Journal of Physics and Chemistry of Solids 121 (2018) 102–109

Contents lists available at ScienceDirect

Journal of Physics and Chemistry of Solids

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

Synthesis of Fe3O4 nanoparticles functionalized polyvinyl alcohol/chitosan T

magnetic composite hydrogel as an efficient adsorbent for chromium (VI)
removal
Eryun Yana,∗, Minglu Caoa, Xiqing Renc, Jinyu Jianga, Qinglong Ana, Zuoyuan Zhanga,
Jianwei Gaob, Xiuying Yanga, Deqing Zhanga,∗∗
a
College of Material Science and Engineering, Qiqihar University, Qiqihar, 161006, PR China
b
College of Food and Biological Engineering, Qiqihar University, Qiqihar, 161006, PR China
c
ZhongKe Pilot Technology Co., Ltd, Tianjin, 300384, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Fe3O4 nanoparticles functionalized polyvinyl alcohol/chitosan magnetic composite hydrogel (Fe3O4-MCH) was
Fe3O4 successfully synthesized via crosslinking method. The Fe3O4-MCH was explored to be used as an adsorbent for
Composite removing chromium (Ⅵ) (CrⅥ) from aqueous solution and it exhibited encouraging adsorption performance for
Hydrogel CrⅥ both under neutral and acidic conditions. In neutral condition, sharing electron may be one of the possible
CrⅥ removal
adsorption reasons, while in acidic condition, the electrostatic attraction was a possible adsorption mechanism.
Adsorbent
The pseudo-first-order rate model can be well described the adsorption and the equilibrium isotherm was better
matched with the Langmuir model. In addition, the swelling ratio of the blank hydrogel was conspicuously
higher than that of the hydrogel containing Fe3O4 nanoparticles (Fe3O4 NPs). The loading capacity of CrⅥ on the
adsorbent remained at a high level even after five cycles, which showed that the as-prepared hydrogel can be
widely used for repeated CrⅥ removal in wastewater in near future.

1. Introduction
Chromium is a common contaminant in wastewater since a wide
range of industries use chromium in their processes. Chromium exhibits
two oxidation states: chromium (Ⅵ) (CrⅥ) and chromium (Ⅲ) (CrⅢ).
Compared with CrⅢ, CrⅥ is more dangerous, and it can cause poisoning
symptom, such as abdominal discomfort, allergic dermatitis or eczema
[1,2]. Moreover, it can cause pharyngitis and bronchitis by its corro-
sivity [3]. Hence, CrⅥ removal is very significant in today's research.
Until now, various treatment technologies, such as adsorption [4,5],
precipitation [6], reverse osmosis [7] and reduction [8] have been
utilized to treat CrⅥ from the contaminated water system, among which
adsorption has been proved to be the most convenient and low-cost
method.
A great deal of materials can be used as adsorbents, such as carbon
fibers [9], montmorillonite [10], active carbon [11], diatomite [12],
polymer hydrogel [13], and so on. Among them, polymer hydrogel with
three-dimensional cross-linked network has attracted special attention
for its high porosity, excellent conductivity, large surface area and
unique mechanical properties [14,15]. During the process of
adsorption, the heavy metal ions could interpenetrate into the network
of the hydrogel with water quickly and bind to the hydrophilic func-
tional groups in the hydrogel effectively, such as -COOH, -NH2 and -OH
[16]. In considering of environmental-friendly, the polymers with
nontoxic, biodegradable, and biocompatible properties are ideal can-
didates for constructing the hydrogel adsorbents.
In previous study, polymer composite hydrogel based on chitosan
(CS) and polyvinyl alcohol (PVA) has received increasing interests.
Since CS had excellent low toxicity, biocompatibility, degradability and
low cost, and PVA had good mechanical strength and flexibility in the
hydrogel. And that, the hydrogel possessed good chemical stability,
which due to the specific intermolecular interactions between PVA and
CS. Thus, the PVA/CS based hydrogel has been extensively studied in
disposal of heavy metals in wastewater, such as Cu(II) and Hg(II)
[16–18]. Although successful, the separation and collection of the ad-
sorbents was still a problem.
To overcome the difficulty of separation and collection of the PVA/
CS hydrogel, in the present study, Fe3O4 NPs were dopped into the
hydrogel. It was well known that Fe3O4 NPs can be easily separated,
collected and reused by external magnetic field. Further more, they

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: yaney359@126.com (E. Yan), zhdqing@163.com (D. Zhang).

