Chemical Engineering Journal 351 (2018) 462–472

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Chemical Engineering Journal

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A facile synthesis of core-shell/bead-like poly (vinyl alcohol)/alginate@ T

PAM with good adsorption capacity, high adaptability and stability towards
Cu(Ⅱ) removal
⁎
Wei Zhanga, Qian Denga, Qiulai Hea, Jianyang Songa, Shilu Zhanga, Hongyu Wanga, ,
Jinping Zhoub, Huining Zhangc
a
School of Civil Engineering, Wuhan University, Wuhan 430072, China
b
College of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, China
c
School of Civil Engineering, Lanzhou University of Technology, Lanzhou 730050, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Core-shell/bead-like PVA/SA@PAM
biosorbent was firstly prepared by a
facile route.
• Itamino
was factionalized by introducing
groups and achieved better Cu
(Ⅱ) removal.
• Aofbetter adsorption capacity than most
reported similar alginate-based
biosorbent.
• Ithighexhibits excellent adaptability and
mechanical and chemical stabi-
lity.

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

Keywords: A facile route of poly (vinyl alcohol)/alginate@ polyacrylamide (PVA/SA@PAM) for heavy metal adsorption
Alginate was prepared by crosslinking with PAM onto PVA/SA, which complemented both benefits of natural and syn-
Poly (vinyl alcohol) thetic polymers, resulting from the design of core–shell/bead-like structure and polymer blending. Fourier
Polyacrylamide transform infrared (FT-IR), scanning electron microscopy and energy-dispersive X-ray spectrometry (SEM-EDS)
Cooper
and X-ray photoelectron spectroscopy (XPS) etc. were applied to characterize as-synthesized beads. The results
Adsorption
showed the optimal pH value was 5.0. The adsorption process of Cu(Ⅱ) fitted well with the Freundlich isotherm
model and the pseudo-second-order model in batch system. The experimental maximum adsorption capacity was
79.5 ± 1.6 mg/g under the optimal condition, which is approximately 2.3 and 2 times higher than that of plain
SA beads and PVA/SA beads, respectively. Thermodynamic studies revealed the adsorption process was spon-
taneous and endothermic in nature. Thomas model was fitted better than Bohart-Adams model with break-
through curves under different initial Cu(Ⅱ) concentration in a column system. More importantly, the PVA/SA@
PAM showed excellent mechanical stability and resistance for interference of co-existing ions. Besides, its re-
moval ability only decreased slightly even after eleven cycles in reusability tests. Overall, PVA/SA@PAM ex-
hibits attractive characteristics of simple production process, low cost, good adsorption capacity, excellent
adaptability and chemical and mechanical stability.

⁎
Corresponding author.
E-mail address: hywang96@126.com (H. Wang).

https://doi.org/10.1016/j.cej.2018.06.129
Received 30 March 2018; Received in revised form 18 June 2018; Accepted 19 June 2018
Available online 20 June 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
W. Zhang et al.
1. Introduction
Recently, emerging utilization of natural polymers (e.g., SA, chit-
osan and cellulose) for the design of biosorbent has attracted great at-
tention from acknowledging costs and security concerns. SA is a natural
polysaccharide with abundant carboxyl (–COOH) and hydroxyl (–OH)
functional groups. Strikingly, SA can react with multivalent metal ions
to form a three-dimensional network structure and just make up for the
limitation of separation and regeneration of the adsorbent [1]. Besides,
its excellent properties such as better metal ions binding ability, bio-
compatibility, biodegradability and easily available in natural re-
sources, further make it an ideal material for potential heavy metal
adsorption. However, it still restricted by disintegration and weak
mechanical strength [2]. Naturally, these make people explore some
physicochemical modifications to improve it. Among various methods,
polymer blending provides an idea for developing adsorbents with
desirable properties. Successful attempts also involved with one or
more kinds of polymers, such as chitosan [2], gelatin [3] and cellulose
[4]. Among them, synthetic polymers such as PVA have attracted ex-
tensive attention due to its excellent mechanical and chemical proper-
ties [5]. For instance, Jiang et al. [6] prepared PVA/SA hydrogels to
combine the benefits of both polymers with high toughness. However, it
is still limited by the small quantities of binding sites themselves. To
enhance adsorption capacity, Mahdavinia et al. [7] developed magnetic
hydrogel beads by initially mixing of SA, PVA and magnetic laponite
and then physically crosslinking by Ca2+. Considering these, devel-
oping adsorbents with high adsorption capacity is always the key area
in basic and applied research.
Based on the theory hard and soft acid and base (HSAB), functional
groups containing elements such as O, N and S are conducive to the
formation of complex with specific adsorbate [8,9]. For instance, Wu
et al. [10] employed cyclodextrin modified PVA hydrogel beads for
benzene ions removal. The cyclodextrin addition has positive effects on
both the removal efficiency and rate. Yan et al. [1] synthesized a
polyethyleneimine-modified alginate beads with abundant amino
groups for hexavalent chromium removal. Additionally, Song et al. [11]
prepared a xanthated carboxymethyl chitosan for the uptake of lead
ions from aqueous solution. As we can see, the introducing of functional
groups facilitates adsorption. Strikingly, PAM is a well-known cheap
and easily available synthetic polymer with abundant of acyl amino
groups and it has been widely used as an adsorbent material [12–14].
Accordingly, it is simple to blend PAM with other polymers and further
form bead-like structure, while some of PAM will be embedded inside
rather than exposed to the outside of the adsorbent. Thus, some of PAM
could not be utilized for direct adsorption, resulting in lower removal
rate and even adsorption capacity. Considering with these concerns, we
discussed the design and prepared with a core-shell-like hydrogel beads
for adsorption.
In the present work, a novel bio-sorbent with core-shell/bead-like
structure was prepared to remove copper (Cu(Ⅱ)) from aqueous solu-
tion. The bio-sorbent was synthesized by using PVA/SA hydrogel beads
as supporting materials to graft PAM onto the surface through physi-
cochemical crosslinking reaction. Intermolecular hydrogen bonding
could be formed between the hydroxyl groups of PVA/SA and amino
groups (–NH2) of PAM after physical stirring. Besides, a one-step con-
jugation method was used through simply adding glutaraldehyde to the
mixture, where glutaraldehyde may easily react with some polar groups
in nucleophilic reactions. In the first option, a glutaraldehyde molecule
may react with two amino groups (to form a Schiff base linkage) of
intra-or intermolecular of PAM branched chain [15]. Herein, the final
product could complement both benefits of natural and synthetic
polymers. The physicochemical characterization of the synthesized
beads was conducted by FT-IR, SEM-EDS, FESEM-EDS, XPS and other
conventional methods. Batch experiments were carried out for pH,
adsorption isotherms, kinetics behaviors, adsorption thermodynamic
and interference ions studying. Further, column studies under different
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Chemical Engineering Journal 351 (2018) 462–472
Cu(Ⅱ) concentration and adsorption-desorption experiments were also
investigated to demonstrate the potentiality of this novel bio-sorbent.
