Chemical Engineering Journal 417 (2021) 127930

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Chemical Engineering Journal

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High–performance nanofiltration membrane blended by Fe3O4@SiO2–CS

bionanocomposite for efficient simultaneous rejection of salts/heavy metals
ions/dyes with high permeability, retention increase and fouling decline
Soran Kamari, Afsaneh Shahbazi *
Department of Environmental Technologies, Environmental Sciences Research Institute, Shahid Beheshti University, 1983969411 Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: A high–performance nanofiltration (NF) membrane was fabricated by blending Fe3O4@SiO2–CS biocompatible
Wheat straw and green bionanocomposite, which was synthesized by a core–shell of Fe3O4 magnetic nanoparticles and
Fe3O4@SiO2–CS bionanocomposite amorphous SiO2 extracted from wheat straw and functionalized by chitosan groups. The characteristics analyses
Nanofiltration membrane
confirmed fine structure of the synthesized bionanocomposite and the fabricated NF–membranes. Among the
Multicomponent filtration
Long–term filtration
fabricated membranes, the unblended membrane (NFM–1) by 47.3 L m–2h− 1 showed the lowest pure water flux,
while it was significantly increased for the blended membranes (NFM–2, NFM–3 and NFM–4) and in the best case
reached 70.6 L m–2h− 1 for NFM–3 membrane. All the membranes showed the highest salt rejection for Na2SO4
with ~ 90% and the lowest salt rejection for MgCl2 with ~ 10%, confirming the nanofiltration behavior of the
fabricated membranes. The removal of heavy metals ions by NF–membranes increased from NFM–1 membrane
by 14.95, 15.45 and 16.11% to NFM–3 membrane by 98.11, 98.61 and 98.86% for Pb2+, Cu2+ and Cd2+,
respectively. All the NF–membranes indicated more than 98.2% dyes retention for both cationic and anionic dyes
such as MB, CR and RB5. Also, the efficiency of NFM–3 membrane was very high for the filtration of multi­
component solutions and increasing the concentration of Na2SO4 had a limited effect on the removal of Pb2+ and
MB. Regarding the 120 h continuous filtration test, NFM–3 membrane depicted a slight reduction in water flux
and rejection of Na2SO4, Pb2+ and MB.

1. Introduction contain various kinds of carcinogenic organic dyes such as methylene

The population growth and industrialization have created many
environmental issues such as water crisis problem for human societies
by contaminating water with industrial pollutants especially inorganic
salts, heavy metals ions and organic dyes, which have necessitated the
development of water and wastewater treatment technologies [1].
Release of inorganic salts such as Na2SO4, MgSO4, NaCl and MgCl2 in the
human water sources through industrial wastewaters can cause salinity
of water and reduces its quality for human consumption [2]. High–toxic
heavy metals ions including lead (Pb2+), copper (Cu2+) and cadmium
(Cd2+) are extensively discharged into the surface waters through in­
dustrial wastewaters. These toxic ions are stable and non–biodegradable
in the environment, thus they can cause the bioaccumulation in the food
chains even at very low concentrations and consequently result in a wide
range of complications and disorders including acute poisonings, can­
cers and mental–physical injuries [3]. Many industrial wastewaters
blue (MB), congo red (CR) and reactive black 5 (RB5); releasing these
dyes in the surface waters causes various diseases and genetic mutations
in human, reduction in transparency of water, loss of light penetration in
the water and disrupting the photosynthetic activities of living organ­
isms in water [4].
Of course, it should be noted that the industrial wastewaters can be
considered as a valuable water source for human consumption especially
in countries with water scarcity, if well organized by effective treatment
and purification methods [5]. Hence, the use of new, cost–effective and
efficient methods for treatment of industrial wastewaters is completely
essential. So far, various technologies have been applied to remove
pollutants from water and wastewaters including chemical precipita­
tion, ion exchange, chemical oxidation, adsorption and membrane
filtration (microfiltration (MF), ultrafiltration (UF), nanofiltration (NF)
and reverse osmosis (RO)) [6]. Among these technologies, NF has
attracted intensive interest as a sustainable, low expense, ease of

* Corresponding author.
E-mail address: a_shahbazi@sbu.ac.ir (A. Shahbazi).