https://doi.org/10.1016/j.jpcs.2018.05.028
Received 20 October 2017; Received in revised form 16 April 2018; Accepted 18 May 2018
Available online 19 May 2018
0022-3697/ © 2018 Elsevier Ltd. All rights reserved.
E. Yan et al.
played a positive role in the adsorption of the heavy metal ions. The
resulting Fe3O4 nanoparticles functionalized PVA/CS magnetic com-
posite hydrogel (Fe3O4-MCH) was constructed via crosslinking method.
It was very desired that abundant of holes existed on the hydrogel,
which provided a channel for some matters for passing in. The as-pre-
pared hydrogel was explored to be used as an adsorbent for CrⅥ, which
exhibited outstanding adsorption performance under both neutral and
acidic environments. Moreover, the hydrogel can be separated and
collected due to the appearance of Fe3O4 NPs easily. Pseudo-first-order
and Langmuir model were used to analyze the kinetics and mechanism
for the adsorption of CrⅥ. The loading capacity of CrⅥ on the adsorbent
remained at a high level even after five cycles, which showed that the
as-prepared hydrogel can be widely used for repeated CrⅥ removal in
wastewater in near future. Fe3O4-MCH was characterized by SEM, TEM,
VSM and FT-IR. It was anticipated that this composite hydrogel showed
promising potential for wastewater treatment.
2. Experimental section
2.1. Materials
FeCl2·4H2O and ammonium hydroxide were supplied by Tianjin
Fuyu Chemical Co., LTD (Tianjin, China), FeCl3·6H2O by Tianjin
Yaohua Chemical Reagent Co., LTD (Tianjin, China), K2Cr2O7 by
Xianshuigu Industrial Park (Tianjin, China); polyvinyl alcohol (PVA) by
Tokyo Chemical Industry Co., LTD (Tokyo, Japan), chitosan (CS) with a
deacetylation degree of 91.1% by Nantong Shuanglin Biological
Products Co., LTD (Jiangsu, China). All of the other chemicals were
used as received without any purification.
2.2. Preparation of Fe3O4 colloid
Fe3O4 colloid was prepared according to our previous study [19].
Part of the Fe3O4 colloid obtained was frozen at minus 70 °C for about
48 h and dried in a freezing dryer.
2.3. Preparation of Fe3O4-MCH
Firstly, 10% PVA solution (2.1 g) and 2% CS solution (0.9 g) were
mixed together. Secondly, 0, 0.4, 0.9 and 1.8 g Fe3O4 colloid was
added, respectively. The mixture was stirred vigorously for 10 min to
ensure the well dispersion of the NPs. After that, 5 drops of glacial
acetic acid were introduced into the mixture. After cross-linked in
glutaraldehyde vapor for 24 h, the Fe3O4-MCH was obtained. The
compositions and abbreviation of the Fe3O4-MCH were presented in
Table 1.
2.4. Adsorption experiments
2.0 g of Fe3O4-MCH with different amount of Fe3O4 NPs was soaked
in 500 mL of 100 mg/L K2Cr2O7 solution, which was shaken at 200 rpm
on a magnetic stirrer. Under a certain period of time (0, 5, 10, 20, 30,
50, 120, 150, 300, 450 and 1440 min), 5 mL of the solution was taken
out and the concentration of CrⅥ was measured on a UV–vis
Spectrometer at 540 nm after complexing with 1,5-diphenylcarbazide.
Finally, the adsorption capacity was calculated using eq. (1):
Table 1
Compositions and abbreviation of the Fe3O4-MCH.
Sample Fe3O4 colloid/g 10% PVA solution/g 2% CS solution/g
Hydrogel0 0 2.1 0.9
Hydrogel0.4 0.4 2.1 0.9
Hydrogel0.9 0.9 2.1 0.9
Hydrogel1.8 1.8 2.1 0.9
103
Journal of Physics and Chemistry of Solids 121 (2018) 102–109
(C0 − Ct ) V
q=
mA (1)
Ⅵ
Where q (g/g) is Cr adsorption capacity in the per gram adsorbent at
time t (min); C0, Ct are the initial CrⅥ concentration and the CrⅥ
concentration at time t in the solution (g/L), respectively; mA is the
mass of the used adsorbent (g); V is the volume of the text solution (L).
The effect of pH value on the adsorption of CrⅥ ions was also ex-
plored. 50 mL of 100 mg L−1 CrⅥ solution with pH value ranging from
