Carbohydrate Polymers 150 (2016) 201208

Contents lists available at ScienceDirect

Carbohydrate Polymers
j o u r n a l h o m e p a g e : w w w. e l s e v i e r.c o m / l o c a t e / c a r b p o l

A recyclable and regenerable magnetic chitosan absorbent for dye

uptake
a,b
Weifeng Zhao , Xuelian Huang a , Yilin Wang a , Shudong Sun a
, Changsheng Zhao
a,

a
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, 610065 Chengdu, China
b
Fiber and Polymer Technology, School of Chemical Science and Engineering, Royal Institute of Technology (KTH), Teknikringen 56-58 SE-100 44,
Stockholm, Sweden

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

Article history:
A recyclable and regenerable magnetic polysaccharide absorbent for methylene blue (MB) removal was
Received 16 March 2016
prepared by coating magnetic polyethyleneimine nanoparticles (PEI@MNPs) with sulfonated chitosan
Received in revised form 5 May 2016
Accepted 12 May 2016
(SCS) and further cross-linked with glutaraldehyde. The driving force for coating is the electrostactic
Available online 16 May 2016 interaction between positively charged PEI and negatively charged SCS. Infrared spectra, zeta potential,
thermal gravimetric analysis and X-ray diffraction demonstrated the successful synthesis of magnetic
Keywords:
polysaccharide absorbent. The self-assembly of polysaccharide with magnetic nanopartices did not
Magnetic chitosan absorbent alter the saturation magnetization value of the absorbent conrmed by vibrating sample
Recyclable magnetometer. The nanoparticles showed fast removal (about 30 min reached equilibrium) of MB. In
Regenerable particular, the removal ability of MB after desorption did not reduce, demonstrating an excellent
Self-assembly regeneration abil- ity. Our study provides new insights into utilizing polysaccharides for
Post-crosslinking environmental remediation and creating advanced magnetic materials for various promising
applications.
2016 Elsevier Ltd. All rights reserved.

1. Introduction cylic acid (PAA) is a commonly used synthetic polymer for MB

Nowadays, water pollution by dyes and heavy metal ions has
become a serious issue for the environment. Among these pollu-
tants from industries (Wang et al., 2012), methylene blue (MB) is
one typical toxic dye with known harmful effects on human
beings (Wang, Ding et al., 2015). The presence of MB in aquatic
system even at a low concentration of 1 ppm could inhibit the
sunlight transis- tence and affect the photosynthetic process of
aquatic livings (Guo
& Wilson, 2012). Therefore, removal of MB prior to its discharge
into environment is needed to be considered. Cost-effective
wastewater treatment techniques are required to reduce the
concentration of MB under permissible levels. Among these
techniques, dye adsorp- tion based on magnetic separation
technique has been receiving considerable attention owing to its
low-cost, high efciency, easy operation process and good
mechanical stability (Chen et al., 2014).
Many polymers including synthetic polymers and natural poly-
mers have been used with magnetic materials for MB removal
due to the large amount of active sites in polymers. Polya-
Corresponding author.
E-mail addresses: zhaoscukth@163.com (W. Zhao), huangxlscu@163.com
(X. Huang), 525642600@qq.com (Y. Wang), sunshudong@scu.edu.cn (S. Sun),
zhaochsh70@163.com, zhaochsh70@scu.edu.cn (C. Zhao).
removal. Mak et al. developed PAA/Fe3 O4 nanoparticles for the
adsorption of MB from an aqueous solution (Mak & Chen, 2004).
Recently, a PAA functionalized magnetic Fe3 O4 nanoparticle-
graphene oxide nanocomposite (PAA/MGO) was synthesized, and
the higher adsorption capacity of PAA/MGO was mainly attributed
to the functionalization of PAA and its higher content of charged
carboxyl groups than MGO (Zhang et al., 2015). However, these
syn- thetic polymers cannot be degraded, which creats the
secondary pollution after the removal of MB. Thus, the scientists
turn their attention towards fabrication of magnetic adsorbents
using natural polymers.