https://doi.org/10.1016/j.cej.2020.127930
Received 28 July 2020; Received in revised form 22 November 2020; Accepted 26 November 2020
Available online 2 December 2020
1385-8947/© 2020 Elsevier B.V. All rights reserved.
S. Kamari and A. Shahbazi
operation, low energy consumption and high efficiency technology [7].
NF–membranes are capable of retaining multivalent ions and dissolved
organics with molecular weight cut–off (MWCO) above 200 Da [8].
Among the NF–membranes, polyethersulfone (PES) membrane has
special value because of its unique properties such as mechanical,
thermal and chemical stability [3]. However, the separation perfor­
mance of this membrane is naturally low due to the lack of effective
adsorptive functional groups in its structure and its separation perfor­
mance significantly decrease due to the rapid fouling caused by removed
pollutants, which subsequently dramatically increase its energy con­
sumption and maintenance costs [9]. Therefore, to enhance its separa­
tion performance along with increment of its pure water flux and decline
of its fouling attributes, PES matrix must be modified by embedding
effective nanocomposites in its structure [10].
Today, synthesis of non–toxic, biocompatible and low–cost bio­
nanocomposites has been huge prospective desired for wastewater
treatment functions, which can be supported by both scientific and
environmentally approaches. The ferric oxide magnetic nanoparticles
(Fe3O4 MNPs) can be considered as a potential candidate for PES
membrane modification due to its high mechanical and thermal stability
along with its non–toxic and biocompatible nature [11]. However, the
Fe3O4 MNPs without a protective coating layer tends to aggregation and
oxidation, which reduce its specific surface area and makes the mem­
brane to crack [12]. To deal with these negative features, amorphous
materials such as silica (SiO2) is suggested as one of the most important
protective coating materials for Fe3O4 MNPs [10]. In this study, to
achieve biocompatible, sustainable and very low–cost amorphous SiO2
for coating the surface of Fe3O4 MNPs, a highly pure SiO2 was extracted
from wheat straw (WS) as a cheap agro–based waste material, which is
rich in amorphous SiO2 [12]. Since the SiO2 is poor in terms of
adsorptive target groups and also it has limited hydrophilicity nature,
the SiO2 surface was subsequently functionalized by chitosan (CS)
groups. Indeed, CS is a biopolymer that can be used as an efficient
material for functionalization of SiO2 surface due to its high content of
–OH/NH2 functional groups, high adsorption capacity, high hydrophi­
licity, environmental compatibility and availability [13].
Therefore, in this study, first Fe3O4@SiO2 was synthesized and then
functionalized by CS. Fe3O4@SiO2–CS was applied as a new, biocom­
patible, non–toxic and low–cost bionanocomposite to modify the
structure of PES membrane. The physico–chemical characteristics of the
synthesized bionanocomposite and the fabricated NF–membranes were
studied comprehensively. The fabricated NF–membranes were applied
for the pure water flux measurement, desalination, removal of heavy
metals ions, retention of organic dyes and antifouling properties eval­
uation experiments, and finally the membrane with optimum efficiency
was determined. Based on the literature, the effects of pollutants con­
centration on NF separation performance, multicomponent solutions
filtration, reusability and long–term filtration of NF–membranes have
been less studied. Therefore, the effect of mentioned parameters on
NF–membranes performance were applied for the membrane with op­
timum efficiency.
2. Materials and methods
2.1. Materials
The WS agricultural waste was obtained from wheat fields of Rasht,
Iran. All the chemicals were purchased from Merck, Germany and their
characteristics are summarized in supporting information. The prepa­
ration of all solutions was conducted using deionized water (DIW).
2.2. Synthesis of Fe3O4@SiO2–CS bionanocomposite
The Fe3O4@SiO2–CS bionanocomposite was synthesized by a
four–step process. In the first step, the Fe3O4 MNPs was synthesized by
chemical co–precipitation method [12]. For this aim, 10.4 g of
2
Chemical Engineering Journal 417 (2021) 127930
FeCl3⋅6H2O and 4.0 g of FeCl2⋅4H2O were dissolved mechanically in
400 mL of DIW under N2 atmosphere and sonicated at 50 ◦ C for 1 h.
Afterwards, 120 mL of 14.8 M NH4OH solution was added dropwise into
the mixture under N2 atmosphere and agitated mechanically for 30 min
until its pH reached around 8. The resulted Fe3O4 MNPs was separated
by a magnet (4 T) and washed with DIW several times and dried in an
oven at 70 ◦ C for 24 h. In the second step, the extraction of amorphous
SiO2 from WS was optimized by acid leaching method [14]. For this
purpose, 50 g of dried WS, which was previously washed with DIW
several times, was treated by 1 L of various 1 N acidic solutions including
HCl, H2SO4, HNO3 and H3PO4 at 100 ◦ C for 1 h. Afterwards, it was
washed with DIW several times to neutralize its pH and dried in an oven
at 70 ◦ C for 24 h. Finally, it was combusted in an electric furnace at
600 ◦ C for 6 h with a gentle temperature gradient (10 ◦ C min− 1). Sub­
sequently, 4.1 g of extracted SiO2 and 2.0 g of NaOH were mixed in 40
mL of DIW and refluxed at 80 ◦ C for 24 h to obtain a 1 N sodium silicate
solution. In the third step, 2.0 g of obtained Fe3O4 MNPs was added in
400 mL of DIW under N2 atmosphere and sonicated at 80 ◦ C for 1 h to
attain a good dispersion. Afterwards, the sodium silicate solution was
added dropwise into the mixture under severe mechanical mixing where
its pH was adjusted to 6 by HCl solution and refluxed at 80 ◦ C for 5 h.
The resulted Fe3O4@SiO2 core–shell was separated using a magnet and
washed with DIW several times and dried at 70 ◦ C for 24 h. In the fourth
step, the synthesized Fe3O4@SiO2 was functionalized by CS groups [13].
For this aim, the Fe3O4@SiO2 was pre–dried in a vacuum oven at 100 ◦ C
for 6 h until its moisture was fully removed. Afterwards, 3.0 g of CS was
added in 300 mL of 3% acetic acid solution and 1.0 g of Fe3O4@SiO2 was
added to this solution. Afterwards, 2 mL of glutaraldehyde (as linker)
was added to this mixture and refluxed at 60 ◦ C for 2 h. The synthesized
Fe3O4@SiO2–CS bionanocomposite was separated using a magnet and
washed with DIW until its pH reached about 7 and dried at 50 ◦ C for 24
h. Fig. 1 shows the schematic diagram of Fe3O4@SiO2–CS bio­
nanocomposite synthesis process.
2.3. Fabrication of blended NF–membranes
The blended NF–membranes were fabricated by embedding various
Fe3O4@SiO2–CS loadings, related to the total solution weight, in the PES
matrix by phase inversion method [10]. The amounts of ingredients of
the casting solutions are shown in Table 1. First, the accurate amounts of
Fe3O4@SiO2–CS were dispersed in the precise amounts of DMAc (as
solvent bath) by 1 h sonication. Afterwards, the accurate amounts of
PVP (as porosity former agent) were dissolved in the mixtures by 1 h
sonication. Then, the accurate amounts of PES (as substrate polymer)
were dissolved in the mixtures by 1 h sonication and were shaken at
room temperature for 24 h to reach homogenous solutions. The obtained
homogenous mixtures were heated in an oven at 50 ◦ C for 2 h to remove
all air bubbles. After cooling to room temperature, the mixtures were
poured on a clean scratch–resistant glass plate and casted using a 0.2
mm–thick casting knife and immediately immersed in DIW (as non­
–solvent bath) at room temperature to coagulate membranes. The
fabricated NF–membranes were stored in the fresh DIW for 24 h to
complete phase separation and dried between the pad of filter papers at
room temperature for 24 h. The schematic diagram of the NF–mem­
branes fabrication process is illustrated in Fig. 2.
2.4. Characterization
In order to characterize the structure of the synthesized bio­
nanocomposite and the fabricated NF–membranes, the analyses of XRF,
XRD, FT–IR, VSM, FE–SEM, EDX, TEM, zeta potential, water contact
angle measurement, molecular weight cut–off (MWCO), porosity and
mechanical properties were performed. The detailed explanations about
each characterization method is described in supporting information.
The average particle size of bionanocomposite was computed by
Debye–Scherrer equation (Eq. (S1)) [12]. The mean pore diameter of
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

Step 1: Synthesis of Fe3O4 Step 3: Synthesis of Fe3O4@SiO2 core-shell

2 3
NH4OH
1 1
Reflux
N2 gas FeCl2.4H2O
Separation
+
+
FeCl3.6H2O Fe3O4 MNPs Fe3O4 MNPs Sodium silicate Fe3O4@SiO2

Step 2: Extraction of SiO 2 & synthesis of sodium silicate Step 4: Functionalized of Fe 3O4@SiO2 with chitosan (CS)

2 4
Acid leaching Reflux by 3 O
HO
O
O

(HNO3) NaOH
O HO NH2
O
OH O NH2 HO OH

Reflux
+
HO O

Combustion O HO H 2N
O
O
O O HN OHO
HO O 2

Wheat straw Amorphous

O H2 N
NH 2 OH
O
OH

Sodium silicate
O O
HO

(WS) silica (SiO2) Fe3O4@SiO2 Chitosan (CS) Fe3O4@SiO2-CS

Fig. 1. Schematic diagram of Fe3O4@SiO2–CS bionanocomposite synthesis process.

cm2). All the experiments were repeated three times and the average
Table 1
values were reported. Fig. 3 displays the schematic diagram of the
Amounts of ingredients of the casting solutions of the fabricated NF–membranes.
NF–setup.
Membrane PES (wt. PVP (wt. Fe3O4@SiO2–CS (wt. DMAc (wt.
code %) %) %) %)
2.5.2. Effect of pressure on pure water flux
NFM–1 20 1 0.0 79.0 The pure water flux was measured for NF–membranes at various
NFM–2 20 1 0.1 78.9
pressures of 0.2, 0.4, 0.6 and 0.8 MPa at room temperature. For this
NFM–3 20 1 0.5 78.5
NFM–4 20 1 1.0 78.0 purpose, the NF–membranes were immersed in DIW for 12 h, placed in
NF–cells and compacted through filtration of DIW at 0.2 MPa higher
corresponding pressures for 30 min to attain a steady water permeation
fabricated NF–membranes was determined based on MWCO results by flux. Subsequently, the pure water flux was measured every 10 min for
Eq. (S2) [8,15]. 120 min. The Eq. (1) was applied for calculation of the membranes pure
water flux [16]:
2.5. NF–membranes filtration experiments
V
Jw,1 = (1)
A × Δt
2.5.1. NF–setup characteristics
A batch type dead–end stainless steel NF–setup was used to perform where Jw,1 is the pure water flux (L m–2h− 1), V is the permeated pure
the NF–membranes filtration experiments including pure water flux water volume (L), A is the membranes effective surface area (m2) and Δt
measurement, desalination, heavy metals ions removal, dyes retention is the water permeation time (h).
and antifouling properties. The setup included an air compressor, a feed
tank (with a capacity of 20 L) and four NF–cells (with a capacity of 250
mL, a stirring speed of 300 rpm and an effective filtration area of 19.62

PES/PVP/DMAc/Fe3O4@SiO2-CS
bionanocomposite solution Casting solution

Casting knife
Pouring Casting
(0.2 mm)
Polymeric film
Glass plate
Shaker
Soaking

(300 rpm, 24 h)

NFM-4 NFM-3 NFM-2 NFM-1

Cutting Coagulation

Fe3O4@SiO2 -CS bionanocomposite

Flat sheet Glass plate DIW bath (25 °C)
blended NF-membranes

Fig. 2. Schematic diagram of the NF–membranes fabrication process by embedding various amounts of Fe3O4@SiO2–CS related to the total solution weight by phase
inversion method.

3
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

Feed tank

Measurement
& analysis

Pressure gauge NF-cells

Magnetic
Air compressor stirrer

Permeate

Fig. 3. Schematic diagram of the NF–setup equipped with four NF–cells (feed tank capacity = 20 L, cells capacity = 250 mL, stirring speed = 300 rpm, effective
filtration area = 19.62 cm2).

