Separation and Purification Technology 235 (2020) 116185

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Separation and Purification Technology

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

PAN/PVDF chelating membrane for simultaneous removal of heavy metal T

and organic pollutants from mimic industrial wastewater
⁎ ⁎
Shugang Xu, Yuanfa Liu , Yue Yu , Xitong Zhang, Jun Zhang, Yanfen Li
School of Textile and Material Engineering, Dalian Polytechnic University, Dalian, China

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

Keywords: The polyacrylonitrile/polyvinylidene fluoride (PAN/PVDF) chelating membrane with amidoxime groups was
Chelating membrane prepared to simultaneously remove metallic and organic pollutants from mimic industrial wastewater. The main
Organic pollutants purpose of this study is to investigate the interaction between metal ions and protein molecules, and synergistic
Heavy metal ions effects on the pollutant removal efficiency through the chelating membrane. Lysozyme and bovine serum al-
Metal-organic complexes
bumin (BSA) were used as organic pollutants and Cu2+, Pb2+ and Cd2+ were used as metal components in this
Metal-protein interaction
study. As one of the metal ions (Cu2+, Pb2+ or Cd2+) and one of the proteins (lysozyme or BSA) are present in
the solution, the metal removal rate is improved due to the interaction of metal ions with protein, to form a
metal-protein complex. At the same time, the lysozyme rejection efficiency decreases, but the BSA rejection
efficiency increases. For the mixture consisting of one metal ion and two proteins, the metal removal rate is
higher than that for the case (one metal ion + lysozyme), but lower than that for the case (one metal ion + BSA).
Meanwhile, the protein retention efficiency decreases, since the interaction between lysozyme and BSA disturbs
the retention efficiency of each protein. As three metal ions and two proteins are present in the solution, the ion
removal efficiency is significantly improved, and the protein retention efficiency is increased as well, which is
due to the fact that there are much more chances for forming metal-protein complexes.

1. Introduction cadmium from aqueous streams by using a polymer to enhance UF

Nowadays, pollution of water environment has gained widely public
attention with the rapid development of global industrialization, due to
the fact that a great deal of industrial wastewater is discharged arbi-
trarily. The industrial wastewater usually contains a large amount of
toxic [1] and harmful substances including organic pollutants and
heavy metal ions [2–4], which poses a potential threat to human health.
It is of great significance to remove the hazardous materials from
wastewater to obtain clean or non-toxic threatened water.
It is well-known that ultrafiltration (UF) membrane [5,6] can ef-
fectively remove the macromolecular organic contaminants [7] from
aqueous solution. However, the function of traditional UF membrane is
limited because it is incapable of removing the metal ions [8–10] from
the polluted water. Therefore, polymer-assisted ultrafiltration (PAUF)
has been developed, which consists in the addition of water-soluble
metal-binding polymers prior to ultrafiltration. The metal ions in aqu-
eous solution can be retained by PAUF membrane due to the formation
of metal ion-polymer complexes. There are a lot of literature focusing
on the application of PAUF membrane to remove the polluted materials
from the aqueous solution. For instances, Llorens et al. separated the
performance, and investigated the effect of pH and polymer/metal ratio
on the removal performance of cadmium [11]. Juang et al. used chit-
osan to enhance filtration performance for the removal of divalent
metal ions including Cu2+, Co2+, Ni2+ and Zn2+ from aqueous solu-
tions [12]. Nicolas Fatin-Rouge et al. removed the divalent cations from
the wastewater by membrane with the assistance of alginate and de-
monstrated the binding affinity of alginate with divalent cations was
increased with increasing polymer concentration [13]. Sanli et al. uti-
lized the alginic acid to enhance UF performance for the removal of
Fe3+ ions from aqueous solutions and investigated the complexation
behavior of alginic acid and the effect of pH on the rejection of ion [14].
Moreno-Villoslada et al. developed the graphical analysis concerning
the metal ion enrichment of water-soluble polymers by the ultrafiltra-
tion technique, and established an equilibrium between the polymer
and Cu2+ ion [15]. Vijayalakshmi et al. prepared the cellulose acetate/
polycarbonate blend membrane to reject various proteins and toxic
heavy metal ions from aqueous solutions by complexation with poly-
ethyleneimine (PEI) [16].
Recently, the chelating membrane has been regarded as one of the
most promising methods for removing metal ions from the aqueous

⁎
Corresponding authors.
E-mail addresses: Liuyf@dlpu.edu.cn (Y. Liu), yuyue@dlpu.edu.cn (Y. Yu).