Among natural polymers, polysaccharides are abundant,
biodegradable, hydrophilic and low-cost, therefore commonly used
as adsorbent materials for wastewater treatment (Lu et al., 2015).
It has been reported that pectin (Rakhshaee & Panahandeh, 2011),
activated carbon/alginate (Ai, Li, & Li, 2011), GO/calcium alginate
(Song, Wu, Zhong, Lin, & Chen, 2015), cellulose/GO (Shi, Li, Zhong,
& Xu, 2014), corn straw (Zhao, Xia, Yang, Wang, & Zhao, 2014),
carboxymethyl starch/poly(vinyl alcohol) (Gong, Zhang, Cheng,
& Zhou, 2015) and -cyclodextrin (Badruddoza, Hazel, Hidajat,
& Uddin, 2010; Zhou et al., 2016) could been used to fabricate
magnetic absorbents for MB removal. As an important family
of polysaccharides, chitosan is also attracted much attention for
MB removal. Uniform chitosan coated magnetic mesoporous sil-

http://dx.doi.org/10.1016/j.carbpol.2016.05.037
0144-8617/ 2016 Elsevier Ltd. All rights reserved.
 W. Zhao
W. Zhao
et al.et/ al.
Carbohydrate
/ Carbohydrate
20
ica nanoparticles with good adsorption capacity and magnetic
response were synthesized to remove MB dyes (Li, Zhou, Nie,
Song,
& Chen, 2015). Zeng et al. (2015) synthesized a magnetic
adsorbent of chitosan/organic rectorite-Fe3 O4 intercalated
composite micro- spheres for the removal of MB. In order to
employ the promising properties of GO, a magnetic composite
bioadsorbent composed of magnetic chitosan and GO was
prepared as the magnetic adsor- bent toward MB (Fan et al.,
2012). For preparing a stable adsorbent,
ethylenediaminetetraacetic dianhydride-modied magnetic chi-
tosan complex was fabricated using glutaraldehyde as a cross-link
agent for the MB removal (Xia et al., 2013). By using the same
strat- egy, we hypothesize that a self-assembly of negatively
charged polysaccharides and positively charged magnetic
nanoparticles, and then followed by cross-linking, could
produce recycled and regerated magnetic particles for MB
removal.
The aim of this study is to fabricate a recyclable and regen-
erable magnetic adsorbent for MB removal by coating magnetic
polyethyleneimine nanoparticle (PEI@MNP) with sulfonated chi-
tosan (SCS) and further cross-linking with glutaraldehyde. SCS
was rstly synthesized by a sulfonation of CS with HSO3 Cl. A
solvothermal reaction was applied to produce PEI@MNP. After
a self-assembly of SCS onto PEI@MNP by electrostatic interac-
tion, the SCS was subsequently cross-linked by glutaraldehyde.
As a consequence, the functional SCS is stabilized onto magnetic
nanoparticles so that these magnetic hybrid materials could be
regenerable and recyclable during wastewater treatments. Infrared
spectra (IR), nuclear magnetic resonance (NMR), gel permeation
chromatography (GPC) and elemental analysis were applied to
characterize SCS. Additionally, IR, zeta potential, thermal
gravimet- ric analysis (TGA) and X-ray diffraction (XRD) were
used to follow the self-assembly and post cross-linking of SCS
onto the mag- netic nanoparticles. The magnetization of the
magnetic particles was demonstrated by vibrating sample
magnetometer (VSM). The adsorption, desorption and re-
adsorption of the magnetic nanopar- ticles towards MB were also
investigated.
2. Experimental
2.1. Chemicals
Chitosan (CS) with a degree of deacetylation of 95% and a
viscos- ity of 100200 mpa s was purchased from Aladin Inc. Iron
chloride
hexahydrate (FeCl3 6H2 O, 99%, Aladin), polyethyleneimine (PEI,
M.W. 10 000, Aladin), diethylene glycol (DEG, 99%, Aladin), acetic
acid (99.8%, Aladdin), chlorosulfonic acid (HSO3 Cl, 99%, Kelong),
ethanol (EtOH, 98%, Kelong), sodium hydroxide and normal saline
solution (Kelong) were used as received. N,N-Dimethylformamide
(DMF, 98%, Kelong) was distilled under vacuum prior to use. Deion-
ized (DI) water was used throughout the study.