2.5.3. Desalination, heavy metals ions removal and dyes retention
experiments
The NF–membranes efficiency for rejection of Na2SO4, MgSO4, NaCl
and MgCl2 salts (with different ionic and hydrated radiuses; Table 2),
Pb2+, Cu2+ and Cd2+ heavy metals ions (with different ionic and hy­
drated radiuses; Table 2) and MB, CR and RB5 azo dyes (with different
molecular weights, maximum absorption wavelengths, charges and
chemical structures; Table 2) was assessed. The feed solution pH/feed
solution concentration of salts, heavy metals ions and dyes was 7.0/0.5 g
L–1, 5.0/0.1/g L–1 and 7.0/0.2 g L–1, respectively. All the filtration ex­
periments were conducted at pressure of 0.4 MPa and room temperature
for 120 min. The rejection percentage (R (%)) was determined by Eq. (2)
[2]:
( )
Cp
R(%) = 1 − × 100 (2)
Cf
where Cp and Cf are the pollutants concentration in permeated waters
and feed solutions (g L–1), respectively.
2.5.4. Effect of pollutants concentration and multicomponent filtration tests
In order to evaluate the performance of the NF–membranes for
filtration of pollutants, various concentrations of Na2SO4 (0.1, 0.25, 0.5,
1 and 5 g L–1), Pb2+ (0.01, 0.05, 0.1, 0.15 and 0.2 g L–1) and MB (0.05,
0.1, 0.2, 0.5 and 1 g L–1) single–component solutions were filtered using
optimum membrane.
Furthermore, in order to carry out the multicomponent solutions
filtration and study the effect of Na2SO4 concentration on Pb2+/MB
mixture retention, solutions containing simultaneously various con­
centrations of Na2SO4 (0.1, 0.25, 0.5, 1 and 5 g L–1) and fixed concen­
trations of Pb2+ (0.1 g L–1) and MB (0.2 g L–1) were filtered by optimum
membrane. The Eq. (2) was applied to compute the pollutants rejection
percentage.
2.5.5. Reusability and long–term filtration experiments
The reusability experiments were carried out by filtration of Na2SO4,
Pb2+ and MB single–component solutions using optimum membrane
and repeated for five continuous filtration cycles. In order to regenerate
the membrane, in the case of Na2SO4, the membrane was backwashed
with DIW at pressure of 0.6 MPa for 1 h [17]. In the case of Pb2+, the
membrane was agitated in 250 mL of 0.1 M EDTA solution (as chelating
agent) for 1 h and washed with DIW [3]. In the case of MB, the mem­
brane was agitated in 500 mL of 0.3 M HCl solution (as chelating agent)
for 6 h and washed with DIW [17].
The long–term filtration experiments were conducted using optimum

Table 2
Attributes of various salts, heavy metals ions and dyes used in this study [17–19].
Salts Attributes Naþ SO2−
4
Mg2þ Cl–
Ionic radius (Å) 0.95 2.9 0.65 1.8
Hydrated radius (Å) 3.6 3.8 4.3 3.3
Heavy metals Attributes Pb2þ Cu2þ Cd2þ –
ions Ionic radius (Å) 2.02 1.40 1.03 –
Hydrated radius (Å) 4.01 4.19 4.26 –
Dyes Attributes MB CR RB5 –
Molecular weight (Da) 319.85 696.66 991.82 –
Maximum absorption wavelength 664 498 595 –
(nm)
Charge Cationic Anionic Anionic –
Chemical structure –

4
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

membrane by filtration of Na2SO4, Pb2+ and MB single–component so­ ( )

Jp
lutions for 120 h continuous filtration; permeated water flux and pol­ Rt = 1− × 100 (4)
lutants rejection were measured every 2 h by applying Eqs. (1) and (2), Jw,1
respectively. The filtration conditions were the same as the primary ( )
Jw,2 − Jp
tests. Rr = × 100 (5)
Jw,1
2.5.6. Antifouling properties tests ( )
Jw,1 − Jw,2
In order to evaluate the antifouling properties of the fabricated Rir = × 100 (6)
Jw,1
NF–membranes, a 0.5 g L–1 BSA solution filtration was used (as the
representative organic and protein foulant) at pH of 7.0, pressure of 0.4
MPa and room temperature. In this regard, DIW was filtered through the 3. Results and discussion
membranes and the first pure water flux (Jw,1) was measured for 120
min using Eq. (1). In the next step, the BSA solution was replaced in the 3.1. Characterization of the synthesized Fe3O4@SiO2–CS
feed solution and the BSA solution flux (Jp) was measured for 120 min. bionanocomposite
Afterwards, the membranes were washed with DIW several times and
rested in DIW for 30 min. Finally, DIW was filtered through the washed The results of XRF analysis for determination of the purity (wt.%) of
and cleaned membranes and the second pure water flux (Jw,2) was extracted SiO2, which was obtained by leaching using various acid so­
measured for another 120 min. The Eq. (3) was used to calculate the lutions are presented in Table S1. One of the effects of acid leaching is
percentage of flux recovery ratio (FRR) of membranes [20]: removal of the metallic impurities especially K2O, CaO and P2O5 oxides.
( ) The purity of SiO2, which is one of the most important parameters, in the
FRR(%) =
Jw,2
× 100 (3) treated samples was significantly higher than that for the untreated
Jw,1 sample. Meanwhile, the sample treated by HNO3 acid solution had the
In order to determine the antifouling properties of the membranes in highest purity of SiO2 (96.52 wt%). On the other hand, the LOI
more detail, the Eqs. (4–6) were used to calculate the total fouling ratio parameter, which indicates the amount of unburned and residual
(Rt), reversible fouling ratio (Rr) and irreversible fouling ratio (Rir) [17]: organic matter in the ash [14], was the lowest in the sample treated by
HNO3 acid solution. Therefore, the treatment method using 1 N HNO3

(a) 311 (b)

Fe 3 O4 Fe O
Transmittance (a.u.)

SiO2 Si O Si
220 (asym.)
440
Intensity (a.u.)

400 511
111
Fe 3 O4 4 2 2 Si O Si
Fe 3 O4 @SiO2 (sym.)

SiO2
Fe 3 O4 @SiO2 -CS
Fe 3 O4 @SiO2
H O H NH2
Fe 3 O4 @SiO2 -CS (str.) Si O Si
(bend.)
10 20 30 40 50 60 70 80 90 95 4000 3400 2800 2200 1600 1000 400

2 (degree) Wavenumber (cm 1 )

(d)
60 30
(c)
40 20
Magnetization (emu g )
1

20 10

0 0

-20 -10

Fe3O4
-40 -20
Fe3O4@SiO 2
Fe3O4@SiO 2-CS
-60 -30
-10000 -5000 0 5000 10000 SiO2
Magnetic field (Oe)

Fig. 4. (a) XRD (high angle from 10 to 95◦ ), (b) FT–IR (wavenumber from 4000 to 400 cm− 1), (c) VSM (magnetic field from –9000 to 9000 Oe), (d, e and f) FE–SEM
images, (g) TEM and (h) zeta potential (pH value from 2 to 10) analyses of Fe3O4, SiO2, Fe3O4@SiO2 and Fe3O4@SiO2–CS.