1.0 to 8.0 was added with 0.2 g of adsorbent, which was kept for
15 min. After that, the concentration of CrⅥ was tested as mentioned
above.
According to above exploration, batch experiment of adsorption
CrⅥ was conducted under the pH value in which the adsorption was
maximum.
2.5. Repeatability and reproducibility of the Fe3O4-MCH adsorbent
To investigate the repeatability and reproducibility of the Fe3O4-
MCH, the same adsorption step was carried out as the previous section
firstly. After adsorption of CrⅥ, the adsorbent was put into 20 mL of
0.01 mol L−1 NaOH solution, which was shaken in a shaker at 180 rpm
for 30 min. Then, the treated Fe3O4-MCH adsorbent was washed twice
with ultrapure water, and activated using 10 mL of 0.01 mol L−1 HCl
solution. At last, the adsorbent was dried in drying cabinet and used for
next cycle.
2.6. Characterization
Fourier transform infrared spectra (FT-IR) were recorded on a
Spectrum One instrument (PE, U.S.). The microstructure of the Fe3O4-
MCH was observed on S-4300 scanning electron microscope (SEM,
Hitachi, Japan), H-7650 transmission electron microscope (TEM,
Hitachi, Japan) and Tecnai G2 F30 S-TWIN high-resolution transmis-
sion electron microscopy (HR-TEM, FEI, U.S.). The magnetic property
of the samples was determined by VL-072 vibrating sample magneto-
metry (Quantum Design Co., U.S.). The nitrogen adsorption-desorption
isotherm and pore size distribution of the hydrogel were carried out on
a AUTOSORB-I automatic physical/chemical adsorption analyzer
(Quantachrome, U.S.). A ESCALAB 250Xi X-ray photoelectron spec-
trometer (XPS, Thermo, U.S.) was used in the surface analysis of the
Fe3O4 NPs and the as-prepared Fe3O4-MCH before and after CrⅥ ad-
sorption.
3. Results and discussion
3.1. Morphology and size distribution of the Fe3O4 NPs
TEM was used to measure the morphology and particle size of the
Fe3O4 NPs, presented in Fig. 1. As can be seen (Fig. 1A), the Fe3O4 NPs
dispersed well with the help of the stabilizer trisodium citrate, and al-
most no aggregation was observed. Via measuring and calculating, the
particle size of Fe3O4 NPs concentrated from 5 to 20 nm, and the
average diameter was about 12 nm, as Fig. 1B showed.
3.2. Magnetic properties of the Fe3O4 NPs and the Fe3O4-MCH
The magnetism of the Fe3O4 NPs and the Fe3O4-MCH was measured
by VL-072 vibrating sample magnetometry. Magnetization versus field
curves were shown in Fig. 2. For the NPs, at 300 K, the slim hysteresis
loop with saturation magnetization (Ms = 75.8 emu/g) indicated that
the Fe3O4 NPs had a good superparamagnetic nature. For the Fe3O4-
MCH, with the increase of Fe3O4 colloid added, the magnetization of
the Fe3O4-MCH was obviously strengthened (Ms of Hydrogel0, Hy-
drogel0.4, Hydrogel0.9 and Hydrogel1.8 was 0, 4.8, 10.2 and 20.9
emu/g, respectively), although they were all lower than the Fe3O4 NPs'.
E. Yan et al.
Fig. 1. (A): TEM image of the as-prepared Fe3O4 NPs and (B): Size histogram of the particles in TEM image (150 particles were measured to obtain the average
diameter).
Fig. 2. VSM magnetization of the Fe3O4 NPs, Hydrogel1.8, Hydrogel0.9,
Hydrogel0.4 and Hydrogel0.
It can be interpreted as following: the content of Fe3O4 was reduced in
the Fe3O4-MCH comparing with the standing Fe3O4 NPs, and that,
Fe3O4 NPs were clad by the PVA and CS network, both of which re-
sulted in the weakness of the magnetization of the hydrogel.
3.3. Morphology of the Fe3O4-MCH
The SEM images of the Fe3O4-MCH were shown in Fig. 3. Just as can
be seen, with the changing of the Fe3O4 colloid amount, the surface
morphology of hydrogel showed great differences. With the increase of
Fe3O4 colloid added, the surface of hydrogel became much rougher. At
the same time, more and more holes appeared in the Fe3O4-MCH. It was