2.2. Preparation of magnetic polyethyleneimine (PEI)
nanoparticles (PEI@MNPs)
The PEI@MNPs were synthesized by a modied solvothermal
reaction. Firstly, 0.8 g of NaOH was added into 20 mL of DEG at
120 C for 1 h under N2 , and cooled down to 70 C to produce a
NaOH/DEG stock solution. Then, 1 g of PEI and 1 g of FeCl3 6H2 O
were dispersed in 40 mL DEG, and heated to 220 C under the pro-
tection of nitrogen ow and constant stirring. Afterwards, 5 mL of
NaOH/DEG stock solution was injected rapidly into the hot
mixture.
and then The resulting mixture was kept at 220 C for further 1 h,
allowed to cool to room temperature. With the aid of a magnet,
the black products were washed with DI water for several times
to remove the solvent and unreacted chemicals, and then stored in
normal saline solution.
Polymers
Polymers
150150
(2016)
(2016)
201208
201208
20
2.3. Sulfonation of chitosan
10 g of CS was dissolved in acetic acid/DMF (w/w 1/10) at 60 C
for several hours, and the solution was then cooled down to 0 C.
Then HSO3 Cl/DMF (v/v 1/2) was added within 1 h under the pro-
tection of nitrogen gas, and the reaction was kept at 0 C for 10 h.
Sulfonated CS was extracted by diethyl ether, and then puried
with ethanol. The product was then dried in a vacumm oven at
50 C for 48 h.
2.4. Characterization of SCS
Fourier transform infrared (FTIR) spectra for the modied SCS
was obtained using a FTIR spectrometer (Nicolet 560, America). 1 H
NMR data were obtained with a BRUKER spectrometer (400
MHz). The molecular weight and molecular weight distribution
were mesured by gel chromatography (HLC-8320GPC, Japan).
Elemen- tal analyses were performed on a CARLO ERBA 1106
elemental analyzer (Italy) for carbon (C), hydrogen (H), nitrogen
(N) and sul-
fur (S) with a carrier gas (He, at a ow rate of 100 mL min1 ) at a
combustion temperature of 1000 C using the solid
samples.
2.5. Self-assembly and cross-linking of SCS onto magnetic
nanoparticles
20 mL of PEI@MNPs (1 mg/mL) was added dropwise into 10 mL
of SCS (5 mg/mL) aqueous solution. The self-assembly was carried
out under shaking for 1 h. The obtained PEI@MNP/SCS was washed
with 20 mL of DI water for 35 times to remove the excess SCS.
For the cross-linking of SCS onto the magnetic nanoparticles, 1
mL of 50% glutaraldehyde solution was added to PEI@MNP/SCS,
the
cross-linking reaction was performed at 70 C for 3 h, named as
PEI@MNP/SCSCL . In order to compare the effect of the acid addtion
on the cross-linking of SCS, 100 L of acetic acid was added during
the cross-linking of PEI@MNP/SCS, and named as PEI@MNP/SCSCLA .
The preparation of PEI@MNP/SCSCLA was illustrated in Scheme 1.
2.6. Characterization of magnetic nanoparticles
ATR-FTIR analysis was performed on a Nicolet 560 instrument,
equipped with a single-bounce attenuated total reection cell, a
detector, and a ZnSe single crystal. All the IR spectra were col-
lected with a resolution of 4 cm1 within a range of 4000600 cm1
.