5
S. Kamari and A. Shahbazi
(e)
Fe3O4
30
(g)
20
10
Zeta potential (mV)
-10
-20
-30
-40
-50
Fe3O4@SiO2
Fig. 4. (continued).
acid solution was used as optimum method for the extraction of SiO2
from WS.
The XRD patterns of Fe3O4, SiO2, Fe3O4@SiO2 and Fe3O4@SiO2–CS
are displayed in Fig. 4a. The seven characteristic peaks agree with the
standard cubic spinel structure of Fe3O4 MNPs (65–3107 JCPDS)
[10,21], which indicated that the crystalline structure of Fe3O4 MNPs
can be preserved after surface modification by SiO2 and subsequently by
CS functional groups. The spectra of SiO2 showed a broad mound–like
peak in the range of 2θ = 20–40◦ , which is the main characteristic of
amorphous SiO2 [14]. This indicates the activity and capability of the
extracted SiO2 to participate in chemical reactions [12]. The average
particle size of Fe3O4, Fe3O4@SiO2 and Fe3O4@SiO2–CS calculated by
Debye–Scherrer equation was ~ 10, ~13 and ~ 15 nm, respectively.
The FT–IR analysis of Fe3O4, SiO2, Fe3O4@SiO2 and Fe3O4@SiO2–CS
are illustrated in Fig. 4b. In the spectra of Fe3O4 MNPs, the absorption
band in the range of 579 cm− 1 is attributed to the Fe–O groups stretching
vibrations, which is related to the magnetic property of Fe3O4 MNPs
[21]. In the spectra of SiO2, the absorption bands in the ranges of 472,
807 and 1089 cm− 1 are related to the bending, symmetric and asym­
metric stretching vibrations, respectively, of the siloxane (Si–O–Si)
network structure. These three major absorption bands are the main
characteristic of amorphous SiO2 [14]. All the peaks mentioned above
are also appeared in the spectra of Fe3O4@SiO2 and Fe3O4@SiO2–CS,
6
Chemical Engineering Journal 417 (2021) 127930
(f)
Fe3O4@SiO2
(h)
Fe 3 O4
SiO2
Fe 3 O4 @SiO2
Fe 3 O4 @SiO2 -CS
2 3 4 5 6 7 8 9 10
pH
displaying the SiO2 coating location on the surface of Fe3O4 MNPs. The
broad absorption band in the range of 3405 cm− 1 corresponds to the
hydroxyl (O–H) groups stretching vibrations of absorbed water mole­
cules on the SiO2 surface. The absorption band at 1572 cm− 1 is associ­
ated with the amine (N–H) groups bending vibrations in CS groups on
the surface of Fe3O4@SiO2–CS [13].
The results of VSM analysis of Fe3O4, Fe3O4@SiO2 and
Fe3O4@SiO2–CS are indicated in Fig. 4c. The magnetic property of Fe3O4
MNPs was about 55.48 emu g− 1 at 9000 Oe, showing its super­
paramagnetic behavior. As Fe3O4 MNPs were surrounded by SiO2, the
magnetic property of resulted Fe3O4@SiO2 reduced to about 19.60 emu
g− 1 at 9000 Oe, which is due to the non–magnetic SiO2 surrounding
Fe3O4 MNPs [21]. The magnetic hysteresis rings showed that the mag­
netic saturation of Fe3O4@SiO2–CS also reduced to about 17.55 emu g− 1
at 9000 Oe, depicting the successful location of CS groups on the surface
of Fe3O4@SiO2 [14].
The FE–SEM image of the extracted SiO2 from WS is shown in Fig. 4d.
As can be seen, the extracted SiO2 particles are not spherical in shape
and have irregular and fiber–like structures. The spherical shape of
Fe3O4 MNPs (with ~ 10 nm diameter) and its cluster arrangement (due
to the magneto dipoles and Van der Waals forces between the particles)
were approved by FE–SEM image (Fig. 4e). The spherical shape of
Fe3O4@SiO2 particles is also confirmed by FE–SEM image (Fig. 4f).
S. Kamari and A. Shahbazi
However, Fe3O4@SiO2 showed a higher average particle size (~13 nm)
in comparison with Fe3O4 MNPs due to the presence of SiO2 surrounding
the Fe3O4 MNPs [12].
As can be clearly seen from the TEM image of Fe3O4@SiO2 (Fig. 4g),
there are two regions with different electron densities; the region with
high electron density with a diameter of ~ 10 nm in the middle, which is
related to Fe3O4 MNPs and the region with lower electron density with a
diameter of ~ 3 nm around the middle region, which is related to SiO2
NFM–1
NFM–2
NFM–3
NFM–4
Fig. 5. Top–surface and cross–sectional (with two different magnifications) FE–SEM images of the fabricated NF–membranes.
7
Chemical Engineering Journal 417 (2021) 127930
coating. This, proves that Fe3O4 MNPs were successfully coated with
SiO2 and Fe3O4@SiO2 core–shell was successfully synthesized with a
fine structure [22].
Based on the results of zeta potential of Fe3O4@SiO2–CS (Fig. 4h),
the isoelectric point of Fe3O4@SiO2–CS bionanocomposite was 3.6.
Therefore, Fe3O4@SiO2–CS could be negatively charged at pH greater
than 3.6. Hence, when the membrane and consequently the nanofiller
particles (Fe3O4@SiO2–CS), which are dispersed all around the
S. Kamari and A. Shahbazi
membrane matrix and on the membrane-pore walls, are in contact with
feed solutions, two layers (electric double layer, EDL) of oppositely
charged ions are made on the surface of nanofiller particles. The inner
layer is called stern (strongly bounded ions) and the outer layer is diffuse
layer (ions loosely bound) [23]. In fact, the voltage at the edge of the
diffuse layer where it meets the surrounding liquid (slipping plane) is
defined as zeta potential [24]. In this study, the pH of feed solution for
treatment of various salts, heavy metals ions and dyes by fabricated
NF–membranes were 7.0, 5.0 and 7.0, respectively, which is higher than
the isoelectric point of Fe3O4@SiO2–CS bionanocomposite. A quite high
value of negative surface charge of Fe3O4@SiO2–CS, which is between
–15.4 and –29.9 mV within the range of studied pH (5–7) implies more
extended surface electric field acting towards the bulk of pore flow, i.e. a
thicker electric double layer enhances the interfacial effect to drag the
cations or reject of anions.
3.2. Characterization of the fabricated NF–membranes
3.2.1. Morphological properties
The morphological properties of the fabricated NF–membranes were
studied using top–surface and cross–sectional FE–SEM images (Fig. 5).
The top–surface FE–SEM image showed the smooth surface of the
membranes without crack or any aggregation of Fe3O4@SiO2–CS, which
indicated that the membrane formation ability remained unchanged
after embedding Fe3O4@SiO2–CS in the membranes matrix [25]. The
cross–sectional FE–SEM image displayed the asymmetrical structure of
the membranes with three sections including (i) a dense selective barrier
on the top surface, (ii) a sub–layer with finger–like structure and (iii) a
bottom with much thicker porous substructure and macro–voids.
Increasing Fe3O4@SiO2–CS loading in the casting solutions up to 0.5 wt
%, increased the finger–like pores of sub–layer of the membranes, which
is due to the change in kinetic and thermodynamic of the system.
Addition of Fe3O4@SiO2–CS in the casting solutions affects the kinetic
and thermodynamic of the phase inversion process by increasing the
mass transfer rate between the solvent and non–solvent phases during
Area of imaging Fe–element map
top–surface
cross–section
Fig. 6. EDX mapping analysis of Fe–element (yellow dots) of top–surface and cross–section of NFM–3 membrane including area of imaging, Fe–element map and
combined image and map. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
8
Chemical Engineering Journal 417 (2021) 127930
the coagulation of the membranes and finally affects the asymmetrical
structure of the membranes through formation of larger pores [26]. In
other words, increasing Fe3O4@SiO2–CS loading in the casting solution
during the phase inversion process results in more water diffusion in the
coagulating membrane due to the presence of hydrophilic amine func­
tional groups on the surface of Fe3O4@SiO2–CS [10]. Therefore,
Fe3O4@SiO2–CS works as a pore modifier and porosity increaser agent.
However, increasing Fe3O4@SiO2–CS loading in the casting solutions
from 0.5 to 1.0 wt% results in increasing the viscosity of the casting
solution and low exchange rate between the solvent and non–solvent
phases and reduces the coagulation rate of the membrane, which finally
results in dense structure with low porosity sub–layer of the membrane
[27]. Therefore, once nanofiller particles are added into the casting
solutions with high concentration can induce the aggregation of nano­
particles (Fig. S1), causing in an imperfect pore formation and decrease
the permeability of membrane [28].
In order to investigate the presence and dispersion of
Fe3O4@SiO2–CS in the membrane structure, the EDX mapping analysis
was performed. The EDX mapping analysis of Fe–element (as the
representative of Fe3O4@SiO2–CS) of top–surface and cross–section of
NFM–3 membrane (Fig. 6) revealed a good spatial distribution of the
nanofiller (yellow dots) within the polymer. This distribution seems
quite homogenous without aggregation in the membrane matrix [29].
3.2.2. Surface hydrophilicity properties
The dynamic water contact angle of the fabricated NF–membranes,
which is representative of their hydrophilicity are plotted in Fig. 7. It
was observed that the initial water contact angle of unblended mem­
brane (NFM–1) sharply decreased from 68.1◦ to 62.9◦ (the reduction of
~ 7.6%) after 60 s. While, the blended membranes (NFM–2, NFM–3 and
NFM–4) not only showed a shorter equilibrium time (<45 s) and lower
reduction of water contact angle after reaching to equilibrium state
(<2%) but also exhibited lower water contact angles, which confirms
their higher surface tendency for wetting. Moreover, the water contact
angle of blended membranes significantly reduced by increasing
Combined image and map
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