https://doi.org/10.1016/j.seppur.2019.116185
Received 7 August 2019; Received in revised form 4 October 2019; Accepted 7 October 2019
Available online 08 October 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
S. Xu, et al.
solution. The common feature of chelating membranes is containing
various functional groups that can form strong complexes with metal
ions. Many scientists have carried out the experimental research about
the utilization of chelating membrane for the removal of metal ions
from the wastewater. For instance, Anne B. et al. prepared a novel
complexing membrane by grafting titanate coupling agents bearing
ethylenediamine (EDA) groups on inorganic membranes. They found
that the retention of Cu2+ was enhanced up to 80–90% with the EDA
grafted membrane due to the occurrence of formation of a strong
complex with EDA groups [17]. Antonina K. et al. prepared the che-
lating membrane using PEI as a chelating agent in purification of the
water contaminated by Co(II) and Ni(II) ions and found that the max-
imum retention coefficient of Co(II) and Ni(II) ions by the chelating
membrane was up to 95.0% and 99.9% respectively [18]. Kyoichi et al.
prepared a porous hollow-fiber membrane containing an imino-
diethanol (IDE) group as the chelating group for the recovery of anti-
mony in the permeation mode [19]. Bing et al. prepared the mercapto-
functionalized polysulfone affinity membrane for the adsorption of
Hg2+ through the coordination of mercapto group with Hg2+, and in-
vestigated the effects of the morphology and the structure of affinity
membrane on the chelating properties [20]. Lebrun et al. prepared
chelating membranes for the removal of metal ions by blending of poly
(vinyl alcohol) (PVA) with poly(acrylic acid) (PAA) or PEI. The results
showed that the removal rate of Cu(II) and Pb(II) by the chelating
membrane was 40.8% and 70.0%, respectively [21]. They also in-
vestigated the performances of PVA/PEI blending membrane for the
removal of Hg(II) from aqueous solutions, and demonstrated the re-
moval rate of Hg(II) was close to 99% [22], and the maximum capacity
of the membrane was 120 mg/g [23]. Song et al. prepared the mela-
mine-diethylenetriaminepentaacetic acid/polyvinylidene fluoride
(PVDF) chelating membrane to remove Ni(II) from wastewater effluents
[24]. Wang et al. prepared the thioamido-based chelating nanofiber
membrane by electrospun method to efficiently adsorb Au(III) ions
from the aqueous solution [25].
The chelating membrane is commonly prepared through the che-
mical modification of UF membrane to immobilize functional groups,
which endows chelating membrane with dual filtration efficiency for
both heavy metal ions and organic pollutants. Luo et al. fabricated the
chelating membrane by introducing the amidoxime groups into the
surface of polyacrylonitrile (PAN) UF membrane, which can simulta-
neously reject the bovine serum albumin (BSA) and remove Cu2+ and
Pb2+ from the aqueous solution[26]. Kanagaraj et al. prepared the PEI/
CSMM blend UF membranes to separate macromolecular proteins in-
cluding BSA, egg albumin and pepsin, and reject toxic heavy metal ions
from aqueous solutions [27]. Ruan et al. fabricated the PEI-grafted
porous membranes with excellent rejection efficiency for calcium al-
ginate (CA) microsphere (~98.5%) and high adsorption capacity for Co
(II) (51.0 mg/g). PEI-grafted membrane was proved to be highly effi-
cient for removing heavy metal ions and suspended particles simulta-
neously from wastewater [28]. In the actual life, there are various or-
ganic pollutants and plenty of metal ions in the industrial wastewater at
the same time. It is no doubt that there is an interaction between or-
ganic pollutants and metal ions to form various metal-organic com-
plexes. The complicated metal-organic interactions definitely affect the
removal efficiency for both metal ions and organic pollutants during the
membrane filtration process. To the best of our knowledge, however,
the study on this aspect has been rarely reported.
In this study, we fabricated the PAN/PVDF chelating membrane
with amidoxime groups to simultaneously remove the metallic and
2
Separation and Purification Technology 235 (2020) 116185
organic pollutants from the mimic industrial wastewater. Cu2+, Pb2+
and Cd2+ were used as components of heavy metal ions and lysozyme
and BSA were used as organic pollutants in this study. To simulate
various types of industrial wastewater, we classified four kinds of mixed
solutions in terms of pollutant components. Dynamic filtration of mix-
tures consisting of metal ions and proteins was conduct, and the re-
moval efficiency for metal ions and proteins by chelating membrane
were examined in different cases. The influences of the complicated
interaction between metal ions and proteins on the performance of
chelating membranes were investigated.
2. Experimental
2.1. Material
PAN powder (Mw = 60,000 g/mol) was purchased from Tianjin
Kemiou Chemical Reagent Co. Ltd. (China). PVDF powder (FR904) was
obtained from Shanghai 3F New Materials Co. Ltd. (China).
Hydroxylamine hydrochloride was obtained from Aladdin (China). N,N-
dimethylacetamide (DMAc), copper (II) chloride (CuCl2, > 99%), lead
(II) nitrate (Pb(NO3)2, > 99%) and cadmium nitrate tetrahydrate (Cd
(NO3)2·4H2O, > 99%) were purchased from Tianjin Kemiou Chemical
Reagent Co. Ltd. (China). Bovine serum albumin (BSA, Mw = 68,000 g/
mol) was obtained from Solarbio (China). Lysozyme (L,
Mw = 14,000 g/mol) was obtained from Shanghai Macklin Biochemical
Co. Ltd. (China). All of the chemicals are in analytical grade.
2.2. Instrument
Fourier transform infrared (FT-IR) spectrometer (Perkin Elmer Inc.
USA) was employed to analyze the chemical structure. Scanning elec-
tron microscope (SEM) (JSM-7800F, JEOL, Japan) was used to char-
acterize the membrane morphology and structure. Atomic absorption
spectroscopy (AAS) (Spectra 180–80, Hitachi, Japan) was used to
measure the metal ion concentration in solution. Ultraviolet spectro-
photometer (UV-1700PC, Macy Instruments Inc. China) was employed
to analyze the protein concentration in solution.
2.3. Methods
2.3.1. Preparation of PAN/PVDF UF membrane
PAN and PVDF were dried at 60 °C for 24 h before use, and then
dissolved in DMAC (casting solution concentration is 17 wt%) by stir-
ring at room temperature, with a proportion of PAN to PVDF of
96.5:3.5. Vacuum degassing was performed to eliminate air bubbles in
the casting solution. The PAN/PVDF UF membrane (namely original
membrane) was prepared by the L-S phase exchange method. The
prepared PAN/PVDF UF membrane was immersed in deionized water
for use.
2.3.2. Preparation of PAN/PVDF chelating membrane
The PAN/PVDF UF membrane was chemically modified to prepare
the chelating membrane with amidoxime groups. Hydroxylamine hy-
drochloride and sodium carbonate were dissolved in deionized water,
and then PAN/PVDF UF membrane was immersed in the solution. The
amidoximation reaction, as shown in Fig. 1, was carried out for 2 h at
60 °C. The nitrile group in PAN was partially converted to the ami-
doxime group. After the reaction, the PAN/PVDF chelating membrane
was washed several times with deionized water to remove residual
Fig.1. Scheme of amidoximation reaction.
S. Xu, et al. Separation and Purification Technology 235 (2020) 116185