Prior to thermal analysis, all of the samples were pre-dried at 30
C
for at least 24 h under vacuum. TGA of the specimens was per-
formed on a TG209F1 (Netzsch Co., Germany), and the samples
were heated from 30 to 700 C at a rate of 10 C min1 , protected
by
dry nitrogen. XRD measurement was performed on Empyrean X-
ray diffraction device (PANalytical B.V., Netherland) by using CuK
radiation ( = 0.154 ). The operation voltage and current were
kept
at 40 kV and 35 mA, respectively. The 2 range was 1070 in steps
of 0.03 with a count time of 0.2 s. The zeta potentials of magnetic
nanoparticles were determined by dynamic light scattering (DLS)
(ZETA-SIZER, MALVERN Nano-ZS90). The temperature was 25 C
and the scattering angle was 90 . The nanoparticle solution was
diluted to 0.1 mg/mL prior to test. The TEM images were taken
using a Tecnai G2 F20 S-TWIN (FEI, America) transmission electron
micro- scope with a tungsten lament at an accelerating voltage of
200 kV. The magnetic properties of the nanoparticles were
measured by a vibrating sample magnetometer (VSM) at room
temperature over
the magnetic density range from 10 to 10 kG.
2.7. Adsorption experiments
The dye.
model dye 10
removal was performed
mg magnetic using methyl
nanoparticles blue (MB)into
were dispersed as a
 Scheme 1. Illustrating synthesis of magnetic particles.
4 mL of 100 mol/L MB with continuous stirring. Once the equilib-
rium reached, the dye adsorbed hybrid was magnetically
separated using a magnet and the equilibrium concentration of
the dyes was then determined using an UVvis spectrophotometer
at = 631 nm. The adsorption amount was calculated using the
difference in the MB concentrations in the aqueous solution
before and after adsorp- tion as follows:
Q e = (Cb Cf )V/m
where Qe is the equilibrium concentration of MB on the
adsorbent
(mg g1 ); Cb and Cf are the concentrations of MB before and after
the adsorption, respectively; V is the volume (mL) of the MB
solu-
tion; and m is the weight (g) of the magnetic nanoparticles. The
dye removal experiments were repeated for three times to get
reliable data.
3. Results and discussion
Fe3 O4 nanoparticles have been paid considerable attention due
to their alluring properties and a wide range of potential applica-
tions such as bio-separation (Deng et al., 2005; Wang, Bao, Wang,
Zhang, & Li, 2006), magnetic resonance imaging (Gelbrich,
Reinartz,
& Schmidt, 2010; Kania et al., 2015; Wang, Niu et al., 2015; Zhu
et al., 2013), drug delivery (Yu, Park, Jeong, Moon, & Jon, 2010;
Zhu et al., 2013), catalysis (Mojtahedi, Abaee, & Eghtedari, 2008)
and environmental remediation (Li, Liu, Wu, Kim, & Fortner,
2014). For environmental concern, the current Fe3 O4 -based
polymers are much concentrated on their removal ability of dyes
and/or heavy metals. The magnetic Fe3 O4 nanoparticles aid to
separate the adsor- bent from the wastewater after use.
However, the regeneration and stability of magnetic materials
have not gained enough attrac- tion. Therefore, we propose an
approach combining self-assembly and post-cross-linking
towards magnetic materials to function- alize and stabilize the
functional polymers onto magnetic Fe3 O4 nanoparticles.
Sulfonated chitosan (SCS) was rstly synthesized by a istic amide carbonyl stretching band at approximately1631 cm1
sulfonation of CS with HSO3 Cl. A solvothermal reaction was
applied to produce PEI@MNP. After a self-assembly of SCS onto
PEI@MNP by electrostatic interaction, the SCS was subsequently
cross-linked by glutaraldehyde. As a consequence, the functional
SCS was stabilized onto the magnetic nanoparticles so that these
magnetic hybrid materials could be regenerated and recycled
dur- ing wastewater treatments.