70 diameter of fabricated NF–membranes was calculated using MWCO re­

NFM 1
sults and Eq. (S2) [8,15]. The results of the mean pore diameter of
NFM 2
fabricated NF–membranes are summarized in Table 3. It appears that
NFM 3
NFM 4
the mean pore diameter of the blended membranes is greater than for
Water contact angle (°)

65 the unblended membrane. Increasing the loading of Fe3O4@SiO2–CS in

60
55
51
0 10 20 30
Time (s)
Fig. 7. Dynamic water contact angle of the fabricated NF–membranes during
60 s from the moment the water drop reached the surface of the membranes.
Fe3O4@SiO2–CS loading in the membrane matrix and NFM–3 mem­
brane showed the lowest equilibrium state of water contact angle of
51.9◦ . In other words, during the blended membranes formation most of
hydrophilic Fe3O4@SiO2–CS tend to migrate towards top–layer of the
membranes, which reduce the interface energy at the membrane surface
[16,30]. Thus, hydrophilic Fe3O4@SiO2–CS originating from the mem­
branes surface easily absorb water molecules and wet the membrane
surface, resulting in lower water contact angle of the blended mem­
branes. However, the water contact angle slightly increased by
increasing Fe3O4@SiO2–CS loading in the membrane matrix from 0.5 to
1.0 wt%, which may be due to the aggregation of Fe3O4@SiO2–CS in the
membrane matrix (Fig. S1) that strengthens the interface energy at the
membrane surface [16].
3.2.3. Molecular weight cut–off (MWCO) measurement and calculation of
mean pore size
MWCO of fabricated NF–membranes was obtained when the rejec­
tion of PEG (a standard chemical with negligible adsorption onto the
membranes) with different molecular weight of 200, 400, 600, 800 and
1000 Da reached to 90% [15]. The value of MWCO of each membrane
was obtained by interpolation from the MWCO curve, which is a plot of
solute rejection against molecular weight (Fig. 8). The mean pore
110
100
90
PEG rejection (%)
62.9
the casting solution from 0.0 to 0.5 wt% increased the mean pore
diameter from 1.06 to 1.23 nm. This phenomenon is due to the migra­
tion of Fe3O4@SiO2–CS towards top–layer of the membranes during the
coagulation process, which makes the exchange of the solvent and
non–solvent phases faster during the phase inversion process, resulting
56.1 in increased the overall porosity and mean pore radius during the DMAc
and water replacement process [10,27]. However, by increasing
54.1 Fe3O4@SiO2–CS loading in the casting solution from 0.5 to 1.0 wt%, the
51.9
mean pore diameter decreased, which can be due to the agglomeration
of Fe3O4@SiO2–CS (Fig. S1) and increasing the viscosity of the casting
solution that reduces the exchange rate of the solvent and non–solvent
40 50 60 phases and subsequently decreases the overall porosity and mean pore
radius of the membrane [31].
3.2.4. Mechanical properties
The results of measuring the NF–membranes mechanical properties,
which indicates their resistance to the tensile stress are illustrated in
Fig. 9. The mechanical stability of the unblended membrane was typical
inferior with a tensile strength of 8.1 MPa and elongation at break of
4.7%. While, the mechanical stability of the blended membranes was
significantly enhanced by increasing Fe3O4@SiO2–CS loading in the
membranes structure from 0.0 to 0.5 wt%. This is due to the increase in
interconnection density because more interconnection in polymer
network makes less mobility of polymer chains under tensile stress
[10,29]. Rising Fe3O4@SiO2–CS loading in the membrane matrix from
0.5 to 1.0 wt%, however, decreased the membrane mechanical stability,
which is because of the agglomeration of Fe3O4@SiO2–CS (Fig. S1) that
hinders the slippage, growth and interconnection of polymer chains
between Fe3O4@SiO2–CS particles. Therefore, the increase of
Fe3O4@SiO2–CS in the membranes matrix more than 0.5 wt% makes the
membrane more crystalline and fragile [16].
3.2.5. Surface charge properties
The results of surface charge of the fabricated NF–membranes, one of
the most important membrane properties strongly affecting its separa­
tion performance especially for salts rejection, are demonstrated in
Fig. 10. All the membranes indicated negative zeta potential range from
–10 to –52 mV in the pH range of 4–10. It is well established that the
negative surface charge of PES membrane is due to the O = S = O groups
of PES polymer and O = C–N groups of PVP agent [32]. The blended
membranes showed extensive negative surface charge compared with
the unblended membrane. Also, by increasing Fe3O4@SiO2–CS loading
in the membrane structure up to 0.5 wt%, the isoelectric point of related
membrane drifted to a lower pH value, which is predominantly due to
the increasing the amine functional groups of Fe3O4@SiO2–CS

embedded in the membrane matrix [10]. Nevertheless, by increasing

80 Fe3O4@SiO2–CS loading in the membrane structure from 0.5 to 1.0 wt%,
the zeta potential showed a declining trend from –46 to –43 mV (pH of
70 7), which can be because of the aggregation of Fe3O4@SiO2–CS in the
membrane structure (Fig. S1) that weakens the surface charge of the
60
NFM membrane [16,33]. In addition, the charge density on the surface of the
NFM 2 blended membranes increased with increasing Fe3O4@SiO2–CS loading,
NFM 3
50 NFM 4
Table 3
40
MWCO and mean pore diameter of the fabricated NF–membranes.
100 200 300 400 500 600 700 800 900 1000 1100
Membrane code MWCO (Da) Mean pore diameter (nm)
PEG molecular weight (Da)
NFM–1 398 1.06
Fig. 8. PEG rejection of the fabricated NF–membranes (PEG concentration = NFM–2 442 1.12
NFM–3 519 1.23
0.1 g L− 1, PEG molecular weight = 200, 400, 600, 800 and 1000 Da, at pressure
NFM–4 502 1.21
of 0.4 MPa).

9
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

12 12 140
NFM 1
10 10 120 NFM 2

Pure water flux (L m h )

NFM 3

1
Elongation at break (%)
Tensile strength (MPa)

NFM 4

2
8 8
100

6 6
80
4 4
60
2 2

40
0 0
NFM 1 NFM 2 NFM NFM 4
25
Membrane code 0.2 0.4 0.6 0.8

Fig. 9. Mechanical properties (tensile strength and elongation at break) of the

Pressure (MPa)
fabricated NF–membranes (loading speed = 1 mm min− 1).
Fig. 11. Pure water flux of the fabricated NF–membranes under various pres­
sures of 0.2, 0.4, 0.6 and 0.8 MPa.