2. Materials and methods
2.1. Materials
All chemicals and reagents were of analytical grade or higher and
directly used without any purification. All solutions were prepared with
deionized water unless otherwise stated throughout this study. SA
[(C6H7NaO6)m] was purchased from Qiangsong Fine Chemicals Co., Ltd
(Wuhan, China). In addition, other reagents such as PVA [(C2H4O)n],
PAM [MW ≥ 3000000, (CH2CH(CONH2))x], calcium chloride (CaCl2),
glutaraldehyde aqueous solution (25%, C5H8O2), cupric nitrate [(Cu
(NO3)2·3H2O)] hydrochloric acid (HCl), sodium hydroxide (NaOH), and
sodium chloride (NaCl) were obtained from Sinopharm Chemical
Reagent Co., Ltd (Shanghai, China). A stock Cu(Ⅱ) solution of 1000 mg/
L was prepared and further diluted to the desired levels for later use.
2.2. Preparation of PVA/SA@PAM hydrogel beads
The facile synthesis route of PVA/SA@PAM was depicted in Scheme
1. Initially, 2.0 g of sodium alginate was added into 100 mL of polyvinyl
alcohol solution (1%, w/v) under continuously stirring for 24 h. Then
the mixture was dropped carefully into a 400 mL of CaCl2 solution (5%,
w/v) and further aged for 24 h. The PVA/SA hydrogel beads were
collected by filtration and repeatedly washed with deionized water. In
the control trials, plain SA hydrogel beads were fabricated only without
the addition of PVA. Then, the PVA/SA beads were mixed in 200 mL of
polyacrylamide solution, and the mixture was stirred at room tem-
perature for 12 h to allow the formation of intermolecular hydrogen
bonding among the aforementioned substances. After that, the mixture
was immediately transferred into 200 mL glutaraldehyde reaction so-
lution (1%, w/v) while stirring gently for 1 h under 50 °C water-bath
condition to allow cross-linking reaction [1]. Finally, the PVA/SA@
PAM hydrogel beads were collected, washed and stored for further use
in experiments.
Corresponding to the different contents of functional reagent PAM
(0.5, 1.0, 1.5 and 2.0 g), the as-synthesized PAM modified PVA/SA were
named as PVA/SA@PAM-0.5, PVA/SA@PAM-1.0, PVA/SA@PAM-1.5
AND PVA/SA@PAM-2.0 respectively. In the control trials, blending
PAM into form PVA/SA/PAM bead-like adsorbent was also prepared.
2.3. Batch adsorption experiments
Batch experiments were performed to determine the optimal con-
ditions for Cu(Ⅱ) adsorption process from aqueous solution. Typically,
0.05 g of dried bio-sorbent was added into a 50 mL covered tube with
given concentration (20–500 mg/L) of Cu(Ⅱ) solution at desired pH
values (26). The tubes were incubated at different temperature
Scheme 1. Schematic presentation for synthesis of PVA/SA@PAM beads.
W. Zhang et al.
conditions (20–40 °C) on a rotary shaker (180 rpm). Besides, the effect
of co-existing ions in the 0–0.2 M ranges was also investigated. Mean-
time, four kinds of Cu(Ⅱ) solutions were modeled, including tap water,
deionized water, lake water and river water to compare and survey the
application in real water samples. The initial pH values of the aqueous
solution were controlled by HCl or NaOH (1.0 M). After adsorption
reached equilibrium, the samples were filtered, appropriately diluted
and then determined by the Standard Method. The removal efficiency
(R%) and adsorption capacity values at any time t and at equilibrium (qt
and qe (mg/g)) were calculated with the equations below:
C0−Ce
R(%) = × 100
C0 (1)
C0−Ce
qe = ×V
m (2)
C −C
qt = 0 t × V
m (3)
where C0, Ct and Ce represents the initial, t time and equilibrium Cu(Ⅱ)
ions concentration (mg/L), respectively, m is the weight of dry ad-
sorbent used (g) and V is the volume of Cu(Ⅱ) solution (L). All ex-
perimental data used were an average of twice or more than duplicate
experiments.
2.4. Column adsorption experiments
Continuous column adsorption experiments were carried out in a
mini fixed bed column reactor with an inside diameter of 1.6 cm, a
length of 15 cm (bed depth of 10 cm) and 9.3 g of wet bio-sorbent
(approximately equal to 0.4 g of air drying weight of biosorbent). The
Cu(Ⅱ) solution at a desired concentration (50, 100 and 200 mg/L) was
passed through the packed bed of sorbent from the bottom to top at a
specific flow rate (1 mL/min, 2 mL/min and 3 mL/min) by a peristaltic
pump. A serial of effluent samples was collected at predetermined time
intervals and then analyzed as described above. The experiments were
continued until exhaust concentration of Cu(Ⅱ) ions achieved. The total
adsorption amounts of Cu(Ⅱ) (qtotal (mg)), volume of solution to reach
the exhaustion point at Ct/C0 = 0.9 (VE (L)) and the maximum ad-
sorption capacity (qe (mg/g)) in the column studies were calculated
with the equations:
VE
qtotal = ∫ (C0−Ct ) dV
0 (4)
VE = vte (5)
qtotal
qe =
m (6)
Fig. 1. (a) The effect of pH on the Cu(Ⅱ) adsorption onto SA, PVA/SA, PVA/SA@PAM-1.0 hydrogel beads (biosorbent dosage, 0.05 g; volume of solution, 50 mL;
initial concentration of Cu(Ⅱ), 50 mg/L; contact time, 24 h and room temperature, approximately 25 °C), (b) the pHZPC of abovementioned biosorbent.
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Chemical Engineering Journal 351 (2018) 462–472
where C0, Ct and represents the initial Cu(Ⅱ) ions concentration of the
influent (mg/L) and t time Cu(Ⅱ) ions concentration of the effluent,
respectively, v is the flow rate (mL/min), te is the horizontal time of
exhaustion point (min) and m is the dry weight of the sorbent (g).
2.5. Adsorption-desorption experiments
For the repeated adsorption-desorption cycles, 0.05 g PVA/SA@
PAM-1.0 was added to 50 mL of 50 mg/L Cu(Ⅱ) solution under the same
procedure as adsorption experiments. The PVA/SA@PAM-1.0- Cu(Ⅱ)
was regenerated in 50 mL of 0.2 mol/L HCl solution for 2 h, and then
reused after repeated washing by deionized water until the pH was
neutral for succeeding cycles.
2.6. Characterization analysis
Attenuated Total Reflection (ATR) of FTIR spectroscopy of the as-
prepared products (i.e., SA, PV/SA and PVA/SA@PAM-1.0 beads) and
after adsorption product (PVA/SA@PAM-1.0-Cu) were recorded using a
Nicolet 5700 FTIR spectrometer instrument. SEM-EDS were obtained
utilizing a PEI Quanta 200 scanning electron microscopy scanning
electron microscope, which equipped with an energy dispersive spec-
troscope. FESEM-EDS was imaged by a Zeiss Merlin Compact field
emission scanning electron microscope, which also equipped with an
energy dispersive spectroscope [16]. XPS measurements of the ad-
sorbent before and after modification as well as adsorption were ob-
served with a Thermo Fisher ESCALAB 250Xi spectrometer. While the
other conventional items such as pHPZC and swelling ratio were listed in
Supplementary Material.
