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Chemical Engineering Journal 284 (2016) 13971405

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Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

pH-tunable surface charge of chitosan/graphene oxide composite


adsorbent for efcient removal of multiple pollutants from water q
Han Yan, Hu Yang , Aimin Li, Rongshi Cheng
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, PR 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

 Chitosan/graphene oxide composite

adsorbent (CSGO) was prepared by


self-assembly.
 CSGO shows pH-tunable surface
charge and morphology.
 CSGO can be efcient removal of
various pollutants with opposite
charges.
 CSGO bears high selective
adsorption of MB over Cu(II) at low
pH in their mixture.
 Diverse adsorption mechanisms are
involved in removal of various
pollutants.

a r t i c l e

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

Supported by the Natural Science Foundation of China (Grant Nos. 51438008


and 51378250).
Corresponding author. Tel./fax: +86 25 89681272.
E-mail address: yanghu@nju.edu.cn (H. Yang).
http://dx.doi.org/10.1016/j.cej.2015.06.030
1385-8947/ 2015 Elsevier B.V. All rights reserved.

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,

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H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

including adsorption [3], occulation [4], oxidation [5], and


biotechnology [6]. Developing highly efcient methods based on
the aforementioned conventional techniques are important to deal
with these complicated wastewater.
Among them, adsorption is one of the most commonly applied
ones. However, this method still faces several challenges, such as
selective recovery and reuse of valuable pollutants [7],
co-removal of the coexisting multiple types of pollutants [8], fast
and efcient separation after saturated adsorption [9], and removal
of trace highly-toxic contaminants [10]. Since high-performance
absorbent material is the key to solve aforementioned problems,
to date, different kinds of novel adsorbents have been reported,
such as carbon-based nanomaterials, natural polymers and so on
[9,11,12]. These adsorbents have specic features that meet the
growing needs for complicated or rened wastewater remediation
[12,13].
Two-dimensional graphene oxide (GO), which is the most
important precursor/derivative of graphene [14] with atomic
thickness and large planar size, has been widely recognized as a
potential superior adsorbent because of its high surface area and
abundant oxygen-containing functional groups with anionic property [1318]. Despite ne afnity to many anionic and aromatic
pollutants for electrostatic interactions or pp stacking effects
[1318], the adsorption efciency of GO for anionic pollutants is
usually unsatisfactory for electrostatic repulsion effects. To
improve this shortcoming, researchers have used various chemical
or physical modications on GO [1927]. One of the most efcient
methods is to complex GO with other functional materials
[19,2127].
Chitosan
(CS),
a
high-performance
and
environmental-friendly natural polymeric material with extensive
sources, bears abundant free amino groups that are cationically
charged in a wide pH range [28]. Moreover, many metal ions and
anionic pieces can be easily bound to CS because of the chelating
effects or electrostatic interactions [29]. Integrating GO with CS
obtains a versatile adsorbent because of their advantages
[2123,3032]. However, previous reports about the CS and GO
composite mainly focused on the preparation method or adsorption properties in certain single pollutant system [2123,3032].
Little work has been done to investigate the removal efciency of
the composite for various types of pollutants and their mixtures
from water. Since CSGO has amphoteric characteristics for containing both cationic and anionic functional groups [29,33] that
exhibits various surface charge and morphology at different pH
conditions, it is expected to be efcient removal of various pollutants with different charge natures.
In this work, CSGO has been prepared by self-assembly
method, which could be crosslinked in dimethylformamide