20
the pure water flux was noticeably enhanced (~1.5 times) with
increasing the dosage of Fe3O4@SiO2–CS from 0.0 to 0.5 wt%, which
was in agreement with the increasing of water contact angle/hydro­
0 philicity (Fig. 7). Actually, the improved hydrophilicity of membranes
Zeta potential (mV)

can enhance water permeability by attracting water molecules inside the

NFM 1 membrane matrix and facilitating them to pass through the membrane
NFM 2
[34]. In addition, increasing the dosage of Fe3O4@SiO2–CS in the
-20 NFM 3
membrane matrix considerably enhanced the loose degree of blended
NFM 4
membranes and generate more porous voids (Table 3), which resulted in
higher pure water flux [27]. However, with a further increase of the
-40 Fe3O4@SiO2–CS content (1.0 wt%; NFM–4), water permeability was
reduced compared with NMF–3. This phenomenon could be due to the
partially agglomeration of nanofiller particles and the resulted abste­
miously closure of water’s pathway by them [35].
-60
2 3 4 5 6 7 8 9 10 3.3.2. Desalination, heavy metals ions removal and dyes retention
pH
3.3.2.1. Desalination. In order to investigate the performance of fabri­
Fig. 10. Zeta potential analysis of the fabricated NF–membranes at various pH
cated NF–membranes for nanofiltration applications, the single–solute
values of 2–10.
filtration of four types of salts solutions including Na2SO4, MgSO4, NaCl
and MgCl2 were tested. Fig. 12 portrays the desalination performance of
which is due to the migration of negatively charged Fe3O4@SiO2–CS the membranes. Generally, in all the membranes the salt rejections
towards top–layer of the membranes [16].

100
Na2SO4
3.3. Filtration performance of the fabricated NF–membranes
MgSO4
80 NaCl
3.3.1. Effect of pressure on pure water flux
MgCl2
Besides membrane properties, the operating conditions such as
operating pressure has crucial influence on membranes pure water flux
60
and separation performance. Hence, the effect of operating pressure
R (%)

(0.2, 0.4, 0.6 and 0.8 MPa) on the pure water flux of the fabricated
NF–membranes were studied (Fig. 11). It is clearly observed that pure
40
water flux of all the NF–membranes linearly increased by increasing the
operating pressure from 0.2 to 0.8 MPa [16]. Nevertheless, the slop of
this growth was different for various fabricated NF–membranes. For
20
NFM–3, which showed the most satisfactory permeability, the pure
water flux was enhanced at least 2.7 times (from 45.3 to 122.7 L m–2h− 1)
by the quadrupling the operating pressure (from 0.2 to 0.8 MPa). In each 0
pressure, the highest and lowest pure water flux was related to NFM–3 NFM 1 NFM 2 NFM NFM 4
and NFM–1, respectively. For example, at the pressure of 0.4 MPa, the
Membrane code
highest and the lowest pure water flux was related to NFM–3 (70.6 L
m–2h− 1) and NFM–1 (47.3 L m–2h− 1) membranes, respectively. Gener­ Fig. 12. Desalination of the fabricated NF–membranes for various salt solutions
ally, the water permeability is mainly related to hydrophilicity and pore of Na2SO4, MgSO4, NaCl and MgCl2 (salts concentration = 0.5 g L–1, pH = 7 ±
structure of composite membranes [10]. In this case, it was found that 0.1, 0.4 MPa, at room temperature, 120 min).