3. Results and discussion
3.1. Adsorption studies by batch and column experiments
3.1.1. Effect of pH
The pH value of aqueous solution is a crucial parameter that can
simultaneously affect the adsorbate species and physicochemical
properties of adsorbent [17]. Due to the formation of precipitation of
copper hydroxide at pH higher than 6.0 (i.e., copper mainly present as
free ionic forms at pH below 6.0), and thus the effect of pH on Cu(Ⅱ)
adsorption on SA, PVA/SA, PVA/SA@PAM-1.0 beads, was examined at
room temperature in the pH range from 2.0 to 6.0, respectively [18]. As
is shown in Fig. 1(a), the removal rate of Cu(Ⅱ) by three kinds of ad-
sorbent at different initial pH values of the solution shows significant
similarity but somewhat different variation tendency. The removal ef-
ficiency of Cu(Ⅱ) increased with growing pH, from its minimum value
at pH 2.0 until it reached the maximum value at pH approximately 4.0,
W. Zhang et al.
5.0 and 6.0 for SA, PVA/SA, PVA/SA@PAM-1.0 beads, respectively.
Besides, PVA/SA@PAM-1.0 presented the highest removal efficiency in
the pH range studied.
The phenomena was attributed to different amounts, kinds and
availability of active sites (e.g., carbonyl groups, hydroxyl groups and
amino groups) on the adsorbents surface [19]. At very low pH values,
poor Cu(Ⅱ) removal can be ascribed to the competitive effects between
H+ and Cu(Ⅱ) ions for the active sites in the sorbent surface [20]. When
the pH was increased, the aforementioned competition reduced, leaving
more unoccupied sites for free Cu(Ⅱ) ions. The poor Cu(Ⅱ) removal at
pH 6 observed in present study was expected to formation of Cu(Ⅱ)
hydroxide, while functional groups such as carboxyl and amino groups
could not bind with this state of Cu(Ⅱ) [21].
Besides, different adsorbent surface charge caused by adsorbent
property can be also partially explained for these maximum removal
rate observed at specific pH values [18]. As is shown in Fig. 1(b), the
pHPZC of both SA and PVA/SA lied in 6–7, while that of PVA/SA@PAM-
10 was closely above 6. Thus, the adsorbent exhibited negative charge
and further favored the positive charged Cu(Ⅱ) ions in almost all of
situations of present experiments. Usually, the adsorption of cationic
molecules is inclined to enhance with increasing pH, deriving from the
reduction of repulsion between adsorbate and adsorbent surface [22].
Considering that the optimal pH value of 5 was chosen for PVA/SA@
PAM-1.0 in subsequent experiments.
3.1.2. Adsorption isotherms and kinetics
Adsorption isotherms can describe the interaction mechanism be-
tween adsorbent and adsorbate and be applied in assessing the
Fig. 2. (a) Sorption isotherms of Cu(Ⅱ) by as-prepared adsorbents from aqueous solution, (b) sorption kinetics of Cu(Ⅱ) by PVA/SA@PAM-1.0 beads from aqueous
solution, (c) The effect of temperature on the adsorption of Cu(Ⅱ) onto PVA/SA@PAM-1.0 beads (adsorbent dosage, 0.05 g; volume of solution, 50 mL; pH, 5.0; initial
concentration of Cu(Ⅱ), 50 mg/L and contact time, 12 h; and (d) the Van’t Hoff’s plot for the adsorption of Cu(Ⅱ) on PVA/SA@PAM-1.0 beads in the range of
293–313 K.
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Chemical Engineering Journal 351 (2018) 462–472
adsorption capacity of sorbent. Fig. 2(a) shows the adsorption iso-
therms of Cu(Ⅱ) adsorption on plain SA, PVA/SA, PVA/SA@PAM-0.5,
PVA/SA@PAM-1.0, PVA/SA@PAM-1.5 and PVA/SA@PAM-2.0 hy-
drogel beads at room temperature, respectively. It was clearly found
that the adsorption capacities in these cases increased sharply at the
lower initial Cu(Ⅱ) concentrations range, and then continued to in-
crease slowly in the extended range. To participate in bonding with the
adsorbate, the number of active sites available on the adsorbent sur-
faces can be responsible for these cases [23]. The results also displayed
that the total amount of adsorbed Cu(Ⅱ) increased with increasing in-
itial Cu(Ⅱ) concentration, and the adsorption capacities for PVA/SA@
PAM-1.0 hydrogel beads were higher than that of plain SA, PVA/SA,
PVA/SA@PAM-0.5, PVA/SA@PAM-1.5 and PVA/SA@PAM-2.0 hy-
drogel beads. As a functional modifier, more PAM resulted in more
carbonyl groups and amino groups crossing-linked onto the PVA/SA
beads surface. Thus, higher adsorption amounts of Cu(Ⅱ) can be ob-
tained. However, further addition of PAM, led to a slight decrease in
adsorption capacities. This might be due to that the too high crossing-
linked density decreases the opportunities of adsorbate to capture the
bonding sites, which was similar to previously reported work [1]. Thus,
PVA/SA@PAM-1.0 was chosen for subsequent adsorption experiments.
The non-linear isotherm constants and correlation coefficients for
Cu(Ⅱ) onto aforementioned adsorbents obtained from Langmuir and
Freundlich isotherms are listed in Table S1. Taken together, the cal-
culated values of correlation coefficient suggested that both the Lang-
muir model and the Freundlich model are well fitted the data for Cu(Ⅱ)
onto PVA/SA@PAM-1.0 hydrogel beads (R2 = 0.977 for Freundlich
model vs R2 = 0.950 for Langmuir model). Additionally, it was also
W. Zhang et al.
Fig. 3. Actual and predicted breakthrough curves for Cu(Ⅱ) onto PVA/SA@PAM-1.0: (a) different initial Cu(Ⅱ) concentration and (b) different flow rate.
clearly that both obtained values of the constant RL and n lie between 0
and 1, which suggested that these two models were highly favorable for
adsorption process [24,25]. Furthermore, the Langmuir isotherm cal-
culated maximum adsorption capacities of PVA/SA@PAM-1.0 for Cu
(Ⅱ) is 70.45 mg/g, while the experimental values of that was
79.5 ± 1.6 mg/g, which is approximately 2.3 and 2 times higher than
that of plain SA (34.9 ± 2.7 mg/g) and PVA/SA (42.2 ± 2.3 mg/g),
respectively. These results demonstrated that the Cu(Ⅱ) uptake capacity
was apparently enhanced after introduction of modifier PAM onto PVA/
SA blending beads.
Kinetic process is also crucial to assess the practical application of
potential adsorptive materials. Fig. 2(b) shows the adsorption kinetics
of Cu(Ⅱ) adsorption on PVA/SA@PAM-1.0 hydrogel beads at different
initial concentration (50, 100 and 200 mg/L). The rate of Cu(Ⅱ) ad-
sorption was relative fast and achieved approximately 51.0–56.9% of
the ultimate adsorbed amounts within the first 120 min; subsequently, a
progressive rate was obtained with approximately 82.2–88.4% of the
ultimate adsorption in the range from 120 to 360 min; and then slowly
and steadily approach to equilibrium. The initial quick rate of Cu(Ⅱ)
adsorption can be attributed to adequate unoccupied adsorptive sites as
well as driving force of great concentration gradients. With free active
sites become gradually occupied, enhanced repulsive force on solid-li-
quid interface, resulting in a relative low of Cu(Ⅱ) adsorption rate and
then reached to equilibrium [1]. Thus, 720 min was chosen for sub-
sequent experiments.
The non-linear kinetics constants and correlation coefficients for Cu
(Ⅱ) obtained from pseudo-first-order and pseudo-second-order models
are summarized in Table S2. It was clearly shown that the results fit the
pseudo-second-order model (R2 = 0.983, 0.979 and 0.945) better than
pseudo-first-order model (R2 = 0.969, 0.957 and 0.892). Therefore, it
can be revealed that the adsorption process is mainly controlled by
chemisorption [26].