Table 1
Basic information about two proteins.
Protein Number of amino acid residues Molecular weight (Da)

Lysozyme 129 14,000

BSA 583 68,000

chemicals.

2.3.3. Measurement of water flux

The water flux of membrane was measured by the UF cell purchased
from Shanghai SINAP Membrane Tech Co., Ltd (China). The mem-
branes were pre-pressured at 0.15 MPa for 30 min to obtain stable
structure, and then water flux of membrane was measured at 0.1 MPa.
The water flux of membrane (at 25 °C) can be calculated as follows:
V
J=
A×T (1)
where J is the water flux of membrane, V is the volume of water
through membrane, A is the area of membrane, T is the filtration time.
2.3.4. Measurement of protein rejection rate
Two kinds of proteins including lysozyme (L) and bovine serum
albumin (BSA) were used in this study. Lysozyme is an ellipsoidal
proteinase and consists of 129 amino acid residues with four disulfide
bonds [29]. BSA is a water-soluble globular protein and consists of
single polypeptide chain with 583 amino acid residues and 17 disulfide
bonds [30]. The basic information of two proteins are shown in Table 1.
After membrane filtration of the protein solution at 25 °C and
0.1 MPa, the absorbance of the filtrate was determined by the ultra-
violet/visible spectrophotometer, and protein concentration in the fil-
trate can be obtained according to the absorbance-concentration stan-
dard curve. The protein rejection rate (R) of membrane can be
evaluated as follows:
Cp ⎞
R = ⎛1 −
⎜ × 100%
⎟ acteristic extended vibration C]N and NeO absorption bands at
C (2)
⎝ F⎠
where CF and CP is the protein concentrations of the feed and permeate,
respectively.
2.3.5. Measurement of ion removal rate
Three kinds of metal ion (Cu2+, Pb2+ and Cd2+) were used in this
study. Dynamic filtration of metal ion solution (C = 10 mg/L) by che-
lating membrane was carried out using the UF cell. The ion con-
centration in the filtrate was measured by atomic absorption spectro-
scopy. The ion removal rate can be calculated as shown in Eq. (3):
C0 − Ct
γ= × 100%
C0 (3)
where γ is the ion removal rate, C0 is the initial concentration of ion
solution and Ct is the concentration of ions in solution after adsorption
time t.
2.3.6. Classification of mixed solution
In this study, the PAN/PVDF chelating membrane was used to si-
multaneously remove metal ions and proteins from the aqueous solu-
tion. The aim of this study is to investigate the interactions between
metal ions and proteins, and their synergistic effects on the removal
efficiency for both metal ions and protein.
The industrial wastewater contains not only various organic pollu-
tants, but also a variety of metal ions. To mimic the industrial waste-
water, lysozyme and BSA were employed as organic pollutants, and
Cu2+, Pb2+ and Cd2+ were adopted as components of metal ion in this
study. To mimic the industrial wastewater, we classified four kinds of
mixture in terms of pollutant components in this study.
Fig. 2. FT-IR spectra of original membrane and chelating membrane.
Case-1: a mixture consisting of one metal ion and one protein (1 + 1
type);
Case-2: a mixture consisting of one metal ion and two proteins
(1 + 2 type);
Case-3: a mixture consisting of three metal ions and one protein
(3 + 1 type);
Case-4: a mixture consisting of three metal ions and two proteins
(3 + 2 type).
3. Results and discussion
3.1. FT-IR and EDS analysis
The FT-IR spectra of original membrane and chelating membrane
are shown in Fig. 2. Compared with the original membrane, the che-
lating membrane has different characteristic adsorption peaks. Char-
1654 cm−1 and 921 cm−1 are pretty observed. It indicates that the
amidoxime group is successfully introduced into the PAN/PVDF mem-
brane. Furthermore, both original membrane and chelating membrane
have similar characteristic peak at about 2243 cm−1, corresponding to
the nitrile group (eCN). It indicates that the nitrile group in PAN is
partially converted into the amidoxime group, which is consistent with
the scheme of amidoximation reaction, as illustrated in Fig. 1.
The percentage of various elements on the membrane surface was
measured by energy dispersive spectroscopy (EDS), and the results were
shown in Table 2. After the amidoximation modification of PAN/PVDF
membrane, the atomic percentage of C element on the surface of the
chelating membrane is decreased by 7.16%, the content of N element is
increased slightly by 1.12%, while the content of O element is increased
by 6.04%. It indicates that the amidoxime group is successfully in-
troduced onto the surface of PAN/PVDF membrane.
3.2. SEM characterization
SEM images of original membrane and chelating membrane are
shown in Fig. 3. The surface morphology of the original membrane is
smoother than the chelating membrane, as illustrated in Fig. 3(a1) and
Table 2
Weight percent of elements based on EDS analysis.
Element Original membrane Chelating membrane
C 72.17% 65.01%
N 23.17% 24.29%
O 4.66% 10.70%

3
S. Xu, et al. Separation and Purification Technology 235 (2020) 116185

Fig. 3. Surface structure of (a1) original membrane and (b1) chelating membrane, and cross-sectional structure of (a2) original membrane and (b2) chelating
membrane.

(b1). The rough surface of the chelating membrane is primarily due to

the introduction of the amidoxime groups on the surface of PAN/PVDF
membrane. Both original membrane and chelating membrane exhibit
the similar finger-like pore structure, which can be observed from
Fig. 3(a2) and (b2). There is no clear evidence that modification reac-
tion occurs on the pore walls of membrane, indicating that the surface
modification has a negligible effect on the cross-sectional structure of
membrane.