10
S. Kamari and A. Shahbazi
follow the order of Na2SO4 (~90%) > MgSO4 (~60%) > NaCl (~20%)
> MgCl2 (~10%), which greatly corresponds to the rejection order of
NF–membranes with negative surface charge [2]. Indeed, the embed­
ment of negatively charged Fe3O4@SiO2–CS in the membranes structure
enhanced the negative charge density of the membranes surface, which
is approved by zeta potential analysis (Fig. 10). As a result, based on the
electrostatic repulsive interaction mechanism (Donnan exclusion), the
anion valence mainly governs the solute rejection in negatively charged
NF–membrane, i.e. divalent anions (SO24) are strongly repulsed by the
membrane whereas monovalent anions (Cl–) show lower rejections. So
that, the sulfate containing salts could be rejected more than chloride
containing salts. Therefore, the order of the rejections, (Mg/Na)–SO4 >
(Mg/Na)–Cl, corresponds to the decreasing order of the anion valence or
in other words weaker anion repulsion forces [36]. Also, according to
the sieving effect, the hydrated radius of SO2–4 by 3.8 Å is greater than Cl
–
by 3.3 Å (Table 2), which could be the other reason for high rejection of
sulfate salts. The order of the rejections of Na2SO4 > MgSO4 and NaCl >
MgCl2 can be interpreted based on the increasing order of the cation
charge density. The cation charge density (ρ) is defined as the amount of
electric charge per unit volume (ρ = q/(4/3 πr3), where q is the cation
charge and r is the ionic radius (Å) [37]). In this case, the attraction
forces of negatively charged NF–membrane on the Mg2+ are stronger
than Na+ due to its higher charge density (1.66 vs. 0.26), which results in
its lower rejection. For better interpretation of desalination process the
separation mechanisms of NF–membrane is depicted in Fig. 16b.
3.3.2.2. Heavy metals ions removal. The single–solute filtration of three
types of heavy metals ions solutions including Pb2+, Cu2+ and Cd2+ was
employed to evaluate the efficiency of the fabricated NF–membranes for
treatment of polluted waters with heavy metals ions (Fig. 13). Based on
the results, the NFM–3 membrane by 98.11, 98.61 and 98.86% for Pb2+,
Cu2+ and Cd2+, respectively, presented the highest removal of heavy
metals ions and the lowest removal of heavy metals ions by 14.95, 15.45
and 16.11% for Pb2+, Cu2+ and Cd2+, respectively, was relevant to
NFM–1 membrane. The reasons for significantly enhancement of heavy
metals ions removal by blended membranes in comparison to unblended
one could be discussed in the following: (i) basically, soft metals (such as
Pb2+, Cu2+ and Cd2+), which are generally toxic preferably tend to
create covalent/stable bonds with nitrogen–containing (soft donor
atom) ligands [38]. Therefore, the embedment of Fe3O4@SiO2–CS in the
membranes matrix leads to the formation of stable complex of M2+–NH2
between the soft heavy metals ions and amine functional groups of
Fe3O4@SiO2–CS on the blended membranes surface; this causes the
100
Pb2+
Cu2+
Cd2+
80
60
R (%)
40
20
0
NFM 1 NFM 2 NFM NFM 4
Membrane code
Fig. 13. Heavy metals ions removal of the fabricated NF–membranes for
various heavy metals ions solutions of Pb2+, Cu2+ and Cd2+ (heavy metals ions
concentration = 0.1 g L–1, pH = 5 ± 0.1, 0.4 MPa, at room temperature,
120 min).
11
Chemical Engineering Journal 417 (2021) 127930
heavy metals ions to be chelated and removed (Fig. 16b), (ii) increasing
Fe3O4@SiO2–CS loading in the membranes matrix makes the blended
membranes to show more negative surface charge (Fig. 10), resulting in
increasing the electrostatic exclusion of the positively charged heavy
metals ions with the negatively charged blended membranes surface and
consequently increases the removal of the heavy metals ions, and (iii)
the pore radius of the membranes directly affects the removal of the
heavy metals ions, which is in the order of Pb2+ < Cu2+ < Cd2+ for the
heavy metals ions removal based on their hydrated radius (Table 2),
even though, it can be concluded that both adsorption properties and
electrostatic exclusion of the blended membranes are responsible for
removing the heavy metals ions; thus, the blended membranes with
larger pore radius showed higher removal of the heavy metals ions in
comparison with the unblended membrane with smaller pore radius [3].
On the other hand, by increasing Fe3O4@SiO2–CS loading in the mem­
brane matrix from 0.5 to 1.0 wt%, the removal of the heavy metal ions
showed a slight decrease, which may be due to the possible aggregation
of Fe3O4@SiO2–CS (Fig. S1) and the decrease of its effective surface area
and subsequently the decrease of its available active adsorption sites.
3.3.2.3. Dyes retention. The performance of the fabricated NF–mem­
branes for retention of three types of dyes solutions including MB, CR
and RB5 was studied using single–solute filtration (Fig. 14). All the
membranes demonstrated a high dyes retention by more than 98.2% for
all the tested dyes in the order of MB < CR < RB5. The high retention of
anionic dyes can be explained by various factors. Firstly, the molecular
weight of studied anionic dyes (CR = 696 Da and RB5 = 991 Da; Table 2)
is higher than the value of MWCO of all the membranes (398–519 Da;
Fig. 8 and Table 3), so the retention of anionic dyes is mainly caused by
steric exclusion (size exclusion) and approves that the pore diameter of
the membranes is typically smaller than the effective hydrodynamic size
of the dyes [8,15]. Secondly, the negative charge of the membranes
surface (Fig. 10) owing to the Donnan exclusion (Fig. 16b) could
effectively enhance the retention of negatively charged dyes of CR and
RB5 [7]. For MB cationic dye with molecule weight of 319 Da (lower
than the MWCO of membranes), it is reasonable to hypothesize that the
high negative charge on the surface of membranes (from –34 to –46 mV)
and consequently Donnan exclusion, as well the adsorption of MB
molecules by negatively charged nanofillers are the main reasons of high
retention of MB by the membranes. It is worth noting that among the
membranes, the highest dye retention was observed by NFM–3 mem­
brane as 98.47, 98.49 and 98.50% for MB, CR and RB5, respectively.
While, as Fe3O4@SiO2–CS loading in the membranes matrix increased
from 0.5 to 1.0 wt%, the dyes retention decreased slightly, possibly due
98.50
98.45
98.40
R (%)
98.35 MB
CR
RB5
98.30
98.25
NFM 1 NFM 2 NFM NFM 4
Membrane code
Fig. 14. Dyes retention of the fabricated NF–membranes for various dyes so­
lutions of MB, CR and RB5 (dyes concentration = 0.2 g L–1, pH = 7 ± 0.1, 0.4
MPa, at room temperature, 120 min).
S. Kamari and A. Shahbazi
to the changes in the membrane surface charge [4].
In general, the NFM–3 membrane with excellent pure water flux,
good salts rejection, high heavy metals ions removal and great dyes
retention was selected as optimum membrane for further examinations
as follow.
3.3.3. Effect of salt/heavy metal ions/dye concentration
The performance of the fabricated NF–membranes for treatment of
wastewaters containing various concentrations of pollutants were
examined by single–component filtration of solutions containing various
concentrations of Na2SO4, Pb2+ and MB using NFM–3 membrane
(Fig. 15). The rejection of Na2SO4 was decreased from 94.2 to 80.5% by
increasing the salt concentration from 0.1 to 5.0 g L–1, which may be
because of the prolongation of the electrostatic interaction Debye length
between the charged ions and the membrane [7]. In other words, by
tenfold increasing of salt concentration, the cations shield effect on the
negatively charged membrane becomes progressively stronger, leading
to the decrease of the membrane repulsion forces on the anions,
resulting in the salt rejection decrease (~15%) [36]. The results indicate
that by twenty times increasing of Pb2+ concentration (from 0.01 to 0.2
g L–1), the removal of Pb2+ was approximately constant (98.11%)
without significant change. This fact can be attributed to the high
adsorption properties of Fe3O4@SiO2–CS embedded in the membrane
matrix and the electrostatic exclusion of the membrane. Based on the
results, the increasing MB concentration from 0.05 to 1.0 g L–1 (twenty
times) had a limited effect on its retention by 98.47% approximately for
all the tested concentrations. As mentioned previously, MB is a cationic
dye with smaller molecule size than NFM–3 membrane MWCO (319 vs.
519 Da) in which the Donnan exclusion and adsorption through
embedded nanofiller particles in the membrane matrix are the most
important factor in its high removal during NF process (Fig. 16b) Thus,
by increasing dye concentration, MB molecules progressively accumu­
late in the boundary layer of membrane; consequently the local con­
centration of dye in the boundary layer increases and improves steric
exclusion effect, which results in approximately constant dye retention
[39].
3.3.4. Multicomponent filtration: Effect of Na2SO4 concentration on Pb2+/
MB mixture rejection
To evaluate the efficiency of the fabricated NF–membranes for
treatment of real wastewaters, which simultaneously contain various
pollutants, multicomponent solutions containing Na2SO4 with various
Na 2SO4 concentration (g L 1)
0.1 0.25 0.5 1 5
100
95
Na2 SO4
Pb2+
MB
90
R (%)
85
80 Pb2+ concentration (g L 1)
0.01 0.05 0.1 0.15 0.2
77
0.05 0.2 0.5
0.1 1
1 the rejection was almost constant and fluctuated between 90.1 and
MB concentration (g L )
Fig. 15. Effect of Na2SO4, Pb2+ and MB concentration on NFM–3 membrane
filtration performance.
12
Chemical Engineering Journal 417 (2021) 127930
concentrations, and Pb2+ and MB with constant concentrations were
filtered using NFM–3 membrane (Fig. 16a). The results showed that with
increasing Na2SO4 concentration in the mixed feed solution from 0.1 to
1 g L–1, the removal of Pb2+ and retention of MB slightly reduced from
98.45 to 97.75% and 99.07 to 98.25%, respectively. These salt effects
could be explained by different mechanisms. Firstly, the high concen­
trations of Na2SO4 weaken the electrostatic interaction of the membrane
with salts ions accumulated on the membrane boundary layer; this re­
sults in increasing the interaction distance between the membrane sur­
face and the electrolytes in the feed solution and consequently reduces
its retention. Secondly, as many researchers reported [7,40–42], the
significant decreasing of membrane retention with high increasing of
salt concentration could be explained by membrane swelling hypothesis
in which membrane pores are supposed to be more open due to mem­
brane swelling by salt and facilitate the passage of Pb2+ and MB through
the membrane. In this case, membrane swelling occurred due to the
stronger repulsive interaction between ions with same charge inside the
pores when salt was added, implies that electrostatic effect was
enhanced with increasing of salt concentration [40,42]. It can also be
found that Na2SO4 rejection of NFM–3 membrane in the single­
–component and multicomponent solutions was similar, which displays
that the presence of heavy metals ions and dyes in the solution had not a
significant effect on the salt rejection. It is worth mentioning that even at
the highest Na2SO4 concentration (5 g L–1), NFM–3 membrane showed a
97.25% removal for Pb2+ and 98.03% retention for MB, demonstrating
its high potential for treatment of real wastewaters simultaneously
containing salts, heavy metals ions and dyes. In order to summarize all
the effects on simultaneous rejection of salt/heavy metal ions/dye, the
mechanisms diagram is demonstrated in Fig. 16b.
3.3.5. Reusability and long–term filtration
In order to examine the capability of the fabricated NF–membranes
for industrial applications, the reusability of NFM–3 membrane was
assessed by five continuous cycles of single–component filtration of
Na2SO4, Pb2+ and MB solutions. The reusability of NFM–3 membrane for
five continuous cycles is demonstrated in Fig. 17a. The effect of
consecutively cyclic filtration on the salt separation performance
showed that the salt rejection decreased by ~ 7% (90.1 to 83.1%) from
the 1st to the 5th cycle, which is probably because of the weakening the
electrostatic exclusion of the membrane due to the repeated use. The
same results were obtained for Pb2+ removal. In this case, a decrease of
~ 5% (98.11 to 93.58%) was observed from the 1st to the 5th cycle,
which is possibly because of the occupation of the adsorption active sites
on Fe3O4@SiO2–CS embedded in the membrane structure by the ions
not released from the previous cycle. Regarding MB, the retention of
98.47% decreased to 92.38% from the 1st to the 5th cycle (a decrease of
~ 6%), which is probably due to the dilation of pore size of the mem­
brane because of the recovery and reuse [3]. It worth mentioning that
the loss of Fe3O4@SiO2–CS from membrane matrix was controlled
during cycling filtration by Fe–measuring in permeate using atomic
absorption spectroscopy (AAS; Agilent 240Z/280Z equipped with
furnace). The results showed that all permeate did not contain Fe–ele­
ment. This fact proved that the Fe3O4@SiO2–CS nanofiller was not
released from the membrane matrix during cycling filtration. The results
of NFM–3 membrane reusability confirmed it as promising candidate for
consecutively cyclic filtration of pollutants without a tangible loosing of
the separation capability.
In order to verify the stability of the fabricated NF–membranes for
long–term treatment of wastewaters, a continuous 120 h single­
–component filtration of Na2SO4, Pb2+ and MB solutions was conducted
using NFM–3 membrane. The Fig. 17b depicts the long–term filtration of
NFM–3 membrane. For Na2SO4, during 120 h of continuous filtration,
90.7%. Also, the salt solution flux remained virtually unchanged of ~
70.4 L m–2h− 1, which illustrated that the electrostatic exclusion of the
membrane is stable in the long–term filtration. Regarding Pb2+, the
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