3.1.3. Thermodynamic analysis
The thermodynamics studies are conducive to knowing whether
adsorption behavior is endothermic or exothermic process and thus
expanding the practical application of adsorbent. Thermodynamic stu-
dies were performed at five temperatures of 20, 25, 30, 35 and 40 °C
and the results are displayed in Fig. 2(c). With the rise of temperature,
the removal efficiency of PVA/SA@PAM-1.0 hydrogel beads and ad-
sorption capacity increased: the removal efficiency increased from
77.5 ± 0.8% at 20 °C to 90.1 ± 1.1% at 40 °C, with the corresponding
adsorption capacity were from 38.7 ± 0.4 mg/g to 45.1 ± 0.5 mg/g.
Obviously, the adsorption processes consume energy in these cases, i.e.,
it is endothermic in nature. Fig. 2(d) shows the Van’t Hoff’s plot for
these cases, and the calculated values of thermodynamic parameters are
summarized in Table S3. Negative increased in ΔG0 indicates
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Chemical Engineering Journal 351 (2018) 462–472
spontaneous nature of the sorption process and enhanced adsorption
capacity at a higher temperature [24]. Furthermore, the obtained po-
sitive value of ΔH0 (36.9240) confirms endothermic adsorption beha-
vior. The positive values of ΔS0 (0.1355) indicates the affinity of the
sorbents for the adsorbate and reflects that the sorption process makes
the solid-liquid interface disorder as well [26].
3.1.4. Adsorption experiments in a fixed bed column
To further prove adsorbent materials with high adsorption capacity,
continuous column adsorption experiments were carried out at dif-
ferent initial Cu(Ⅱ) concentrations (50, 100 and 200 mg/L). Fig. 3(a)
and Table S4 shows the breakthrough curves and column adsorption
capacity for Cu(Ⅱ) onto PVA/SA@PAM-1.0, respectively. From
Fig. 3(a), we can observe that the column exhaustion time was shor-
tened with the increasing initial Cu(Ⅱ) concentration. At lower influent
Cu(Ⅱ) concentration, poor driving force caused by lower concentration
gradient, resulting in slow mass transfer between adsorbate and ad-
sorbent. While, at higher influent Cu(Ⅱ) concentration, a combination
of limited adsorptive binding sites for Cu(Ⅱ) ions and a fast diffusion at
the solid-liquid interface caused earlier breakthrough time. These re-
sults reveal that the concentration gradient influences the saturation
rate and exhaustion time, which further demonstrates that the diffusion
process is concentration dependent [27]. While, comparing the ad-
sorption capacity between batch and column experiments, we can ob-
serve that the lees-stirred between adsorbent and adsorbate in column
system reduced the Cu(Ⅱ) adsorption capacity on PVA/SA@PAM-1.0.
Besides, continuous fixed bed column tests at different influent flow
rate (1.0, 2.0 and 3.0 mL/min) were also carried out to simulate its actual
application. From the breakthrough curves in Fig. 3(b) and related para-
meters in Table S4, we found that the fixed-bed column exhaustion time
shortened with increasing influent flow rate from 1.0 to 3.0 mL/min. This
may be ascribed to that lower residence time of solute caused insufficient
mass transfer at higher influent flow rates, thereby leading to earlier
breakthrough [28]. It indicates that lower influent flow rates would be
beneficial to Cu(Ⅱ) adsorption in actual application.
The Thomas model and the Bohart-Adams model are employed for
predicting the dynamic properties of the column system. The calculated
curves and parameters at various Cu(Ⅱ) concentration and flow rates is
shown in Fig. 3 and summarized in Table S5, respectively. As showed in
Table S5, it was clear that the results fit Thomas model (R2 were ran-
ging from 0.9291 to 0.9766) better than Bohart-Adams model (R2 were
ranging from 0.7708 to 0.8696). Thus, it can be revealed that the ex-
ternal and internal diffusion were not the rate limiting steps in ad-
sorption process [1]. For example, the results showed that the value of
KT increased with increasing the influent flow rate while the value of q0
declined. It can be explained that the adsorption process was governed
by intraparticle mass transfer.
W. Zhang et al. Chemical Engineering Journal 351 (2018) 462–472

Fig. 4. (a) The effect of coexisting ions on the adsorption of Cu(Ⅱ) onto PVA/SA@PAM-1.0 beads (adsorbent dosage, 0.05 g; volume of solution, 50 mL; pH, 5.0;
initial concentration of Cu(Ⅱ), 50 mg/L; contact time, 12 h and temperature, approximately 25 °C), (b) the influence of aquatic environments on the adsorption of Cu
(Ⅱ) onto PVA/SA@PAM-1.0 beads (volume of solution, 50 mL; pH, 5.0; initial concentration of Cu(Ⅱ), 10 mg/L; contact time, 12 h and temperature, approximately
25 °C) and (c) the reusability of PVA/SA@PAM-.0 for the adsorption of Cu(Ⅱ) (adsorbent dosage, 0.05 g; volume of solution, 50 mL; pH, 5.0; initial concentration of
Cu(Ⅱ), 50 mg/L and contact time, 12 h; temperature, approximately 25 °C).

3.2. Interference of co-existing ions studies
Since aqueous system often contains various co-existing ions which
may affect the adsorption process. Therefore, studying the effect of
background electrolyte on adsorption was carried out with different
ionic strength from 0 to 0.2 M. In addition, in order to compare and
survey the application in real water samples, four kinds of modeling of
Cu(Ⅱ) solutions were performed, including tap water, deionized water,
lake water and river water. All experiments were performed at pH of 5.
Lake water and river water was collected from the Donghu lake and the
Yangtze River located in Wuhan City, China, respectively. Fig. 4(a)
shows the removal efficiency was influenced by the different contents
of co-existing ions. It was obvious that removal performance was
slightly undermined. The removal rates of Cu(Ⅱ) decreased from
81.1 ± 1.6% to 59.0 ± 1.9% with ionic strength changed from 0 to
0.2 M. The reasons for this phenomenon might be explained as follows.
The interference of inorganic salts, especially with high content would
compete with Cu(Ⅱ) ions for finite adsorptive sites onto adsorbent [29].
While, the electrolyte (i.e., sodium ions) with lower electric state as
well as relative lower ionic radius can be responsible for the weak de-
creases of removal ability [30].
Fig. 4(b) shows the PVA/SA@PAM-1.0 performance by applying in
ideal and actual water. There still were gaps of Cu(Ⅱ) removal rate
among different modeling of water samples but not by much. It was
found that the removal efficiency of Cu(Ⅱ) ions were very good in all
tests, which indicated the capability and potential of PVA/SA@PAM for
effective removal of Cu(Ⅱ) in actual applications. The negative effect on
removal performance was in the following order: lake water > river
water > tap water > deionized water. At dose of 1.2 g/L, the Cu(Ⅱ)
removal was 79.0 ± 1.3%, 83.1 ± 0.8% and 86.2 ± 0.8% corre-
sponding to lake water, river water and tap water respectively, relative
to that observed in the absence of the competing ions (i.e., with
96.0 ± 0.8% Cu(Ⅱ) removal in the deionized water). These differences
could be ascribed to the interference of coexisting ions. Overall, these
indicates that PVA/SA@PAM-1.0 could be applied in some certain
aqueous environments for Cu(Ⅱ) removal.