(DMF) by mutual reaction between amino groups on CS and


oxygen-containing acidic ones on GO [34]. Then, the adsorption
performance of this composite adsorbent for removal of multiple
types of pollutants, which far differ in structure and charge properties, has been investigated to evaluate its versatility. These pollutants include methylene blue (MB), methyl orange (MO), Cu(II),
and Cr(VI). Besides the fundamental adsorption behavior of CS
GO for removing the four different pollutants from their respective
single system, i.e. pH effects, adsorption equilibrium, and kinetics,
the selective adsorption in MB/Cu(II) and MO/Cr(VI) binary systems were studied. The adsorption and selective adsorption mechanisms have been discussed in detail. Moreover, the recycling and
reuse of CSGO after saturated adsorption has been performed
because of its great importance in real applications.
2. Experimental
2.1. Materials
Graphite, precursor of GO, was obtained from Nanjing
Chemical Reagent Co. Ltd. Chitosan with 90.5% deacetylation and
3.0  105 g/mol viscosity average molecular weight was purchased
from Shandong Aokang Biological Co. Ltd. Four synthetic pollutants: MB, MO, Cu(NO3)23H2O, and K2Cr2O7, were obtained from
Sinopharm Chemical Reagent Co. Ltd. Other reagents, namely,
KMnO4, H2SO4, NaNO3, H2O2, DMF, acetic acid (HAc), HCl, NaOH,
NaNO2, KI, and Na2S2O3, were all purchased from Nanjing
Chemical Reagent Co. Ltd. All reagents are of analytical grade,
and distilled water was used in each experiment.
2.2. Preparation of CSGO
The GO used for CSGO preparation was synthesized using
modied Hummer method [35] in advance. The contents of various
surface oxygen-containing acidic groups of GO, i.e., carboxyl, lactonic, and phenolic groups, as determined by Boehm titration
method [36], were 1.1, 1.4, and 2.8 mmol/g, respectively. Then,
CSGO has been prepared on the basis of previously preliminary
tests to achieve a suitable amphoteric property. The synthetic conditions are described briey as follows. 0.5 g of freshly prepared GO
was dispersed in 100 mL water with a few drops of ammonia solution. Subsequently, 120 mL of 1.5 wt% chitosan well-dissolved in
1.0 wt% HAc aqueous solution was added to the GO suspension,
and brown aggregates were formed in this process. After that,
the aggregates were fully poured into a 1.0 mol/L NaOH water
ethanol (the volume ratio is 1:1) mixed solution for hydrogelation.

Fig. 1. Schematic demonstration for preparation of CSGO.

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H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

The obtained hydrogel was thoroughly washed with ethanol and


DMF. Then, the hydrogel was placed into a proper volume of
DMF and stirred for 2 days at 308 K for further crosslinking
between CS and GO. Afterwards, the crosslinked amphoteric adsorbent was ltered and washed with dilute HCl to remove
un-crosslinked CS. The water content of CSGO has been determined about 93.7594.30%. A scheme for description of the preparation process and mechanism is shown in Fig. 1.
2.3. Characterization of CSGO
To better investigate the molecular structure of the composite
with amphoteric characteristics, two forms of CSGO, nominated
as CSGO-A and CSGO-B, pre-treated by 0.1 mol/L HCl and
0.1 mol/L NaOH respectively, have been obtained. CSGO-A and
CSGO-B was characterized using Fourier transform infrared spectroscopy (FTIR, Type Thermo Nicolet iS10, Thermo Co. Ltd.; USA)
and X-ray photoelectron spectroscopy (XPS, Type ULVAC-PHI
5000; VersaProbe, Northrop Grumman Co. Ltd.; USA). The morphologies of CSGO at acidic and alkaline conditions were directly
observed by transmission electron microscopy (TEM, Type
JEM-1011; JEOL Co.; Japan). In addition, zeta potential analyses of
CSGO were conducted on a zeta potential instrument (Type
Nano-Z, Malvern Co. Ltd.; UK). The initial solution pH ranged from
2.0 to 12.0 by adjustment using dilute HCl or NaOH aqueous
solutions.
The content of CS in CSGO determined using nitrite titration
method based on the quantitative reaction between amino groups
of chitosan and nitrites NH
3 HNO2 ! N2 2H2 O [34] was
approximately 37 wt% to 39 wt%. The brief determination process
is described as follows. A certain amount of CSGO was rstly dispersed in water with moderately excessive HCl aqueous solution.
Then an excessive and xed amount of NaNO2 solution was added.
The mixture was left to react for sufcient time. Afterwards, certain volume of supernatant was mixed with excessive KI solution
under nitrogen ow. Based on the quantitative reaction
2HNO2 2I 4H ! I2 2NO 2H2 O [37], the yielded iodine
was titrated with Na2S2O3 using starch solution as an indicator.
Blank control was also conducted. The amount of CS was calculated
based on the consumption of nitrite and the chemical quantitative
relationship in aforementioned equations.
2.4. Adsorption experiments
Multiple types of pollutants, including various dyes and metal
ions with different charge properties: cationic [MB and Cu(II)]
and anionic species [MO and Cr(VI)], have been tested to investigate the versatile adsorption performance of CSGO because of
its amphoteric and pH-tunable features. In addition, as the molecular weight of these pollutants greatly differs from each other, the
units of the concentration and adsorption capacity are in molar
scale in this study.
2.4.1. Adsorption of MB, MO, Cu(II) and Cr(IV) in respective single
systems
2.4.1.1. Effect of initial solution pH. First, the effects of initial solution pH on adsorption of these pollutants were studied at 298 K.
The detected initial solution pH range for each pollutant was set
according to its respective pH stability in water, which was
adjusted using dilute HCl or NaOH aqueous solutions. In this experiment, 15.0 mg of CSGO was fully dispersed in 30 mL of a certain
pollutant solution by vigorous agitation at the beginning. The initial concentration of each solution was kept at 1.0 mmol/L. After
reaching adsorption equilibrium, the nal solution was ltered to
remove remnant adsorbent. The concentrations of various