very desired that the holes provided a channel for some small molecules
or functional materials for passing in and out, which would have a
potential application in the field of adsorption.
TEM was employed to characterize the microstructures of the
Fe3O4-MCH, shown in Fig. 4A. It can be observed that Fe3O4 NPs have
been doped completely into the hydrogel, exhibiting as the black par-
ticles in the image. What's more, the Fe3O4 NPs were well distributed in
the hydrogel by employing the ultrasonic dispersion. It seemed that a
few aggregations existed. In fact, it was resulted from that the hydrogel
sample in certain parts was relatively thick. Since the hydrogel was in a
dry state, its shape was not as clear as that in the wet state. The ex-
istence of Fe3O4 NPs in the hydrogel was further testified by HRTEM,
presented in Fig. 4B. Seen from the image, Fe3O4 NPs in the PVA/CS
hydrogel arranged out of order. The inset was the FT-electron
104
Journal of Physics and Chemistry of Solids 121 (2018) 102–109
diffraction of the Fe3O4-MCH, showing that the Fe3O4 NPs presented in
polycrystal structure.
3.4. Adsorption-desorption isotherm and pore size distribution
To study the porous structures of the Fe3O4-MCH, nitrogen ad-
sorption-desorption isotherm for the hydrogels with different mass of
Fe3O4 colloid was carried out under 30 °C using a conventional gas
adsorption apparatus, shown in Fig. 5A. Depending on the surface
properties of the given hydrogels, obviously, the isotherms for all the
samples belonged to Type Ⅲ, since the curves were convex in the whole
pressure range. It meant that there can be weak forces between the
adsorbent and the adsorbate. The BET surface area was calculated to be
5.887, 4.352, 3.341 and 1.096 m2/g for the samples of Hydrogel1.8,
Hydrogel0.9, Hydrogel0.4 and Hydrogel0, respectively. It was con-
sistent with the results from SEM images, since more and more pores
appeared with the increase of Fe3O4 colloid added. Pore size distribu-
tion of the Fe3O4-MCH was calculated from the adsorption data using
the BJH method, presented in Fig. 5B. As can be seen, for the four
samples, the pore size mainly centered in the mesopores range (be-
tween 2 and 50 nm), in other words, the Fe3O4-MCH was a mesoporous
material.
3.5. FT-IR spectra analysis
The FT-IR spectra of Fe3O4 NPs (A), PVA/CS composite hydrogel (B)
and Fe3O4-MCH (C) were shown in Fig. 6. In general, the curve shape of
the PVA/CS composite hydrogel was similar to that of the magnetic
hydrogel. The broad adsorption band at 3440 cm−1 was attributed to
the stretching mode of -OH in PVA, CS and the adsorbed water. The
peak of free -CH3 (νC-H) in PVA and CS was at 2940 cm−1. The ad-
sorption peaks at 1650 and 1096 cm−1 were ascribed to amideⅠ and C-
O-C of CS, respectively. In the low-frequency region, the adsorption
peak at 838 cm−1 was belonged to δN-H of free -NH2 in CS. For the
Fe3O4 NPs (Fig. 6A), the adsorption peak at 589 cm−1 was ascribed to
νFe-O of Fe3O4. Compared with the standing PVA/CS hydrogel, the peak
at 589 cm−1 in the magnetic hydrogel has been slightly strengthened
because of the addition of Fe3O4 NPs.
3.6. Swelling kinetics
The swelling kinetics curves of the Fe3O4-MCH adsorbent in deio-
nized water was shown in Fig. 7. As can be seen, the swelling ratio of
the hydrogel without Fe3O4 NPs (Hydrogel0) was conspicuously higher
than that of the hydrogel containing Fe3O4 NPs under the same time. It
seemed that the existence of Fe3O4 NPs restricted the water adsorption
of the hydrogel. In addition, with the increase of Fe3O4 NPs added, the
swelling ratio of the hydrogel decreased gradually. It was possible that
E. Yan et al. Journal of Physics and Chemistry of Solids 121 (2018) 102–109