3.3. Adsorption-desorption studies
The regeneration and reusability of adsorbent is essential for the
further assessing the practical application potential. The diluted acid
solution as eluent can facilitate to release the metal ions from the
protonated chelating site of the sorbent surface [31], which was proven
indirectly through the inhibition of lower pH values on Cu(Ⅱ) adsorp-
tion. Fig. 4(c) shows the recycling performance of PVA/SA@PAM-1.0
for the adsorption of Cu(Ⅱ). It was found that PVA/SA@PAM-1.0
showed good properties for the removal of Cu(Ⅱ) ions during entire
adsorption-desorption experiments. Specifically, the removal rate of Cu
(Ⅱ) was only decreased slightly by approximately 9.1% in the first eight
cycle, and then fall further to 67.4 ± 0.8% after the eleventh cycle.
Additionally, the morphology of PVA/SA@PAM-1.0 were nearly un-
changed before and after consecutive reusability tests (data not shown).

467
W. Zhang et al.
Fig. 5. The FT-IR spectra of SA, PVA/SA and PVA/SA@PAM-1.0 before and
after Cu(Ⅱ) adsorption.
3.4. Analysis of the as-prepared composite
3.4.1. FT-IR analysis
The FT-IR spectroscopy of the bio-sorbents before sorption and after
sorption were obtained in the wavenumber range of 4000–650 cm−1.
Fig. 5 displays the spectra of SA, PVA/SA, PVA/SA@PAM-1.0, and
PVA/SA@PAM-1.0-Cu, respectively. For the spectra of SA and PVA/SA,
the characteristic absorbance peaks at around 1620, 1430, 1080 and
1050 cm−1 correspond to the absorption band of C=O and CeO of
carboxyl group, bridge CeO–C stretching and stretching vibration of
CeO of alcoholic hydroxyl group, respectively [1,26,32]. Besides, dif-
ferent intensity of the stretching vibrations of CeH in –CH or –CH2 in
the range of 2800–3000 cm−1 and stretching vibrations of –OH groups
in the range of 3100–3700 cm−1 were observed in all three as-prepared
Fig. 6. SED-EDS mapping micrographs of (a and e) SA, (b and f) PVA/SA, (c, g, i and k) PVA/SA@PAM-1.0 and (d, h, j and m) PVA/SA@PAM-1.0-Cu.
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Chemical Engineering Journal 351 (2018) 462–472
materials [33]. Owing to the PVA contains large amounts of –OH
groups and has its own backbone structure with –CH and –CH2. After
blending PVA with SA, the intensity of –OH stretching vibration and
CeH stretching signals became stronger than that of plain SA. While,
after PAM being crosslinked with PVA/SA surfaces, a noticeable feature
of PVA/SA@PAM-1.0 is that the spectra showed a minor shift and
overlap. For example, the CeO stretching of carboxyl group shifted to
lower frequency, resulting from the modification of PAM. The char-
acteristic peaks of –COO– stretching around 1430 cm−1 and CeN
stretching around 1400 cm−1 seem to merged into a new band at
1415 cm−1 [8]. Besides, owing to the overlap of –OH groups that the
stretching and bending vibrations of NeH of in the range of
3100–3700 cm−1 became inapparent [5,34]. Another noticeable fea-
ture of PVA/SA@PAM-1.0 is that the spectra display two inherent
characteristic peaks at 1594 and 1026 cm−1 corresponding to NeH
bonding and CeN stretching, which is similar to previous literature
[35,36]. Previously reported work pointed that the Cu(Ⅱ) adsorption
onto alginate-based materials can cause shift of functional groups in the
frequencies, resulting from associations between high electron density
of Cu(Ⅱ) ions and these groups [37]. In the spectra of PVA/SA@PAM-
1.0-Cu, the absorption band of CeO of carboxyl group, the NeH
bonding of amino group and –OH groups shifted to the lower frequency
(from 1415 to 1407 cm−1, 1594 to 1589 cm−1 and 3284 to 3245 cm−1,
respectively). These obvious changes in the peaks after Cu(Ⅱ) adsorp-
tion suggested that the ion exchange, between Cu(Ⅱ) ions and calcium
ions, is not the main adsorption mechanism but multiple reaction in-
volved in adsorption processes, supporting from the introduction of
PAM. Hence, the FT-IR results indicate that PAM was successfully
crossing-linked with PVA/SA, and thus formed into core-shell/bead-like
PVA/SA@PAM, and further reveal adsorption properties of Cu(Ⅱ) onto
PVA/SA@PAM beads.
3.4.2. SEM-EDS analysis
Fig. 6(a–h) shows the SEM images of SA, PVA/SA and PVA/SA@
PAM-1.0 before and after adsorption. As can be seen from the SEM
images, all samples were found to be shrank because of dehydration.
For example, the final dried PVA/SA@PAM-1.0 beads had spherical
W. Zhang et al.
shape with an average size of approximately 1.5 mm, and that of wet
state was approximately 4.1 mm (Fig. 6i). Interestingly, blending PVA
with SA did influenced the morphology of PVA/SA beads. It shows
smooth surface comparing to plain SA bead surface (Fig. 6a and b).
Beside, PVA/SA beads surface was found to be loaded with irregular
aggregates (Fig. 6e and f), which may be attributed to the crystal-
lization of PVA [38]. Expectedly, the PVA/SA@PAM-1.0 beads exhibit
rugged surface with much irregular wrinkles after introducing PAM
onto PVA/SA beads, cracks and openings (Fig. 6c and j), which may
provide more accessible and adsorptive points directly for Cu(Ⅱ) ions.
After Cu(Ⅱ) adsorption, some irregular agglomerates and uneven
cluster could be observed in the PVA/SA@PAM-1.0-Cu surface (Fig. 6d
and h). EDS spectra showed that C, O, Na, Ca are the mainly elements in
PVA/SA@PAM, and that C, O, Ca and Cu exist in PVA/SA@PAM-Cu
(the presence of Au can be ascribed to spraying pretreatment) (Fig. 6k
and m). After Cu(Ⅱ) adsorption, the contents decreased of C, O and Ca
were obtained, which could be assigned to the ion exchange and
complexation involved in adsorption process. Additionally, EDS map-
ping results revealed that the distribution of most of N element was
nearer to the surface than the inner of PVA/SA@PAM-Cu (Fig. S1).
Considering that N source from PAM, it clearly indicates directly or
indirectly that PAM was successfully crossing-linked with PVA/SA
beads surface to form a core-shell/bead-like structure.
3.4.3. XPS analysis
Fig. 7 shows the XPS spectra of PVA/SA@PAM-1.0 before and after
modification as well as adsorption. For the spectra of PVA/SA and PVA/
SA@PAM-1.0, it is easy to see major C1s signal at around 284.8 eV,
Ca2p peaks at around 347 eV and O1s peaks at around 532 eV (Fig. 7a
Fig. 7. The XPS spectra of PVA/SA@PAM-1.0 before and after modification as well as adsorption.
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Chemical Engineering Journal 351 (2018) 462–472
and 7b). Most importantly, the observed N1s signal at 399.65 eV de-
monstrated that PAM was successfully crossing-linked onto PVA/SA
surface (Fig. 7(b)). After Cu(Ⅱ) adsorption, the peak of Cu2p appeared
(Fig. 7(c)), suggesting that the heavy metal was adsorbed on PVA/SA@
PAM-1.0. It was also found that the binding energy of N1s was shifted
to higher binding energy (approximately 0.3 eV), confirming that the
interaction between N-containing functional groups and Cu(Ⅱ) ions.