3.3. Membrane filtration properties

The pure water flux and protein rejection rate by different mem-
branes are shown in Table 3. The pure water flux of chelating mem-
brane is far less than that of original membrane, which is due to the fact
that the surface morphology of chelating membrane becomes coarse
after the introduction of amidoxime groups. Interestingly, the rough Fig. 4. Removal rate of metal ions by chelating membrane for pure individual
surface of chelating membrane facilitates the retention of protein in ion solution (ion concentration is 10 mg/L).
solution. As a result, for the same protein, the rejection rate of protein
by chelating membrane is higher than that of original membrane. For
3.4. Pure individual ion solution
the same membrane, although the molecular weight of lysozyme is far
less than that of BSA, the rejection rate of lysozyme is much higher than
For pure individual ion solution (in the absence of protein), the
that of BSA. It is due to the fact that lysozyme is prone to agglomerate
removal rate of different ions by the PAN/PVDF chelating membrane is
into larger particle in the aqueous solution. The aggregated lysozyme
shown in Fig. 4. Under the same condition, the removal rate of Cu2+,
can be easily captured by membrane, resulting in higher protein re-
Pb2+ and Cd2+ is 72.19%, 52.11% and 34.27%, respectively, which is
jection rate.
due to the strong interactions between metal ions and amidoxime
groups on the membrane surface. It indicates that chelating membrane
preferentially interacts with Cu2+, and Cd2+ is least preferentially in-
teracted. Removal of metal ions by chelating membrane follows this
Table 3
order: Cu2+ > Pb2+ > Cd2+. For the original membrane, the ion re-
Filtration properties of different membranes.
moval rate is almost zero (data is not shown) due to the absence of
Membrane Water flux (J) Rejection rate of Rejection rate of chelating functional groups.
(L/m2·h) BSA (%) lysozyme (%)