Fig. 3. SEM images of the Fe3O4-MCH with different mass of Fe3O4 colloid: (A) Hydrogel0, (B) Hydrogel0.4, (C) Hydrogel0.9 and (D) Hydrogel1.8; the ratio of PVA/
CS was 7:3.

Fe3O4 NPs occupied the space in the hydrogel, as a result, less and less relatively decreased compared with Hydrogel0.9, so that, the remaining
water went into the interior of the hydrogel. -NH2 and -OH were not enough to combine with CrO42−. As a con-
sequence, the saturated absorption was unexpectedly decreased. In
addition, for the Hydrogel1.8, it reached to absorption equilibrium at
3.7. Adsorption experiments
less than 10 min, faster than the other three samples, which originated
from that it possessed more pores relative to the other samples, as ob-
As a porous material, the as-prepared Fe3O4-MCH can be an ideal
served by SEM.
adsorbent for adsorbing and releasing external matters. So, in the pre-
The adsorption of CrⅥ on the Fe3O4-MCH under the pH of 3.0 was
sent study, we attempted to explore the feasibility of the Fe3O4-MCH in
also researched and the result was shown in Fig. 9. For the sample
adsorbing the heavy metal ion CrⅥ. The adsorption capacity of the
Hydrogel1.8, the saturated absorption was 0.228 g/g, which was the
Fe3O4-MCH with different mass of Fe3O4 for CrⅥ under different time
highest among the four samples (0.223 g/g for Hydrogel0.9 and
was presented in Fig. 8. In general, when the amount of Fe3O4 was
0.200 g/g for Hydrogel0.4). Of course, the saturated absorption of the
lower than 1.8 g, the absorption was dependent on the amount of
Hydrogel0 was the lowest (0.123 g/g), indicating that the introduction
Fe3O4. When 0.9 g of Fe3O4 colloid was added, the saturated absorption
of Fe3O4 played an important role in the absorption of CrⅥ. Under the
was 0.281 g/g, which was the highest among the four samples (0.055 g/
pH of 3.0, the predominate ionic specie of CrⅥ was HCrO4−, which was
g for Hydrogel0, 0.244 g/g for Hydrogel0.4 and 0.255 g/g for Hy-
well adsorbed by the hydrogel. As we can see in Fig. 8, the adsorption
drogel1.8). For the Hydrogel1.8, its saturated absorption was less than
equilibrium was reached as quick as 10 min for the hydrogel samples
that of the Hydrogel0.9. It was well known that the -NH2 and -OH on
with Fe3O4. In acidic condition, H+ promoted the oxidation-reduction
the surface of hydrogel or in the holes would coordinate with Fe in
reaction between Fe3O4 and HCrO4− as time going, and that, the
Fe3O4. For the Hydrogel1.8, the number of free -NH2 and -OH was