This was due to that the N atoms donate lone pair electrons to co-
ordinate covalent bonds with Cu(Ⅱ) ions, and thus leading to the de-
creasing the charge density of N, which further resulting in increasing
of its photoelectron binding energy [39]. The high resolution N1s
spectrum is shown in Fig. 7(d). The peak of N1s can be further de-
convoluted into three peaks at binding energies of 398.9 eV, 400 eV and
400.3 eV., which originates from quinoid imine (–N=), benzenoid
amine (–NH–) and amine group (–NH2), respectively [1,40]. Ad-
ditionally, the ion exchange between Cu(Ⅱ) ions and calcium ions could
be responsible for very little shifting of the O1s peak and the dis-
appearing of Ca2p peak after adsorption.
3.4.4. Swelling and water stability studies
The swelling capacity of the material is also a crucial factor in ad-
sorption process for functional adsorbents. Fig. 8 shows the effect of pH
on the swelling behavior for SA, PVA/SA and PVA/SA@PAM-1.0 hy-
drogel beads. Obviously, the swelling ratio of PVA/SA@PAM-1.0 hy-
drogel beads was far higher than that of the other two. It was also found
that all hydrogel beads displayed a lower swelling ratio at low pH,
while their swelling ratio increased generally with increasing pH
(especially for PVA/SA@PAM-1.0 hydrogel beads). The high swelling
capacity of PVA/SA@PAM-1.0 hydrogel beads can be ascribed to the
W. Zhang et al.
Fig. 8. The effect of pH on the swelling behavior for SA, PVA/SA and PVA/SA@
PAM-1.0 hydrogel beads.
introduction of hydrophilic acyl-amino from PAM and their three-di-
mensional network structure. The pH-dependent swelling capacity of
these adsorbents can be explained by the dissociation constant (pKa),
resulting from different species and amounts of functional groups on
adsorbent surface [7]. Additionally, it is worth noting that all cases of
beads presented stability and shape keeping characteristics with
varying pH values, except for SA with slight disintegration under al-
kaline conditions later (Fig. S2). While, the water stability of beads is
also an important parameter for adsorbents application. It was also
obtained that the beads were stable (without disintegration) after stir-
ring constantly in 1 M NaCl solution (Fig. S3). And only approximately
20% decreasing of the weight of samples was found after 28 days. The
physiochemical crosslinked PAM part can be mainly responsible for a
better stability of the PVA/SA@PAM-1.0 hydrogel beads. These show
that PAM allows the formation of hydrogel beads with characteristic of
steady increase in swelling ratio under different background electrolyte.
Combined with the above-mentioned results, the as-prepared PVA/SA@
PAM-1.0 hydrogel beads are expected to possess mechanical stability
(i.e., better shape-keeping and water resistance abilities) to provide
sustained adsorption ability.
3.5. Adsorption mechanism discussion
Based on the results of FT-IR analysis, SED-EDS analysis, XPS ana-
lysis and competitive ions studies, multiple adsorption mechanism such
as cation-ion exchange and complexation might be involved in ad-
sorption processes. Usually, ion exchange mainly controls the adsorp-
tion process of divalent metal ions onto alginate beads. Owing to the
modification on PVA/SA surface, the adsorption capacity of Cu(Ⅱ) be-
came much higher that the raw materials, and thus we mainly discuss
the factor in the enhancement of removal ability.
Considering that the species of copper mainly as free ionic forms at
pH below 6.0, in this present work, the Cu(Ⅱ) adsorption mainly de-
pends on these active sites on bio-sorbent. All of these sorption sites
(i.e., –OH, –COOH and –NH2) have vacant electrons, which would have
tendency to share with Cu(Ⅱ) ions to form a Cu(Ⅱ) complexes. Besides,
the binding sites on the adsorbent surface can also be greatly affected
by solution pH. Based on the above results, a proposed scheme of the
enhanced adsorption mechanism is depicted in Scheme 2. According to
the theory of HSAB, the Cu(Ⅱ) ions preferentially to form complexes
with functional groups, following this order: O- < N- < S- containing
groups [41]. After the introduction of PAM chains onto PVA/SA hy-
drogel beads, the adsorbate could be reacted with available binding
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Chemical Engineering Journal 351 (2018) 462–472
Scheme 2. Schematic diagram of possible mechanism for enhancement of Cu
(Ⅱ) removal onto PVA/SA@PAM beads.
groups via mainly complexation between amino groups and the Cu(Ⅱ)
ions, which is the key to enhance the adsorption capacity of adsorbent.
Cu(Ⅱ) ions initially attracted at outside layer and then gradually enter
the inner layer to make full use of PAM. Specifically, at lower pH, there
is a competition effect between H+ and Cu(Ⅱ) ions (as depicted in 3.1.1.
section), leading to the protonation of bio-sorbents and thus leaving Cu
(Ⅱ) ions free in aqueous solution; when the pH increases, resulting in
the deprotonation of bio-sorbents and further attract of the cationic Cu
(Ⅱ) ions onto the binding sites on the hydrogel beads surface; after these
stages, the Cu(Ⅱ) ions and amino groups would form more stable metal
complexes on the bio-sorbent surface [5,19,42]. However, the –COOH
and –OH, not shown in this scheme, can also participate the adsorption
processes.
3.6. Assessment of potential of PVA/SA@PAM
In present study, a core–shell/bead-like structure of PVA/SA@PAM
was prepared by crosslinking with PAM onto PVA/SA blending beads,
which complemented both benefits of natural and synthetic polymers,
and further demonstrated to be effective in Cu(Ⅱ) removal. Herein, it
provides a new sight into the enhanced Cu(Ⅱ) adsorption of PVA/SA@
PAM beads through a facile route.
Concerning the preparation of PVA/SA@PAM, the present work
originally came from concerning the limitation of SA, as an sorbent,
which is restricted by disintegration and weak mechanical strength as
well as relative low adsorption capacity [2,43]. From this view,
blending PVA with SA to form hydrogel beads could be beneficial to its
easy separation and regeneration after adsorption and enhancing its
relative poor mechanical stability. Besides, the blending of PVA with SA
increases the amounts of negatively charged hydroxyl groups, further
demonstrating by pHZPC tests and swelling studies. However, the Cu(Ⅱ)
adsorption capacity of PVA/SA beads still not reach a relative high
value. Thus, simply cross-linking PAM onto PVA/SA beads matrix to
form the core-shell-like structure could remedy this defect by introdu-
cing large quantities of amino groups. It should be said the preparation
route is simple production process.
Though the maximum Cu(Ⅱ) adsorption capacity of PVA/SA@PAM-
1.0 is not as higher than that of some other similar alginate-based
material such as glutaraldehyde cross-linked humic acid immobilized
sodium alginate porous membrane (116.4 mg/g) [44] and carbon na-
notube/calcium alginate (84.8 mg/g) [45]. But, we should note, here
the modifier PAM is easy available and cheap and the functionalized
beads also display better maximum Cu(Ⅱ) adsorption capacity than
some similar biosorbent, as shown in Table S6. It is obvious that PVA/
SA@PAM composites have enhanced adsorption performance towards
Cu(Ⅱ) ions and partially be confirmed a promising candidate biosorbent
for Cu(Ⅱ) ions removal. Additionally, the cost of raw materials such as
SA, PVA and other reagents are very low, especially using in industrial
grade.