Original membrane 186.14 74.86 94.91

Chelating membrane 72.13 88.29 95.91

4
S. Xu, et al.
Fig. 5. Removal rate of metal ions by different membranes from a mixture of
one metal ion and lysozyme (ion concentration is 10 mg/L, lysozyme con-
centration is 100 mg/L).
3.5. A mixture consisting of one metal ion and one protein (1 + 1 type)
Dynamic filtration of a mixture of one metal ion and one protein
was conducted by the chelating membrane. To illuminate the me-
chanism for removing metal ions, filtration experiment by original
membrane was conducted as blank control.
3.5.1. A mixture consisting of one metal ion and lysozyme
Fig. 5 shows the removal rate of metal ions by both original and
chelating membranes in the presence of lysozyme. Theoretically, the
original membrane can't remove metal ions from the aqueous solution
due to the absence of chelating groups. Due to the presence of lyso-
zyme, the metal ions can be partially removed from the aqueous solu-
tion by the original membrane, which is due to the interaction between
metal ions and lysozyme to form the metal-protein complex that can be
rejected by the membrane. The removal rate of Cu2+, Pb2+ and Cd2+
by the original membrane is 5.54%, 21.02%, and 0.46%, respectively, It
indicates that Pb2+ is preferentially interacted with lysozyme, followed
by Cu2+, and the interaction between Cd2+ and lysozyme is insignif-
icant.
Compared with the original membrane, the removal efficiency of
metal ions by the chelating membrane is significantly improved. The
removal rate of Cu2+ by chelating membrane is 17.01 times as much as
that of original membrane. The removal rate of Pb2+ by chelating
membrane is 3.59 times as much as that of original membrane. The
removal rate of Cd2+ by chelating membrane is 87.24 times as much as
that of original membrane. Compared with Fig. 4 (in the absence of
protein), the removal rate of Cu2+, Pb2+ and Cd2+ by chelating
membrane in the presence of lysozyme is increased by 30.50%, 44.83%
and 17.10%, respectively, due to the interaction between metal ion and
lysozyme. There are two possible mechanisms accounting for removal
of metal ion by chelating membrane: (1) interaction between metal ion
and protein, namely metal-protein interaction; (2) interaction between
metal ion and chelating membrane, namely metal-membrane chelation.
Obviously, the metal-membrane chelation plays a crucial role in the
metal removal from a mixture consisting of one metal ion and lyso-
zyme.
As mentioned above, the chelating membrane is prepared through
the amidoxime modification of PAN/PVDF UF membrane, which can
simultaneously remove metal ions and protein from the wastewater. As
illustrated in Fig. 6, for the pure protein solution, the rejection rate of
lysozyme by chelating membrane is 95.91%. In contrast, the rejection
rate of lysozyme by chelating membrane in the presence of Cu2+, Pb2+
and Cd2+ is decreased by 5.92%, 12.02% and 16.42%, respectively. It
may be due to the fact that heavy metal salts such as CuCl2, Pb(NO3)2,
5
Separation and Purification Technology 235 (2020) 116185
Fig. 6. Protein rejection rate by chelating membranes for a mixture of one
metal ion and lysozyme (ion concentration is 10 mg/L, lysozyme concentration
is 100 mg/L).
and Cd(NO3)2 inactivates the lysozyme in the solution, destroying the
conformational structure of protein, breaking the long chain of the
polypeptide, making it easier to pass through the membrane. It in-
dicates Cd2+ has a relatively strong destructive action on the lysozyme
and the destructive action of Cu2+ on the lysozyme is relatively weak.
3.5.2. A mixture consisting of one metal ion and BSA
Fig. 7 presents the removal efficiency of metal ions by both original
and chelating membranes from a mixture consisting of one metal ion
and BSA. The removal rate of Cu2+, Pb2+ and Cd2+ by the original
membrane is 26.06%, 41.58%, and 6.66%, respectively, which is at-
tributed to the interaction between metal ions and BSA. It indicates the
interaction between Pb2+ and BSA is relatively strong and the inter-
action between Cd2+ and BSA is relatively weak. Compared with the
original membrane, the removal rate of metal ions by the chelating
membrane is significantly improved due to the interaction between
metal ions with amidoxime groups of the chelating membrane. The
removal rate of Cu2+, Pb2+ and Cd2+ by the chelating membrane is
3.83, 2.36 and 8.84 times as much as that by the original membrane,
respectively. Compared with Fig. 4 (in the absence of BSA), the pre-