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,

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H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

MO, and Cr(VI). In an adsorptiondesorption cycle, a proper


amount of CSGO was added to a certain pollutant aqueous solution; after reaching adsorption equilibrium, the saturated adsorbent was ltered, regenerated, and then washed with distilled
water; the regenerated adsorbent was then reused in the next
cycle. This experiment conducted ve adsorptiondesorption
cycles totally. The desorption and recovery efciencies of the 5
cycles are calculated by the following equations respectively:

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.

3. Results and discussion


3.1. Characterizations of CSGO
CSGO has been prepared through self-assembly method
[21,30], which is briey described in Fig.1 and Experimental section. FTIR and XPS spectra can both offer some valuable structural
information of the materials. Moreover, two forms of CSGO, nominated as CSGO-A and CSGO-B, pre-treated by dilute HCl and
NaOH aqueous solutions respectively, have been obtained and
characterized through FTIR and XPS to investigate the detailed
structural characteristics of the composite. The corresponding
spectra are both shown in Fig. 2.

(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

3500 3000 2500 2000 1500 1000

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.

H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

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Fig. 3. TEM images of CSGO-A (a) and CSGO-B (b).

due to the presence of amino groups on the chain backbone,


whereas GO has a negative surface charge in the measured pH
range resulting from the oxygen-containing acidic groups.
However, CSGO shows typical amphoteric nature with an isoelectric point of about 4.5 for the combined characteristics of CS and
GO consisting both cationic and anionic functional groups.
According to the zeta potential results, CSGO-A and CSGO-B
have an entirely opposite surface charge. The surface charge of
CSGO could be easily regulated through pH adjustment because
of its amphoteric features. Accordingly, the pH-tunable surface
charge of CSGO is exible and versatile; thus this composite can
treat complicated wastewater bodies containing various types of
pollutants with different charge properties.
Furthermore, the morphologies of CSGO composites
pre-treated under different pH conditions have been directly
observed under TEM (Fig. 3). Apparently, the morphology of this
composite is greatly affected by pH. The morphology of CSGO-A
is swollen and stretched, whereas that of CSGO-B is compact
but not aggregated. The pH dependence of CSGO morphology is
in agreement with the solubility of CS in water. Fig. 1 shows the
available internal microstructure of this composite which is
assumed to be the GO sheets connected by CS chains. CS would
be swollen in lower pH levels but would collapse in alkaline conditions resulting in different morphologies between CSGO-A and
CSGO-B. Moreover, the planar size of CSGO was roughly estimated from TEM images about 1.0 lm to 3.0 lm.
3.2. Adsorption behavior of CSGO in respective single pollutant
system
3.2.1. Effect of initial solution pH
CSGO is used as an efcient adsorbent for the removal of multiple types of pollutants from aqueous solutions including various
dyes and metal ions with different charge properties: cationic [MB
and Cu(II)] and anionic species [MO and Cr(VI)]. The effects of initial solution pH have been examined rst (Fig. 4). Due to the strong
oxidation of Cr(IV), Cr(III) has been tested beforehand by precipitation method using dilute NaOH aqueous solution but Cr(OH)3 precipitates could not be found, indicating that the reduced amount of
Cr(VI) in this case is quite insignicant in measured pH ranges.
From Fig. 4, after the combination of GO with CS, the adsorption
capacities of CSGO have been noticeably improved for the
removal of MO, Cr(IV), and Cu(II) in comparison with those of GO
because of the compensation effects between the two components
in this composite adsorbent. MB uptakes at pH near neutral conditions (5.09.0) are similar to those of GO but decrease evidently at
lower pH levels. These results are ascribed to different adsorption
mechanisms involved.

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

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H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

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)

Fig. 5. Adsorption mechanism of CSGO for removal of various pollutants.

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.

attributed to the higher amount of GO content in CSGO, which is


approximately 61 wt% to 63 wt%, because GO has the main contributions to adsorption of cationic pollutants here. As for the different types of pollutants, dye uptakes of CSGO, MO and MB, are
both higher than respective metal ions ones, Cr(IV) and Cu(II), from
Fig. 4. The additional pp stacking adsorption for dyes is the cause
of this result [1318,40]. To better illustrate the adsorption mechanisms, a schematic demonstration of the different effects for
adsorption of various pollutants is shown in Fig. 5.
From Fig. 5, Cr(VI) is only adsorbed onto CSGO by electrostatic
interactions with CS component. As for the other three pollutants,
besides electrostatic interactions, Cu(II) could still bind to the

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)

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H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

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.