Another advantage of this new material is the high adaptability in
W. Zhang et al.
the presence of interference of coexisting ions. Little gap was found in
the terms of Cu(Ⅱ) removal efficiency among various ions strength and
three other kinds of modeling of Cu(Ⅱ) solutions (tap water, lake water
and river water), relative to that obtained in the absence of competing
ions. All experiments here achieved better removal efficiency under an
optimal sorbent dose, which indicates that the as-prepared PVA/SA@
PAM have excellent adaptability and can be potential in applications in
some certain practical wastewater treatment. More importantly, the Cu
(Ⅱ) removal rate only decreased slightly by approximately 16.5% even
after the eleventh cycle.
Obviously, togethering with these findings, which suggested this
hydrogel beads have attractive characteristics such as simple produc-
tion process, low cost, good adsorption capacity, high chemical and
mechanical stability. Therefore, it illustrates the as-synthesized PVA/
SA@PAM can be a high potential material in some certain practical
wastewater treatment.
4. Conclusions
A facile route based on PVA/SA blending beads was prepared using
PAM as modifier, which was employed for Cu(Ⅱ) removal and exhibited
good adsorption capacity under batch and column experiments. The
results revealed that complexation and cation-ion exchange are the
dominant adsorption mechanism, while the former is contributed by
–NH2 towards enhanced adsorption and the latter is the result of –OH,
–COOH participating in adsorption processes. PVA/SA@PAM-1.0
showed the maximum adsorption capacity of Cu(Ⅱ) (79.5 ± 1.6 mg/g)
under the optimal conditions, which is approximately 2.3 and 2 times
higher than that of plain SA and PVA/SA, respectively. Expectedly,
swelling and water resistance, co-exiting ions and adsorption-deso-
rption studies further demonstrated that the PVA/SA@PAM-1.0 with
excellent adaptability and high chemical and mechanical stability.
Therefore, considering the simple production process, low cost raw
materials, good adsorption capacity, excellent adaptability and high
chemical and mechanical stability, the as-synthesized PVA/SA@PAM
can be feasible for some certain practical wastewater treatment.
Acknowledgments
This work was financially supported by the Fundamental Research
Funds for the Central Universities (Wuhan University, NO.
2042017kf0249).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cej.2018.06.129.
References
[1] Y.Z. Yan, Q.D. An, Z.Y. Xiao, W. Zheng, S.G. Zhai, Flexible core-shell/bead-like
alginate@PEI with exceptional adsorption capacity, recycling performance toward
batch and column sorption of Cr(VI), Chem. Eng. J. 313 (2017) 475–486.
[2] W.S.W. Ngah, S. Fatinathan, Adsorption of Cu(II) ions in aqueous solution using
chitosan beads, chitosan-GLA beads and chitosan-alginate beads, Chem. Eng. J. 143
(2008) 62–72.
[3] J. Bajpai, R. Shrivastava, A.K. Bajpai, Dynamic and equilibrium studies on ad-
sorption of Cr(VI) ions onto binary bio-polymeric beads of cross linked alginate and
gelatin, Colloid Surface. A 236 (2004) 81–90.
[4] H.X. Ren, Z.M. Gao, D.J. Wu, J.H. Jiang, Y.M. Sun, C.W. Luo, Efficient Pb(II) re-
moval using sodium alginate-carboxymethyl cellulose gel beads: Preparation,
characterization, and adsorption mechanism, Carbohyd. Polym. 137 (2016)
402–409.
[5] L. Jin, R.B. Bai, Mechanisms of lead adsorption on chitosan/PVA hydrogel beads,
Langmuir 18 (2002) 9765–9770.
[6] X. Jiang, N. Xiang, H. Zhang, Y. Sun, Z. Lin, L. Hou, Preparation and character-
ization of poly(vinyl alcohol)/sodium alginate hydrogel with high toughness and
electric conductivity, Carbohyd. Polym. 186 (2018) 377–383.
[7] G.R. Mahdavinia, S. Mousanezhad, H. Hosseinzadeh, F. Darvishi, M. Sabzi,
Magnetic hydrogel beads based on PVA/sodium alginate/laponite RD and studying
471
Chemical Engineering Journal 351 (2018) 462–472
their BSA adsorption, Carbohyd. Polym. 147 (2016) 379–391.
[8] G.C. Zhu, J.F. Liu, J. Yin, Z.W. Li, B.Z. Ren, Y.J. Sun, P. Wan, Y.S. Liu,
Functionalized polyacrylamide by xanthate for Cr (VI) removal from aqueous so-
lution, Chem. Eng. J. 288 (2016) 390–398.
[9] M. Hadavifar, N. Bahramifar, H. Younesi, Q. Li, Adsorption of mercury ions from
synthetic and real wastewater aqueous solution by functionalized multi-walled
carbon nanotube with both amino and thiolated groups, Chem. Eng. J. 237 (2014)
217–228.
[10] N. Wu, X. Li, G. Huang, P. Pan, C. Wang, X. Liu, M. Zeng, Adsorption and biode-
gradation functions of novel microbial embedding polyvinyl alcohol gel beads
modified with cyclodextrin: a case study of benzene, Environ. Technol. 1–11
(2018).
[11] Q.P. Song, C.X. Wang, Z. Zhang, J.G. Gao, Adsorption of lead using a novel
xanthated carboxymethyl chitosan, Water Sci. Technol. 69 (2014) 298–304.
[12] S. Yang, J. Hu, C. Chen, D. Shao, X. Wang, Mutual Effects of Pb(II) and Humic Acid
Adsorption on Multiwalled Carbon Nanotubes/Polyacrylamide Composites from
Aqueous Solutions, Environ. Sci. Technol. 45 (2011) 3621–3627.
[13] N. Li, R.B. Bai, C.K. Liu, Enhanced and selective adsorption of mercury ions on
chitosan beads grafted with polyacrylamide via surface-initiated atom transfer ra-
dical polymerization, Langmuir. 21 (2005) 11780–11787.
[14] J.C. Fan, Z.X. Shi, M. Lian, H. Li, J. Yin, Mechanically strong graphene oxide/so-
dium alginate/polyacrylamide nanocomposite hydrogel with improved dye ad-
sorption capacity, J. Mater. Chem. A 1 (2013) 7433–7443.
[15] G.T. Hermanson, Bioconjugation techniques, 2nd ed., Elsevier, New York, 2008.
[16] H.F. Xiong, S.S. Dong, J. Zhang, D.D. Zhou, B.E. Rittmann, Roles of an easily bio-
degradable co-substrate in enhancing tetracycline treatment in an intimately cou-
pled photocatalytic-biological reactor, Water Res. 136 (2018) 75–83.
[17] J.H. Ma, G.Y. Zhou, L. Chu, Y.T. Liu, C.B. Liu, S.L. Luo, Y.F. Wei, Efficient Removal
of Heavy Metal Ions with An EDTA Functionalized Chitosan/Polyacrylamide
Double Network Hydrogel, ACS Sustain. Chem. Eng. 5 (2017) 843–851.
[18] E. Demirbas, N. Dizge, M.T. Sulak, M. Kobya, Adsorption kinetics and equilibrium
of copper from aqueous solutions using hazelnut shell activated carbon, Chem. Eng.
J. 148 (2009) 480–487.
[19] H. Aydin, Y. Buluta, C. Yerlikaya, Removal of copper (II) from aqueous solution by
adsorption onto low-cost adsorbents, J. Environ. Manage. 87 (2008) 37–45.