sence of BSA can greatly improve the removal efficiency of metal ions
by chelating membrane due to the interaction of metal ion with BSA.
The removal rate of Cu2+, Pb2+ and Cd2+ by the chelating membrane
in the presence of BSA is increased by 38.26%, 88.47% and 71.84%,
respectively.
Fig. 7. Removal rate of metal ions by original membrane and chelating mem-
brane in the presence of BSA (ion concentration is 10 mg/L, BSA concentration
is 100 mg/L).
S. Xu, et al.
Fig. 8. BSA rejection rate by chelating membrane for a mixture of one metal ion
and BSA (ion concentration is 10 mg/L, BSA concentration is 100 mg/L).
Compared with Fig. 5 (metal ion + lysozyme), the removal effi-
ciency of metal ions by chelating membrane in the presence of BSA is
much higher than that in the presence of lysozyme. The removal rate of
Cu2+, Pb2+ and Cd2+ by the chelating membrane in the presence of
BSA is increased by 5.94%, 30.13% and 46.75%, respectively. It in-
dicates that BSA exhibits a stronger complexation action with metal
ions than lysozyme. As illustrated in Table 1, BSA has much more
amino acid residues (583) than lysozyme (129), suggesting BSA can
provide much more coordination sites for the formation of metal-pro-
tein complexes.
Similarly, the chelating membrane can effectively reject BSA from
the mixed solution, and the results are shown in Fig. 8. Compared with
pure BSA solution, BSA rejection rate by the chelating membrane in the
presence of Cu2+, Pb2+ and Cd2+ is increased by 13.05%, 11.24% and
4.85%, respectively, which is attributed to the formation of metal-BSA
complexes. Compared with Fig. 6, the rejection rate of BSA by chelating
membrane is higher than that of lysozyme under the same condition. It
suggests the metal ions have a stronger destructive action on lysozyme
than BSA.
3.6. A mixture consisting of one metal ion and two proteins (1 + 2 type)
In this section, dynamic filtration of a mixture consisting of one
metal ion and two proteins was conducted by the chelating membrane.
The interactions between metal ion with a protein mixture is much
more complicated, because rather than interactions between metal ions
with each protein, it consists of the lysozyme-BSA interaction. The in-
teraction between metal ions with one protein will affect the interaction
between metal ions with other protein, indicating metal ions competi-
tively coordinates with two proteins to form the metal-protein com-
plexes. The protein-protein interaction might affect the metal-protein
interactions [31,32].
Fig. 9 shows the removal efficiency of metal ions by chelating
membrane from a mixture consisting of one metal ion and two proteins.
In this case, the removal rate of Cu2+, Pb2+ and Cd2+ by the chelating
membrane is 96.15%, 79.9% and 54.2%, respectively. Compared with
Fig. 5 (one metal ion + lysozyme), the removal rate of Cu2+, Pb2+ and
Cd2+ by the chelating membrane in the presence of a protein mixture is
increased by 2.06%, 5.87% and 35.06%, respectively. It implies the
presence of a protein mixture can improve the removal efficiency of
metal ions, which is mainly due to the additional interaction between
metal ion with BSA. In this case, the removal mechanism of metal ion
depends on the metal-lysozyme interaction, the metal-BSA interaction
and the metal-membrane chelation. The lysozyme-BSA interaction has a
negative effect on the removal efficiency of metal ion. Fortunately, the
positive effect of the metal-BSA interaction overweighs the negative
6
Separation and Purification Technology 235 (2020) 116185
Fig. 9. Removal rate of metal ions by chelating membrane in the presence of
two proteins (ion concentration is 10 mg/L, each protein concentration is
100 mg/L).
effect of the lysozyme-BSA interaction on the removal efficiency of
metal ion. As a result, the removal efficiency of metal ions by chelating
membrane in the presence of a protein mixture is better than that in the
presence of lysozyme.
However, compared with Fig. 7 (one metal ion + BSA), the removal
rate of Cu2+, Pb2+ and Cd2+ by chelating membrane in the presence of
a protein mixture is reduced by 3.67%, 18.64%, and 7.82%, respec-
tively. It indicates, compared with the case in presence of BSA, the
presence of a protein mixture deteriorates the removal efficiency of
metal ions. For the case (one metal ion + BSA) as illustrated in Fig. 7,
the removal efficiency of metal ion by chelating membrane is depen-
dent upon the metal-BSA interaction and the metal-membrane chela-