3.1. Preparation and characterization of sulfonated chitosan (SCS)
The IR of SCS is shown in Fig. 1A. The SCS exhib-
ited a strong characteristic amide carbonyl stretching band at
approximately1631 cm1 , which was slightly shifted from that
(1648 cm1 ) of neat chitosan (Chang & Huang, 2012). The broad
absorption band at about 30003500 cm1 was contributed by the
stretching vibrations of NH2 and OH groups. The signicant
band characteristic
1 of the sulfonamide group ( N SO3 ) appeared
around
cm1 1204 cm . The intensity of the peaks in the 9601100
region ( C O C vibrations from the sugar units) remained con-
stant since there was almost no change for the C O C bonds
during the reaction (Zhao, Glavas, Odelius, Edlund, & Albertsson,
2014a; Zhao, Glavas, Odelius, Edlund, & Albertsson, 2014b). The
1
atH2.16
NMR (DMSO-d
ppm 6 ) spectrum
was assigned to theofmethyl
SCS ishydrogen
shown in (s,
Fig. 1B. A peak
HNCOCH 3 ),
and the peaks at 3.05.0 ppm were attributed to the hydrogen of
pyranose ring (m, C1C6) (Xue, Zhao, Nie, Sun & Zhao, 2013). The
molecular weight and molecular weight distribution were 22.6
kDa and 3.5, respectively. The degree of substitution (DS) of
sulfonic group was determined by elemental analysis, and with a
number
of 0.92. That is to say, there is approximately one-SO3 functional
group in one sugar unit. The high DS of chitosan ensures the pos-
sibility of self-assembly with positively charged PEI, also the high
removal capacity of methylene blue.
3.2. Preparation and characterization of magnetic nanoparticles
PEI@MNP was synthesized by a solvothermal reaction. Subse-
quently, PEI@MNP was immersed into an SCS solution to form
self-assembly clusters. The driving force for self-assembly is the
electrostatic interaction between the positively charged PEI and the
negatively charged SCS. The structure of the magnetic nanoparti-
cles was characterized by FTIR (Fig. 2A). All of the samples showed
a broad hydroxyl band at 3400 cm1 and a characteristic peak
of Fe3 O4 at 587 cm1 . The peak around 1630 cm1 for all of the
samples was assigned to the stretching vibration of NH in PEI.
After self-assembly of SCS onto PEI@MNP, the strong character-
was overlapped with the stretching vibration of NH in PEI.
The PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA exhib-
ited a shifted band of the sulfonamide group at 1236 cm1 . After
the cross-linking of SCS by glutaraldehyde (Fig. 2A (c)), the band
 Fig. 1. FTIR (A) and 1 H NMR (B) of SCS.
Fig. 2. IR (A) and zeta potential (B) of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (c) nanoparticles.
around 1016 cm1 enhanced, which was resulted from the newly
formed C O C groups. Interestingly, the intensity of this band
decreased after the addition of acetic acid during cross-linking, as
shown in Fig. 2A (d). Acetic acid is a commonly used catalyst for
cross-linking of polysaccharide (Zhao, Li, Guo, & Ma, 2015). The
cross-linking of SCS was enhanced by glutaraldehyde. As a subse-
quence, more aldehyde groups were cross-linked with SCS, and
the amount of free aldehyde groups thus decreased.
Additionally, DLS measurement was also applied to follow the
formation of the PEI@MNP/SCSCLA nanoparticles. Zeta potentials
of PEI@MNP, PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA
nanoparticles are shown in Fig. 2B. The zeta potential value of
PEI@MNP was +0.5 mV. The zeta potential value decreased to
25.1 mV when the PEI@MNP was self-assembly with SCS. This
result indicated that the prepared SCS was a highly negatively
charged polymer. The decrease in zeta potential from +0.5 mV to
25.1 mV also revealed that the SCS has been successfully coated
onto the surface of PEI@MNP. The zeta potential of PEI@MNP/SCSCL
increased up to 16.9 mV. The more polymer chains of SCS were
cross-linked, the more negative charges were covered. As the
result,
the cross-linking of SCS beneted the increase of zeta potential,
and the value further increased when the catalyst of acetic acid
was added during the cross-linking reaction.
