsorption experiments
Adsorption kinetics is another fundamental aspect concerning
the adsorption behavior and application potentials of an adsorbent
Fig. 7. Adsorption kinetics of CSGO for removal of various pollutants: (a) anionic
and (b) cationic ones at 298 K and pH 5.0.
qt qe qe ek1 t
qt qe
qe
qe k2 t 1
1404
Table 2
Simulated results of adsorption kinetics of CSGO for removal of various pollutants at 298 K and pH 5.0.
Pollutants
qm,exp (mmol/g)
MO
Cr(VI)
MB
Cu(II)
Pseudo-rst order
0.8
0.55
1.6
1.34
0.6
0.5
Pseudo-second order
q1 (mmol/g)
k1 (1/min)
q2 (mmol/g)
k2 (g/(mmol min))
R2
0.75
0.56
1.72
1.29
0.94
0.9
0.26
0.52
0.9944
0.9938
0.9975
0.9989
0.65
0.87
2.37
1.55
1.74
1.41
0.09
0.38
0.9997
0.9995
0.9948
0.9962
(a)
10
MO
Cr(VI)
Cycle
0.4
6
0.3
1
2
3
4
5
q (mmol/g)
Table 3
Desorption and recovery efciencies of CSGO for removal of various pollutants.
0.2
0.1
0.0
5
10
11
1.0
25
(b)
0.8
20
0.6
15
0.4
MB
Cu(II)
0.2
10
5
0.0
2
D (%)
R (%)
MO
Cr(VI)
MB
Cu(II)
MO
Cr(VI)
MB
Cu(II)
98.35
97.63
96.41
95.58
93.97
99.92
99.33
98.69
97.99
97.45
98.51
97.66
96.38
94.04
94.87
99.35
98.97
97.75
97.02
96.51
97.16
96.01
95.19
93.25
91.04
98.45
97.87
95.67
94.87
94.25
98.2
96.12
95.13
94.04
92
98.43
97.21
96.24
96.48
95.31
where aBA is the selectivity factor of A over B; qe,A and qe,B are the
equilibrium adsorption capacities for pollutant A and B; and Ce,A
and Ce,B are the equilibrium concentrations of A and B, respectively.
The higher aBA is, the stronger selective adsorption of A over B is.
On the basis of the obtained a in Fig. 8, CSGO generally exhibits selective adsorption of dyes over metal ions in those two coexistent systems but different levels in adsorption preference
because of their different charge properties and adsorption mechanisms. For MO/Cr(IV) system being anionic pollutants, CSGO
only shows very slight selectivity for MO over Cr(IV). However,
strongly selective adsorption of MB over Cu(II), i.e. high aMB
CuII ;
pH
q (mmol/g)
pH
Fig. 8. Adsorption of various pollutants onto CSGO in coexistent systems: (a)
anionic and (b) cationic ones at 298 K.
has been observed at acidic solutions (pH < 5.0), which may be
caused by the additional adsorption way for MB through pp
stacking effects [1318,40].
Accordingly, since CSGO does not show specic selectivity for
the four pollutants at near neutral conditions, these pollutants can
be removed simultaneously and efciently in their coexistent systems also. However, CSGO exhibits strongly selective adsorption
for MB over Cu(II) in acidic solutions, which suggests that acidic
eluents may be used for separation and selective recovery of
Cu(II) and MB after adsorption treatment by this composite
adsorbent.
3.4. Recycling and reuse
aBA
qe;A C e;B
C e;A qe;B
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