Fig. 4. TEM image of Hydrogel1.8 (A); the corresponding HRTEM image of the Hydrogel1.8 (B); inset is the FT-electron diffraction of the hydrogel.

105
E. Yan et al.
Fig. 5. Nitrogen adsorption-desorption isotherm (A) and pore size distributions (B) for the Fe3O4-MCH adsorbent (a: Hydrogel0, b: Hydrogel0.4, c: Hydrogel0.9 and
d: Hydrogel1.8) at the temperature of 30 °C.
Fig. 6. FT-IR spectra of Fe3O4 NPs (A), PVA/CS composite hydrogel (B) and
Fe3O4-MCH (C).
Fig. 7. Swelling kinetics of the Fe3O4-MCH adsorbent in deionized water (SR:
swelling ratio; t: swelling time).
negatively charged HCrO4− can be well adsorbed by the positively
charged active groups like -OH2+ and -NH3+. What's more, the re-
pulsive force between -OH2+ and -NH3+ groups made the pores of
hydrogel expand, which was also in favor of the entering and adsorp-
tion of the heavy metal ions.
106
Journal of Physics and Chemistry of Solids 121 (2018) 102–109
Fig. 8. Adsorption kinetics of CrⅥ on the Fe3O4-MCH adsorbent (A: Hydrogel0,
B: Hydrogel0.4, C: Hydrogel0.9 and D: Hydrogel1.8) at neutral condition.
Fig. 9. Adsorption kinetics of CrⅥ on the Fe3O4-MCH adsorbent (A: Hydrogel0,
B: Hydrogel0.4, C: Hydrogel0.9 and D: Hydrogel1.8) under the pH of 3.0.
3.8. Kinetics study
The results of the kinetics of CrⅥ removal on the Fe3O4-MCH sug-
gested that it was really effective (Figs. 8 and 9). About 90% of the
ultimate adsorption capacity was reached in 10 min, and it took less
than 30 min to reach the equilibrium.
Two kinetic models, namely, pseudo-first-order (eq. (2)) and
pseudo-second-order (eq. (3)), were used to fit the experimental data
and evaluate the adsorption kinetic process.
E. Yan et al. Journal of Physics and Chemistry of Solids 121 (2018) 102–109