The zeta potentials of the magnetic nanoparticles are strongly
associated with their stability. Fig. 3A shows the pictures of
PEI@MNP, PEI@MNP/SCS and PEI@MNP/SCSCL magnetic nanopar-
ticles suspended in de-ionized water (1 mg/mL). After 60 min,
the PEI@MNP nanoparticles aggregated at the bottom of the vial,
while the PEI@MNP/SCS and PEI@MNP/SCSCL magnetic nanoparti-
cles were well dispersed in aqueous solution. The reason was that
the electrostatic expulsion of the negative charges in PEI@MNP/SCS
and PEI@MNP/SCSCL magnetic nanoparticles prevented the aggre-
gation of the clusters. Besides the zeta potential, the sizes of the
magnetic nanoparticles also affected their stability in water. Parti-
cle sizes and size distribution of these magnetic nanoparticles
were also investigated by transmission electron microscopy
(TEM). As shown in Fig. 3B, the PEI@MNP nanoparticles exhibited
spherical structure with the mean sizes of about 10 nm. Although
there was no signicant difference in the size after the assembly
of SCS with magnetic nanoparticles, it could be observed that the
number of free PEI@MNP decreased and the cluster
nanoparticles markedly increased, suggesting that the SCS
molecules were successfully assembled onto the PEI@MNP. It
was noteworthy that the clear boarder of PEI@MNP nanoparticles
could not be observed after the cross-linking of SCS (Fig. 3B (c)).
The situation also occurred when acetic acid was added during the
cross-linking reaction.
As shown in Fig. 4A, the X-ray diffraction patterns of PEI@MNP,
PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA nanoparti-
cles are also investigated. All the samples displayed the diffraction
peaks similar to that of naked Fe3 O4 . The peaks at 29.55 , 35.13 ,
43.22 , 53.81 , 57.20 and 62.84 corresponded to the cubic phase
of Fe3 O4 (220), (311), (400), (422), (511) and (440), respectively,
which indicated that all of the magnetic nanoparticles still had
cubic crystal structures as the neat Fe3 O4 nanoparticles (Wan et
al.,
2016). TGA measurement was carried out to determine the per-
cent weight loss of the magnetite complexes, which manifested
the amount of SCS assembly on the surfaces of nanoparticles. All
of the magnetic nanoparticles lost 68% (w/w) of their weights,
cor-
responding to the evaporation of bound water below 200 C
(Zhao,
Nugroho et al., 2015; Zhao, Odelius, Edlund, Zhao, & Albertsson,
Fig. 3. The stability of PEI@MNP (a), PEI@MNP/SCS (b) and PEI@MNP/SCSCL (c) nanoparticles (A). TEM photos of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and
PEI@MNP/SCSCLA (d) nanoparticles (B).
Fig. 4. XRD (A) and TGA (B) curves of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.
2015). The TGA curves of PEI@MNP and PEI@MNP/SCS showed
weight losses of about 90.2% and 93.1% at 400 C, respectively,
indicating that the amount of SCS assembled on the surface of
PEI@MNP was 2.9%. It was noticed that the thermal stability
of PEI@MNP/SCSCL decreased compared to that of PEI@MNP/SCS
above 200 C, which was due to the low degradation tempera-
ture of pendant glutaraldehyde. As we hypothesized, the thermal
stability of the PEI@MNP/SCSCL was enhanced after the addition
of acetic acid, as shown in the TGA curve of PEI@MNP/SCSCLA
(d).
3.3. Reserved high magnetization of nanoparticles
The magnetizations of PEI@MNP, PEI@MNP/SCS, PEI@MNP/
SCSCL and PEI@MNP/SCSCLA nanoparticles are measured using a
vibrating sample magnetometer (VSM) at 298 K, as shown in Fig.