tion. For this case (one metal ion + a protein mixture), rather than the
metal-BSA interaction and the metal-membrane chelation, the metal-
lysozyme interaction also plays a positive role in removing metal ions.
However, the negative effect of lysozyme-BSA interaction exceeds the
positive effect of metal-lysozyme interaction on the removal efficiency
of metal ion. As a result, the removal rate of metal ion by chelating
membrane in the presence of a protein mixture is lower than that in the
presence of BSA.
Fig. 10 shows the rejection rate of proteins by chelating membrane
from a mixture consisting of one metal ion and two proteins. Compared
with Fig. 6 (one metal ion + lysozyme), the rejection rate of lysozyme
by chelating membrane in the presence of Cu2+, Pb2+ and Cd2+ is
increased by 2.02%, reduced by 12.79% and 17.71%, respectively.
Fig. 10. Rejection rate of proteins by chelating membrane in the presence of
one metal ion (ion concentration is 10 mg/L, each protein concentration is
100 mg/L).
S. Xu, et al.
Fig. 11. Removal rate of metal ions by chelating membrane in the presence of
one protein (each ion concentration is 10 mg/L, protein concentration is
100 mg/L).
Compared with Fig. 8 (one metal ion + BSA), the rejection rate of BSA
by chelating membrane in the presence of Cu2+ Pb2+ and Cd2+ is re-
duced by 9.71%, 24.13% and 12.80%, respectively. It suggests that the
co-existence of two proteins deteriorates the rejection rate of each
protein, which is due to the fact that the lysozyme-BSA interaction
might disturb the retention of each protein.
3.7. A mixture consisting of three metal ions and one protein (3 + 1 type)
When three metal ions and one protein are present in the aqueous
solution, each metal ion interacts competitively with the protein to
form the metal-protein complex. In addition, there is the competitive
interactions between each metal ion and the chelating membrane
during the dynamic filtration process. As illustrated in Fig. 11, the re-
moval rate of Cu2+ Pb2+ and Cd2+ by chelating membrane in the
presence of lysozyme is 96.6%, 72.1% and 69.6%, respectively. Com-
pared with Fig. 5 (one metal ion + lysozyme), the removal rate of Cu2+
and Pb2+ has a subtle change. It indicates that the competition of
metal-lysozyme interactions has an insignificant effect on the removal
efficiency of Cu2+ or Pb2+. The improvement of Cd2+ removal rate (by
73.44%) suggests that competitive interactions of Cu2+ or Pb2+ with
lysozyme can promote the removal rate of Cd2+ by chelating mem-
brane. However, the mechanism accounting for this phenomenon is still
unknown.
When three metal ions and BSA are simultaneously present in the
solution, the removal rate of Cu2+ Pb2+ and Cd2+ by chelating mem-
brane is 98.4%, 98.1% and 61.5%, respectively. Compared with Fig. 7
(one metal ion + BSA), the removal rate of metal ions by chelating
membrane has a subtle change. It indicates that the competition of
metal-BSA interactions has a negligible effect on the removal efficiency
of metal ion.
As illustrated in Fig. 12, in the presence of three metal ions, the
rejection rate of lysozyme and BSA by chelating membrane is 82.07%
and 96.27%, respectively. Compared with Fig. 6 (one metal ion + ly-
sozyme), the rejection rate of lysozyme in the presence of three metal
ions is less than that in the presence of Cu2+ (−8.16%) or Pb2+
(−2.31%), due to the destructive effect of Cd2+ on the lysozyme.
Compared with Fig. 8 (one metal ion + BSA), the rejection rate of BSA
in the presence of three metal ions is less than that in the presence of
Cu2+ (−3.54%) or Pb2+ (−1.94%) due to the destructive effect of
Cd2+ on BSA. Cd2+ has a strong destructive action on the structure of
protein, breaking the disulfide bonds in the molecular chain. In addi-
tion, the rejection rate of protein (lysozyme or BSA) in the presence of
three metal ions is higher than that in the presence of Cd2+. It indicates
the interactions of Cu2+ or Pb2+ with protein can alleviate the
7
Separation and Purification Technology 235 (2020) 116185
Fig. 12. Rejection rate of protein by chelating membrane in the presence of
three metal ions (each ion concentration is 10 mg/L, protein concentration is
100 mg/L).
Fig. 13. Removal rate of metal ions by chelating membrane from a mixture of
three metal ions and two proteins (each ion concentration is 10 mg/L, each
protein concentration is 100 mg/L).
destructive action of Cd2+ on the structure of protein.