Na 2SO4 concentration (g L 1)
0.1 0.25 0.5 1 5
100

95
Na2 SO4
Pb2+
MB

R (%)
90

85 (a)
Pb2+ concentration (g L 1)
0.1 0.1 0.1 0.1 0.1
80
0.2 0.2 0.2 0.2 0.2
1
MB concentration (g L )

Fig. 16. (a) Multicomponent filtration efficiency of NFM–3 membrane for simultaneous Na2SO4, Pb2+ and MB solutions and (b) membrane separation mechanisms of
rejection of salt/heavy metal ions/dye.

removal fluctuated in the range of 98.11 and 98.71% and did not show a
significant decrease over 120 h of continuous filtration. Heavy metal
ions solution flux remained approximately unchanged ~ 69.9 L m–2h− 1,
exhibiting good interaction of the amine functional groups of
Fe3O4@SiO2–CS on the membrane surface with the ions. Concerning
MB, the retention slightly increased during 120 h of continuous filtration
and reached from 98.47 to 99.57% while dye solution flux gradually
decreased from 69.6 to 64.6 L m–2h− 1. This may be due to the solution
concentration polarization caused by dye molecules accumulation on
the membrane surface, thereby increases the filtration resistance [16].
The results of long–term filtration of NFM–3 membrane proved its high
stability, promoting further applications in industrial wastewaters
treatment.
3.3.6. Antifouling properties
In order to estimate the life time and maintenance costs of the
fabricated NF–membranes for real wastewater treatment, their anti­
fouling properties was examined using BSA solution filtration
(Fig. 18a–c). In comparison, by switching the feed solution from DIW to
BSA solution, the BSA solution flux of all the membranes abruptly
decreased and stabled over the second 120 min of filtration (Fig. 18a),
which may be because of the protein accumulation on the membranes
surface and blocking the membranes pores [15]. Afterwards, by washing
and cleaning the membranes and switching the feed solution from BSA
solution to DIW, the pure water flux of all the membranes during the
third 120 min of filtration was partially recovered, among which the
recovered pure water flux of NFM–3 membrane was the highest. As
shown in Fig. 18b, the FRR of the unblended membrane (NFM–1) was
only 40.3% while that of NFM–2, NFM–3 and NFM–4 membranes were
much higher by 82.6, 93.2 and 88.3%, respectively. Therefore, during
the entire filtration process, the FRR of NFM–3 membrane was higher
than the other membranes, showing its excellent antifouling properties,
which may be due to the change in the membrane surface chemistry
caused by embedding Fe3O4@SiO2–CS in the membrane structure. In
this way, the hydrophilic amine functional groups of Fe3O4@SiO2–CS
located on the membrane surface create the hydrogen bond with water

13
S. Kamari and A. Shahbazi Chemical Engineering Journal 417 (2021) 127930

120
(a)
Na2SO 4 80 (a)
Pb 2+ DIW BSA solution DIW

Water permeation flux (L m h )

1
100 MB

2
80 60
R (%)

60

40
40

NFM 1
20
NFM 2
20
NFM 3
0 NFM 4
1 2 3 4 5
Cycle number 5
0 100 200 300 360

100 100
Time (min)

Water permeation flux (L m h )

1
100
2
90 90
(b)
80
Na2 SO4
R %)

80 Pb2+ 80
MB
FRR (%) 60

70 70
40
(b)
62 62
0 20 40 60 80 100 120 20
Time (h)

Fig. 17. (a) Reusability for five continuous filtration cycles and (b) long–term 0
filtration for 120 h continuous filtration of NFM–3 membrane for Na2SO4, Pb2+ NFM 1 NFM 2 NFM NFM 4
and MB.
Membrane code

molecules and form a continuous layer of water on the membrane sur­ 80

face, which hinders absorption of foulant on the membrane surface.
(c) Rt
More detail of the membranes antifouling properties including total Rr
fouling ratio (Rt), reversible fouling ratio (Rr) and irreversible fouling
Rir
ratio (Rir) are provided in Fig. 18c. The relevant results demonstrated 60
Fouling resistance (%)

that the Rr of the blended membranes was higher and Rt and Rir of them
were lower than that for unblended membrane. The Rt and Rir of un­
blended membrane were 70.6 and 59.8%, respectively, and in the best
40
case significantly reduced to 50.8 and 6.8% for NFM–3 membrane,
depicting its excellent behavior for real wastewater treatment.

4. Conclusions 20

In this study, the high hydrophilic and amine-rich Fe3O4@SiO2–CS

bionanocomposite was synthesized and applied as nanofiller for modi­
fication of PES–nanofiltration membrane to enhance its filtration effi­ 0
NFM 1 NFM 2 NFM NFM 4
ciency for retention of salts, heavy metal ions and dyes. All well–known
characteristic methods including XRF, XRD, FT–IR, VSM, FE–SEM, EDX, Membrane code
zeta potential, and TEM successfully proved the authenticity and reli­
Fig. 18. (a) Time–dependent permeated water flux (0 to 120 min first pure
ability of physico–chemical properties of the synthesized bio­
water flux, 120 to 240 min BSA solution flux and 240 to 360 min second pure
nanocomposite and the fabricated NF–membranes. The results indicated water flux), (b) FRR (flux recovery ratio) and (c) fouling resistance (Rt, Rr and
that by increasing the loading of nanofiller in the membrane matrix from Rir) of the fabricated NF–membranes.
0.0 to 0.5 wt%, the negative charge of the membranes surface, mean
pore diameter, tensile strength and elongation at break increased by ~ the membranes significantly increase of about 1.5 times (from 47.3 to
35%, ~16%, ~20%, ~25% and ~ 45%, even though, the water contact
70.6 L m–2h–1L). Based on the desalination results, in all membranes the
angle showed a decrease of about 17%. Furthermore, the results of salt rejections follow the order of Na2SO4 (~90%) > MgSO4 (~60%) >
filtration experiments demonstrated that by increasing the loading of NaCl (~20%) > MgCl2 (~10%) and the Donnan exclusion was the
nanofiller in the membranes matrix up to 0.5 wt%, the pure water flux of dominant mechanism in the rejection of salt. In comparison with

14
S. Kamari and A. Shahbazi
unblended membrane, the removal percentage of studied heavy metal
ions (Pb2+, Cu2+ and Cd2+) significantly increased by blending of 0.5 wt
% of amine-rich Fe3O4@SiO2–CS nanofiller in the membrane matrix
(14.95% vs. 98.11%, 15.45% vs. 98.61% and 16.11% vs. 98.86%). The
main reason for this evidence is most probably due to the development
of stable bonds between soft metal ions in the feed solution and nitrogen
atoms in the chitosan structure of Fe3O4@SiO2–CS nanofiller on the
membrane surface. The high retention of anionic dyes (BR5 and CR;
~98.2%) with molecular weight of higher than MWCO of membranes is
mainly caused by both steric exclusion and Donnan exclusion mecha­
nisms. Although, in the case of MB, cationic dye with molecular weight
of lower than MWCO of membranes both, Donnan exclusion and
adsorption of MB molecules by negatively charged nanofillers on the
membrane surface are the main reasons for high retention of MB by
fabricated membranes. Considering all the analyses and results (i.e.
desalination, heavy metals ions removal, dyes retention), the most sig­
nificant achievement here is the remarkable capability of both blended
and unblended membranes for removal of heavy metals ions (i.e., 98.1%
vs. 14.9% for Pb2+) that could be due to high affinity of amine-
containing nanofillers for adsorption/chelating of heavy metal ions.
The ideal membrane (NFM–3) illustrated excellent performance in
filtration of pollutants with various concentrations, multicomponent
filtration, reusability and long–term filtration. In general, the fabricated
NF–membrane in this study is proved to be an efficient, biocompatible
and low–cost membrane for water and industrial wastewaters treatment
polluted with inorganic salts, heavy metals ions and organic dyes, and
can be applied for various environmental applications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
The authors wish to thank Shahid Beheshti University (SBU) that has
financed this research work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2020.127930.
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