5. No remanence was observed from the magnetization curves at
low magnetic eld. The remanence of the four samples was zero
and the coercivity was almost negligible in the case of the
absence of the external magnetic eld. The coercivity (Hc) is the
magnetic- eld strength necessary to demagnetize a magnetic
material that is fully magnetized. The magnetic hysteresis loops of
the composite nanoparticles could reect their coercivities. The
enlarged mag- netic hysteresis loops of the nanoparticles in the
range between
200 and 200 G are shown in the inserted image of Fig. 5. All of
composite nanoparticles exhibited an extremely small hysteresis
loop and very low coercivity (about 130 G). These ndings were
the typically characteristic of superparamagnetic particles. The
satura- tion magnetizations were 68.0, 64.1, 52.4 and 56.9 emu/g
for the PEI@MNP, PEI@MNP/SCS, PEI@MNP/SCSCL and
PEI@MNP/SCSCLA nanoparticles, respectively. In comparison to the
naked PEI@MNP, the saturation magnetization of PEI@MNP/SCS
decreased due to the covers of SCS on the surfaces of the
nanoparticles, which reduced the magnetic moment. The similar
trend was also found in the PEI@MNP/SCSCL and
PEI@MNP/SCSCLA . When acetic acid was added during the
cross-linking, the situation became complicated. The VSM
results suggested that the synthetic PEI@MNP, PEI@MNP/SCS,
PEI@MNP/SCSCL and PEI@MNP/SCSCLA nanoparticles had the
poten- tial to be separated by the magnetic bar when they were
using as adsorbents in wastewater.
3.4. Recycle and regeneration of magnetic nanoparticles for dye
removal
The removal percentage (%) versus time (min) of the magnetic
nanoparticles is conducted, and the results are as shown in Fig.
6A. The magnetic nanoparticles containing SCS exhibited high
removal ability (over 50%) of MB, while the naked PEI@MNP only
adsorbed
 Fig. 5. VSM photos of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.

Fig. 6. The removal percentage (%) of MB versus time (min) for PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles (A). Adsorption,
desorption and re-adsorption of MB curves (B) and photos (C) by PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.

about 15% of MB. To evaluate the recyclability and regeneration of
the magnetic adsorbents, adsorption, desorption and re-
adsorption experiments are conducted and the results are
shown in Fig. 5B and C. As shown in Fig. 6B, the removal
ability of MB by the PEI@MNP was kept at a low level during
adsorption, desorption and
re-adsorption experiments. All of the adsorbents containing SCS
exhibited a high ability to desorb and re-adsorb MB. However, the
un-cross-linked PEI@MNP/SCS showed the reduced ability to re-
adsorb the dye MB. The adsorption, desorption and re-adsorption
of MB were more visualized in Fig. 6C.
 Scheme 2. The illustration of adsorption and desorption of PEI@MNP/SCS and PEI@MNP/SCSCL .
The adsorption process of MB is illustrated in Scheme 2. For
the rst time of MB adsorption, both uncross-linked and cross-
linked SCS magnetic nanoparticles have the ability to adsorb MB
due to the interaction between the active sites of adsorbent and
the cationic group of MB. However, some uncross-linked SCS poly-
mers are lost during the desorption of MB. In the re-adsorption of
MB, the PEI@MNP/SCS has fewer amount of functional SCS, there-
fore it shows decreased removal ability of MB. Compared with
PEI@MNP/SCSCL , the PEI@MNP/SCSCLA has higher removal ability
of MB during re-adsorption process. The reason is that the
trapped acetic acid in the cluster might be removed during the
desorption process, which generated more active sites for the re-
adsorption of MB.
4. Conclusion
Herein, we report an efcient method for creating recyclable
and regenerable magnetic adsorbent for MB removal. The mate-
rials containing SCS showed high negatively charged surfaces. In
addition, due to the presence of Fe3 O4 nanoparticles, the
nanomate- rial exhibited magnetic properties. The cross-linked
PEI@MNP/SCS product was used as an effective adsorbent for the
removal of MB in a short duration. Furthermore, beneting from
their high satu- ration magnetization (over 52 emu/g), the
obtained polysaccharide adsorbent could be easily separated from
the solution by a magnet. The magnetic polysaccharide absorbent
could be regenerated and reused for MB removal. Based on the
experimental results, the pro- posed route can pave a way to
recycle absorbents to provide large amounts of highly valuable
polysaccharide materials in the future.
Acknowledgements
This work was nancially sponsored by the National Natural
Science Foundation of China (Nos. 51433007 and 51503125), and
China Postdoctoral Science Foundation (No. 2015 M580791). We
appreciate Miss Ying Liu for the preparation of Fe3 O4
nanoparticles.
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