Table 2 Table 3
Pseudo-first-order model and pseudo-second-order model for CrⅥ adsorption on Freundlich and Langmuir isotherm parameters for CrⅥ adsorption on the Fe3O4-
the Fe3O4-MCH. MCH.
kinetic models v0 (g/ k (L/min) qe (g/g) qe*(g/g) R2 T/K Freundlich Langmuir
g·min)
n k R2 qm/g·g−1 b R2
pseudo-first- order model 0.420 0.221 0.222 0.9985
pseudo-second- order 0.333 0.213 0.222 0.9104 293 4.67 57.25 0.925 0.2670 0.37 0.995
model 303 4.32 55.17 0.917 0.2469 0.35 0.987
313 3.85 52.81 0.962 0.2415 0.20 0.991
Where qe and qe* are the calculated and measured equilibrium adsorption ca-
pacities of CrⅥ, respectively.
The calculated qe values were close to the theoretical ones, and R-square adsorption of CrⅥ onto the surface of Fe3O4-MCH is a monolayer ad-
showed quite good linearity with R2 above 0.9985. Therefore, the adsorption sorption. What's more, with the increase of temperature, the maximum
kinetics followed the pseudo-first-order model. adsorption capacity was found to be 0.2415, 0.2469 and 0.2670 g/g,
respectively, suggesting that the adsorption capacity was enhanced
ln(qe-qt) = lnqe-k1t (2) with the increase of the temperature.
t 1 t
= +
qt v0 qe (3) 3.10. Possible adsorption mechanism

where qe (g/g) and qt (g/g) represent the adsorption capacity at equi-

librium and at time t, k1 is the pseudo-first-order adsorption rate con-
stant, and v0 is the initial adsorption ratio (g/g·min).
The kinetic parameters of the two models were shown in Table 2.
3.9. Adsorption isotherms
Adsorption isotherms studies were necessary to indicate the ad-
sorption capacity of the adsorbent. Fig. 10 showed the CrⅥ adsorption
isotherms on the Fe3O4-MCH adsorbent (Hydrogel1.8) with various
temperatures. Under the acid condition (pH 3.0), batch experiments
were carried out by changing the concentration of CrⅥ from 0 to
100 mg/L. In this study, Freundlich (eq. (4)) and Langmuir (eq. (5))
models were utilized to correlate the adsorption isotherms.
qm bCe
qe =
bCe + 1
1
qe = kCen
Ⅵ
Where qe and qm are the amount of Cr adsorbed at equilibrium (g/g)
and at maximum (g/g), respectively; Ce is the equilibrium concentration
of CrⅥ (mg/L); b is the constant related to the energy of adsorption; k
and n are the constants of the Freundlich adsorption model.
The parameters calculated from Freundlich and Langmuir models
were listed in Table 3. As can be seen, the Langmuir isotherm fit better
to the experimental data with a higher R2, which indicated that the
Fig. 10. Adsorption isotherm for CrⅥ adsorption on the Fe3O4-MCH.
The full-range XPS was used to characterize the surface states of the
Fe3O4-MCH adsorbent before and after contacting with CrⅥ, as shown
in Fig. 11A. As can be seen, a new peak at 585.17 eV belonging to CrⅥ
appeared after the absorption experiment. It can be learned that CrⅥ
ions were successfully loaded onto the Fe3O4-MCH adsorbent.
For the Fe3O4-MCH after absorption (Fig. 11B), the XPS spectrum
showed three peaks at 584.99, 578.93 and 574.95 eV, which were
characteristic for Cr 2p1/2, Cr 2p3/2 of CrⅥ and Cr 2p3/2 of CrⅢ, re-
spectively. So, it can be deduced that both CrⅥ and CrⅢ co-existed on
the adsorbent. In neutral condition, CrO42− was reduced into CrⅢ by
the reduced groups like -NH2 and FeⅡ of Fe3O4 slowly. While in acidic
condition, CrⅥ existed as HCrO4−, which can be also reduced into CrⅢ
by the protonated groups like -OH2+ and -NH3+. Therefore, CrⅥ and
CrⅢ were simultaneously adsorbed onto the adsorbent and the oxida-
tion-reduction reactions may be one of the possible adsorption reasons.
(4) In addition, the XPS spectrum of Fe in the Fe3O4-MCH adsorbent was
shown in Fig. 11C. Before adsorption, the typical Fe 2p (2p3/2 and 2p1/
(5) 2) peaks were at around 711.50 and 725.00 eV. The peak of Fe 2p3/2 can
be assigned to 2p3/2 of Fe2+ and Fe3+. After the CrⅥ adsorption, the Fe
2p3/2 peak of Fe3+ was still at 712.02 eV, while the Fe 2p3/2 peak of
Fe2+ was removed from 716.96 eV to 713.96 eV (typical Fe 2p3/2 of
Fe3+). It indicated that some of Fe2+ ions in Fe3O4 were oxidized into
Fe3+ by CrⅥ, as a result, the oxidation-reduction reaction between
Fe2+ and CrⅥ may also lead to the appearance of CrⅢ.
Fig. 11D showed the XPS spectrum of O 1s. Before adsorption, the
peak at 532.70 eV can be assigned to C-OH of PVA and CS chains, and
the peak at 531.99 eV can be assigned to Fe-O. After the adsorption of
CrⅥ, the peak of C-OH had a small shift to 532.63 eV and it was weaker
than before, which suggested that -OH has involved in CrⅥ adsorption
via sharing electrons with CrⅥ.
For the N 1s XPS spectrum of the Fe3O4-MCH adsorbent (Fig. 11E),
the peak at 400.13 eV can be assigned to the -NH2 group and the peak at
399.52 eV can be assigned to the C=N group formed by cross-linking
reaction. The peak at 402.02 eV may be belonged to Fe-NH2 in the
hydrogel adsorbent. After CrⅥ adsorption in neutral condition, the peak
of -NH2 group had a small shift to 399.91 eV, revealing that -NH2 group
and CrⅥ occurred electron transfer. What's more, 402.51 eV, the peak of
Fe-NH2, also exhibited a shift and it became stronger. This might be
-NH2 groups on Fe involved in the adsorption of CrⅥ. However, the
peak of C=N group had no obvious change, indicating that C=N group
has not participated in CrⅥ adsorption reaction.
In a word, the results of XPS spectra can infer the possible adsorp-
tion mechanism. In neutral condition, sharing electron may be one of
the possible adsorption reasons since the electronic-rich -OH and -NH2
groups could attract CrⅥ and CrⅢ by the lone pair electrons. While in
low pH environment, the electrostatic attraction is a possible adsorp-
tion mechanism since the negatively charged HCrO4− could be