[44]. The adsorption kinetics curves of CSGO are shown in Fig. 7.


The adsorption equilibrium time of CSGO for each pollutant is less
than 10.0 min, which is relatively fast compared with those of
other reported similar adsorbents [21,22,3032].
To further study the adsorption mechanism, simulation for the
kinetics data was also conducted on the basis of pseudo-rst [45]
and pseudo-second order [46] kinetic models. Pseudo-rst order
and pseudo-second order models are expressed in nonlinear forms
as Eqs. (7) and (8) respectively:

qt qe  qe ek1 t

qt qe 

qe
qe k2 t 1

where qe and qt (mmol/g) are the amount of pollutants adsorbed


onto adsorbents at equilibrium and at time t (min), respectively.
k1 (1/min) and k2 (g/(mmol min)) are the rate constant of
rst-order and second-order adsorption respectively.
The simulated results are listed in Table 2. R2s of both models
for the measured pollutants exceed 0.99, which indicates that both
mechanisms, i.e. physical and chemical adsorption, may be
involved in the adsorption process because of the complicated
structure characteristics of the composite adsorbent. Multiple
effects, including electrostatic interaction, pp stacking, and
chelating effects, work in the adsorption of aforementioned four
pollutants.

1404

H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

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

3.3. Adsorption behavior of CSGO in binary pollutant systems


Furthermore, current wastewater becomes more complicated
and many coexistent pollutants emerge in water because of the
rapid development of modern industry [1,47]. Remediation of
complicated wastewater is of great environmental signicance
[48]. The adsorption performance of CSGO in MO/Cr(IV) and
MB/Cu(II) binary systems has been determined and is shown in
Fig. 8. The adsorption capacity of CSGO for each pollutant in coexistent system retains a relatively high level at near neutral conditions but evidently decreases in comparison with that in the
respective single system (Fig. 4) for competitive adsorptions
between two coexistent pollutants. However, dye uptake is always
higher than metal one in each mixture.
To give a quantitative demonstration about the adsorption
properties of CSGO in respective binary system, the selectivity
coefcient (a) has been estimated based on the following equation
and is shown in Fig. 8:

aBA

qe;A C e;B
C e;A qe;B

Recycling and reuse are also signicant for new adsorbents in


practical applications. After reaching saturated adsorption of the
four pollutants, CSGO could be easily regenerated by acidic or
alkaline eluents, which has been described in Experimental section
in detail. The variations of desorption and recovery efciency in
each adsorptiondesorption cycle are listed in Table 3.
From Table 3, the desorption efciencies of CSGO for the four
measured pollutants are very high. After efcient desorption, only
slight drop in adsorption capacities of the regenerated adsorbent
and more than 90% of its activity for all pollutants are observed
after ve cycles. Moreover, the recovery efciencies for heavy
metal ions are a little higher than those for dyes. However, this
result indicates that the composite adsorbent exhibits ne
reusability for various pollutants, which is quite satisfactory for
its practical applications.
4. Conclusion
In this study, an amphoteric composite adsorbent combination
of CS and GO, CSGO, with CS content of about 3739 wt% has been

H. Yan et al. / Chemical Engineering Journal 284 (2016) 13971405

prepared simply. For the pH-tunable surface charge and structural


characteristics, CSGO shows good adsorption performance for
removing not only various dyes [MO and MB] but also metal ions
[Cr(IV) and Cu(II)] from aqueous solutions. Accordingly, multiple
adsorption mechanisms are involved in pollutants removal by
CSGO which has been conrmed by the results of adsorption isotherms and kinetics also. Besides electrostatic interactions occurring in adsorption of each pollutant, chelating effect exists
between Cu(II) and CS component, whereas pp stacking interactions work in removal of both dyes by GO component. Moreover,
the adsorption equilibrium for the four pollutants has been rapidly
achieved within 10.0 min. In addition, CSGO still exhibits high
selective adsorption of MB over Cu(II) at acidic conditions in their
mixture. MB and Cu(II) can be separated and recovered easily using
acidic eluents. Furthermore, CSGO could be efciently regenerated after reaching saturated adsorption and its adsorption capacity is still more than 90% after ve cycles. Therefore, CSGO is a
exible and tunable adsorbent which has great application potentials in water treatment.
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