[20] X.C. Chen, G.C. Chen, L.G. Chen, Y.X. Chen, J. Lehmann, M.B. McBride, A.G. Hay,
Adsorption of copper and zinc by biochars produced from pyrolysis of hardwood
and corn straw in aqueous solution, Bioresource. Technol. 102 (2011) 8877–8884.
[21] W.S. Tan, A.S.Y. Ting, Alginate-immobilized bentonite clay: Adsorption efficacy and
reusability for Cu(II) removal from aqueous solution, Bioresource. Technol. 160
(2014) 115–118.
[22] B.C. Melo, F.A.A. Paulino, V.A. Cardoso, A.G.B. Pereira, A.R. Fajardo,
F.H.A. Rodrigues, Cellulose nanowhiskers improve the methylene blue adsorption
capacity of chitosan-g-poly(acrylic acid) hydrogel, Carbohyd. Polym. 181 (2018)
358–367.
[23] N. Li, R. Bai, Copper adsorption on chitosan–cellulose hydrogel beads: behaviors
and mechanisms, Sep. Purif. Technol. 42 (2005) 237–247.
[24] M.H. Kalavathy, T. Karthikeyan, S. Rajgopal, L.R. Miranda, Kinetic and isotherm
studies of Cu(II) adsorption onto H3PO4-activated rubber wood sawdust, J. Colloid.
Interf. Sci. 292 (2005) 354–362.
[25] E. Sharifpour, H.Z. Khafri, M. Ghaedi, A. Asfaram, R. Jannesar, Isotherms and ki-
netic study of ultrasound-assisted adsorption of malachite green and Pb2+ ions from
aqueous samples by copper sulfide nanorods loaded on activated carbon:
Experimental design optimization, Ultrason. Sonochem. 40 (2018) 373–382.
[26] Z.-H. Hu, A.M. Omer, X.k. Ouyang, D. Yu, Fabrication of carboxylated cellulose
nanocrystal/sodium alginate hydrogel beads for adsorption of Pb(II) from aqueous
solution, Int. J. Biol. Macromol. 108 (2018) 149–157.
[27] J. Goel, K. Kadirvelu, C. Rajagopal, V.K. Garg, Removal of lead(II) by adsorption
using treated granular activated carbon: Batch and column studies, J. Hazard.
Mater. 125 (2005) 211–220.
[28] S. Chatterjee, S. Mondal, S. De, Design and scaling up of fixed bed adsorption
columns for lead removal by treated laterite, J. Clean. Prod. 177 (2018) 760–774.
[29] D. Chen, H.N. Zhang, K. Yang, H.Y. Wang, Functionalization of 4-aminothiophenol
and 3-aminopropyltriethoxysilane with graphene oxide for potential dye and
copper removal, J. Hazard. Mater. 310 (2016) 179–187.
[30] Y. Wen, Z.R. Tang, Y. Chen, Y.X. Gu, Adsorption of Cr(VI) from aqueous solutions
using chitosan-coated fly ash composite as biosorbent, Chem. Eng. J. 175 (2011)
110–116.
[31] Z.J. Xu, K.J. Wang, Q. Liu, F.R. Guo, Z.D. Xiong, Y.G. Li, Q. Wang, A bifunctional
adsorbent of silica gel-immobilized Schiff base derivative for simultaneous and
selective adsorption of Cu(II) and SO42-, Sep. Purif. Technol. 191 (2018) 61–74.
[32] O.-H. Kwon, J.-O. Kim, D.-W. Cho, R. Kumar, S.H. Baek, M.B. Kurade, B.-H. Jeon,
Adsorption of As(III), As(V) and Cu(II) on zirconium oxide immobilized alginate
beads in aqueous phase, Chemosphere 160 (2016) 126–133.
[33] L. Sun, S.C. Hu, H.M. Sun, H.L. Guo, H.D. Zhu, M.X. Liu, H.H. Sun, Malachite green
adsorption onto Fe3O4@SiO2-NH2: isotherms, kinetic and process optimization, Rsc.
Adv. 5 (2015) 11837–11844.
[34] X. Jin, W.Q. Cai, Z.J. Cai, Amino organosilane grafted ordered mesoporous alumina
with enhanced adsorption performance towards Cr(VI), Rsc. Adv. 7 (2017)
53076–53086.
[35] T.S. Anirudhan, P.S. Suchithra, S. Rijith, Amine-modified polyacrylamide-bentonite
composite for the adsorption of humic acid in aqueous solutions, Colloid Surface. A
326 (2008) 147–156.
[36] T.S. Anirudhan, P.S. Suchithra, Heavy metals uptake from aqueous solutions and
industrial wastewaters by humic acid-immobilized polymer/bentonite composite:
Kinetics and equilibrium modeling, Chem. Eng. J. 156 (2010) 146–156.
W. Zhang et al.
[37] S.-F. Lim, Y.-M. Zheng, S.-W. Zou, J.P. Chen, Characterization of Copper Adsorption
onto an Alginate Encapsulated Magnetic Sorbent by a Combined FT-IR, XPS, and
Mathematical Modeling Study, Environ. Sci. Technol. 42 (2008) 2551–2556.
[38] J.K. Wu, X.L. Gong, Y.C. Fan, H.S. Xia, Physically crosslinked poly(vinyl alcohol)
hydrogels with magnetic field controlled modulus, Soft Matter 7 (2011) 6205–6212.
[39] Y. Liu, P. Qian, Y. Yu, B. Yu, Y. Wang, S. Ye, Y. Chen, Preparation and character-
ization of a novel hybrid chelating material for effective adsorption of Cu(II) and Pb
(II), J. Environ. Sci-China 67 (2018) 224–236.
[40] X. Xu, X.-Y. Jiang, F.-P. Jiao, X.-Q. Chen, J.-G. Yu, Tunable assembly of porous
three-dimensional graphene oxide-corn zein composites with strong mechanical
properties for adsorption of rare earth elements, J. Taiwan Inst. Chem. E. 85 (2018)
106–114.
[41] Y.H. Zhu, J. Hu, J.L. Wang, Competitive adsorption of Pb(II), Cu(II) and Zn(II) onto
472
Chemical Engineering Journal 351 (2018) 462–472
xanthate-modified magnetic chitosan, J. Hazard. Mater. 221 (2012) 155–161.
[42] T. Benhalima, H. Ferfera-Harrar, D. Lerari, Optimization of carboxymethyl cellulose
hydrogels beads generated by an anionic surfactant micelle templating for cationic
dye uptake: Swelling, sorption and reusability studies, Int. J. Biol. Macromol. 105
(2017) 1025–1042.
[43] J. He, F. Bardelli, A. Gehin, E. Silvester, L. Charlet, Novel chitosan goethite bio-
nanocomposite beads for arsenic remediation, Water Res. 101 (2016) 1–9.
[44] J.H. Chen, Q.L. Liu, S.R. Hu, J.C. Ni, Y.S. He, Adsorption mechanism of Cu(II) ions
from aqueous solution by glutaraldehyde crosslinked humic acid-immobilized so-
dium alginate porous membrane adsorbent, Chem. Eng. J. 173 (2011) 511–519.
[45] Y. Li, F. Liu, B. Xia, Q. Du, P. Zhang, D. Wang, Z. Wang, Y. Xia, Removal of copper
from aqueous solution by carbon nanotube/calcium alginate composites, J. Hazard.
Mater. 177 (2010) 876–880.