107
E. Yan et al.
Fig. 11. XPS spectra of the Fe3O4-MCH before and after CrⅥ adsorption (A), Cr 2p (B), Fe 2p (C), O 1s (D) and N 1s (E).
absorbed quickly by the positively charged groups (-OH2+ and -NH3+).
Whether in acidic or neutral condition, the oxidation-reduction reaction
between CrⅥ and the reducing substances (such as Fe2+ in Fe3O4 and
-NH2) should be responsible for the CrⅥ adsorption.
3.11. Repeatability and reproducibility of Fe3O4-MCH
To investigate the repeatability and reproducibility of the Fe3O4-
MCH adsorbent, the same method was used to test the adsorption
ability of hydrogel toward 100 mg/L CrⅥ solution and the result was
shown in Fig. 12. It was clear that the adsorption capacity decreased
continuously after a new cycle. At the last regeneration cycle, the re-
moval rate of CrⅥ was still more than 50%, implying that the synthe-
sized Fe3O4-MCH adsorbent possessed good regeneration power.
4. Conclusion
The three-dimensional Fe3O4-MCH has been successfully
108
Journal of Physics and Chemistry of Solids 121 (2018) 102–109
synthesized via crosslinking method. The Fe3O4-MCH was a meso-
porous material and the Fe3O4 NPs were well dispersed in it. The
swelling ratio of the blank hydrogel was conspicuously higher than that
of the hydrogel containing Fe3O4 NPs. The Fe3O4-MCH was explored to
be used as an adsorbent for removing CrⅥ from aqueous solution and it
exhibited outstanding adsorption performance both under neutral and
acidic conditions. And it can be well separated with external magnetic
fieldt. The adsorption was well described by the pseudo-first-order
model and Langmuir model can be a better equilibrium isotherm. The
as-prepared hydrogel possessed good repeatability and reproducibility,
and the loading capacity of CrⅥ on the adsorbent even remained at a
high level after five cycles.
The possible CrⅥ removal mechanism was provided. In neutral
condition, sharing electron may be one of the possible adsorption rea-
sons since the electronic-rich -OH and -NH2 groups could attract CrⅥ
and CrⅢ by the lone pair electrons. While in acidic condition, the
electrostatic attraction was a possible adsorption mechanism since the
negatively charged HCrO4− could be absorbed quickly by the positively
E. Yan et al.
Fig. 12. Repeatability and reproducibility of the Fe3O4-MCH adsorbent for CrⅥ.
charged groups, such as -OH2+ and -NH3+. Whether in acidic or neutral
condition, the oxidation-reduction reaction between CrⅥ and the re-
ducing substances (Fe2+ in Fe3O4 and -NH2) should be responsible for
the CrⅥ adsorption. It was anticipated that this composite hydrogel
showed promising potential for wastewater treatment.
Acknowledgments
The present study has been supported in part by NSFC (51772160),
Science and Technology Research Project of Heilongjiang Province
Department of Education (12541871).
References
[1] D. Khan, S. Mushtaq, F. Khan, Toxic effects of chromium on tannery W orkers at
sialkot (Pakistan), J. Toxicology & Industrial Health 29 (2013) 209–215.
[2] L.T. Budnik, X. Baur, The assessment of environmental and occupational exposure
to hazardous substances by biomonitoring, J. Deutsches Arzteblatt International
109
Journal of Physics and Chemistry of Solids 121 (2018) 102–109
106 (2009) 91–97.
[3] R.B. Kalahasthi, R.H. Rao, R.B. Murthy, M.K. Kumar, Effects of chromium (VI) on
the status of plasma lipid peroxidation and erythrocyte antioxidant enzymes in
chromium plating workers, J. Chemico Biological Interactions 164 (2006) 192–199.
[4] H.P. Cong, X.C. Ren, P. Wang, S.H. Yu, Macroscopic multifunctional graphene-
based hydrogels and aerogels by a metal ion induced self-assembly process, J. ACS
Nano 6 (2012) 2693.
[5] N.A. Oladoja, I.A. Ololade, S.E. Olaseni, V.O. Olatujoye, O.S. Jegede,
A.O. Agunloye, Synthesis of nano calcium oxide from a gastropod shell and the
performance evaluation for Cr(VI) removal from aqua system, J. Ind. Eng. Chem.
Res. 51 (2012) 639–648.
[6] N. Kongsricharoern, C. Polprasert, Chromium removal by a bipolar electrochemical
precipitation process, J. Water Sci. Technol 34 (1996) 109–116.
[7] K. Chon, S.J. Kim, J. Moon, J. Cho, Combined coagulation-disk filtration process as
a pretreatment of ultrafiltration and reverse osmosis membrane for wastewater
reclamation: an autopsy study of a pilot plant, J. Water Resour. 46 (2012) 1803.
[8] Y.C. Zhang, J. Li, M. Zhang, et al., Size-tunable hydrothermal synthesis of SnS2
nanocrystals with high performance in visible light-driven photocatalytic reduction
of aqueous Cr(Ⅵ), Environ. Sci. Technol. 45 (2011) 9324–9331.
[9] J.H. Zhang, W.B. Zhang, Y. Zhang, Pore structure characteristics of activated carbon
fibers derived from poplar bark liquefaction and their use for adsorption of Cu(II), J.
BioResources 10 (2015) 566–754.
[10] M.E. Ramos, F.J. Huertas, Adsorption of lactate and citrate on montmorillonite in
aqueous solutions, J. Applied Clay Science 90 (2014) 27–34.
[11] M. Jiang, Y.W. Bai, P. Ning, et al., Adsorption removal of arsine by modified
activated carbon, J. Adsorption 21 (2015) 135–141.
[12] J.V. Flores-Cano, R. Leyva-Ramos, E. Padilla-Ortega, et al., Adsorption of heavy
metals on diatomite: mechanism and effect of operating variables, J. Adsorption
Science and Technology 31 (2013) 275–292.
[13] L.Y. Chai, T. Wang, L.Y. Zhang, et al., A Cu-m-phenylenediamine complex induced
route to fabricate poly (m-phenylenediamine)/reduced graphene oxide hydrogel
and its adsorptionapplication, J. Carbon 81 (2015) 748–757.
[14] S. Stankovich, D.A. Dikin, G.H. Dommett, et al., Graphene-based composite mate-
rials, Nature 442 (2006) 282–286.
[15] L. Zhang, G.Q. Shi, Preparation of highly conductive graphene hydrogels for fab-
ricating supercapacitors with high rate capability, J. Phys. Chem. C 115 (2011)
17206–17212.
[16] L.Z. Li, Z. Wang, P.M. Ma, et al., Preparation of polyvinyl alcohol/chitosan hydrogel
compounded with graphene oxide to enhance the adsorption properties for Cu(II) in
aqueous solution, J. Polym. Res. 22 (2015) 149–150.
[17] X. Wang, R. Sun, C. Wang, pH dependence and thermodynamics of Hg(II) adsorp-
tion onto chitosan-poly(vinyl alcohol) hydrogel adsorbent, Colloids & Surfaces A
Physicochemical & Engineering Aspects 441 (2014) 51–58.
[18] X. Wang, W. Deng, Y. Xie, et al., Selective removal of mercury ions using a chitosan-
poly(vinyl alcohol) hydrogel adsorbent with three-dimensional network structure,
Chem. Eng. J. 228 (2013) 232–242.
[19] E.Y. Yan, M.L. Cao, J.Y. Jiang, et al., A novel adsorbent based on magnetic Fe3O4
contained polyvinyl alcohol/chitosan composite nanofibers for chromium (Ⅵ) re-
moval, Solid State Sci. 72 (2017) 94–102.