3.8. A mixture consisting of three metal ions and two proteins (3 + 2 type)
As illustrated in Fig. 13, when three metal ions and two proteins are
simultaneously present in the aqueous solution, the removal rate of
Cu2+, Pb2+ and Cd2+ by chelating membrane is 99.77%, 95.25% and
79.57%, respectively. Compared with Fig. 9 (1 + 2 type), although the
metal ion species in the solution increases, the removal rate of metal ion
is still significantly improved, due to the complicated interactions be-
tween metal ions (Cu2+, Pb2+ and Cd2+) and proteins (lysozyme and
BSA) which stimulates the removal efficiency of metal ions. Compared
with Fig. 11 (3 + 1 type), as the protein species in the solution in-
creases, the removal efficiency of metal ion is still improved as well,
which is due to the fact that the interactions between metal ions and
proteins becomes much easier.
As illustrated in Fig. 14, when three metal ions co-exist with two
proteins in the aqueous solution, the rejection rate of lysozyme and BSA
by chelating membrane is 94.36% and 97.67%, respectively. Compared
with Fig. 10 (1 + 2 type), as the metal ion species in the solution in-
creases, the retention efficiency of each protein is improved, which is
due to the formation of much more metal-protein complexes. Compared
with Fig. 12 (3 + 1 type), as the protein species in the solution in-
creases, the retention efficiency of each protein is improved as well,
indicating that the interactions between metal ions and proteins
S. Xu, et al.
Fig. 14. Rejection rate of protein by chelating membrane from a mixture of
three metal ions and two proteins (each ion concentration is 10 mg/L, each
protein concentration is 100 mg/L).
facilitate the protein retention.
4. Conclusions
In this study, the PAN/PVDF chelating membrane with amidoxime
groups was prepared to simultaneously remove the metal ions and
proteins from the aqueous solution. The presence of one protein (ly-
sozyme or BSA) can greatly improve the removal efficiency of metal
ions due to the interaction between metal ions with protein. Compared
with pure protein solution, the presence of one metal ion promotes the
retention efficiency of BSA, while deteriorates the retention efficiency
of lysozyme.
Compared with the case (one metal ion + lysozyme), the presence
of a protein mixture can improve the removal efficiency of metal ions,
due to the additional interaction between metal ion with BSA.
Compared with the case (one metal ion + BSA), the presence of a
protein mixture decreases the removal efficiency of metal ions.
However, the presence of a protein mixture deteriorates the rejection
rate of each protein, since the lysozyme-BSA interaction disturbs the
protein retention by chelating membrane.
For the case (three metal ions + one protein), the removal efficiency
of Cu2+ and Pb2+ by chelating membrane has a subtle change, in-
dicating that the competition of metal-protein interactions has an in-
significant effect on the removal efficiency of metal ion. Compared with
the case (one metal ion + one protein), the rejection rate of protein in
the presence of three metal ions is less than that in the presence of Cu2+
or Pb2+, due to the destructive effect of Cd2+ on the structure of pro-
tein.
When three metal ions and two proteins are present in the aqueous
solution, compared with the case (1 + 2 type), although the metal ion
species in the solution increases, the removal efficiency of metal ion is
significantly improved, due to the interactions between metal ions and
proteins which stimulates the removal efficiency of metal ions.
Compared with Fig. 11 (3 + 1 type), as the protein species in the so-
lution increases, the removal efficiency of metal ion is still improved,
which is due to the fact that the interactions between metal ions and
proteins becomes much easier. Compared with the case (1 + 2 type), as
the metal ion species in the solution increases, the retention efficiency
of each protein is improved, which is due to the formation of much
more metal-protein complexes. Compared with the case (3 + 1 type),
as the protein species in the solution increases, the retention efficiency
of each protein is improved, indicating that the interactions between
metal ions and proteins facilitate the protein retention.
8
Separation and Purification Technology 235 (2020) 116185
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by the Nature Science Foundation of
Liaoning Province (grant number: 20180550429).
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