Journal of Environmental Management 294 (2021) 112918

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Journal of Environmental Management

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

Research Article

Fabrication of chitosan-aminopropylsilane graphene oxide nanocomposite

hydrogel embedded PES membrane for improved filtration performance
and lead separation
Saba Amiri a, Alireza Asghari a, *, Vahid Vatanpour b, **, Maryam Rajabi a
a
Department of Chemistry, Semnan University, Semnan, 2333383-193, Iran
b
Department of Applied Chemistry, Faculty of Chemistry, Kharazmi University, 15719-14911, Tehran, Iran

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

Keywords: In the present study chitosan-aminopropylsilane graphene oxide (CS-APSGO) nanocomposite hydrogel was
Nanofiltration membrane synthesized and utilized as a hydrophilic additive in different dosages (0.5, 1, 2 and 5 wt%) in fabrication of
Nanocomposite hydrogel porous polyethersulfone (PES) membranes via the phase inversion induced process by immersion precipitation
Heavy metal removal
method for heavy metal ion and dye removal. The modified membranes were characterized using ATR-FTIR,
Dye wastewater
AFM, SEM, water contact angle, overall porosity and mean pore radius evaluations and zeta potential mea­
Antifouling
surement. The addition of CS-APSGO nanocomposite hydrogel to PES doping solutions enhanced membranes
hydrophilicity and consequently pure water flux permeability. Filtration performance of the CS-APSGO
embedded membranes showed promising antifouling properties during BSA filtration test (FRR> 90%) and 1
wt% membranes showed the highest pure water flux of 123.8 L/m2 h with BSA rejection more than 98% and
removal capability more than 82% for lead (II) ion, 90.5% and 98.5% for C.I. Reactive Blue 50 and C.I. Reactive
Green 19, respectively. Therefore, the CS-APSGO nanocomposite hydrogel blending in order to modification of
PES-based membranes have a noticeable potential in improving filtration performance of blended membranes.

1. Introduction to significant damage to aquatic living organisms and poison their biota
even at low concentrations. So, proper treatment of water containing
Growing industrialization and urbanization which, accelerate the dyes and heavy metal ions before discharging in freshwater resources is
industrial emissions comprising hazardous organic and inorganic pol­ of high scientific and practical importance (Kumari et al., 2017). Various
lutants have taken people’s attention on increasing demand for eco- procedures such as chemical precipitation (Alvarez et al., 2007),
friendly purification and reuse of wastewater in order to provide high adsorption (Cui et al., 2015), flotation (Taseidifar et al., 2019), ion ex­
quality and sustainable water (Li et al., 2018). Inorganic heavy metal change (Wong et al., 2014), reverse osmosis (RO) (Tong et al., 2017),
iones and organic dyes are known as the major sources of water pollu­ evaporation (Kekesi et al., 1995), and membrane filtration (Divrikli
tion (Yang et al., 2018). Unlike organic contaminants, the dissolved et al., 2007) have been extensively applied for heavy metal ions removal
heavy metal ions themselves cannot degenerate into less-or-non-toxic including lead ions by toxic nature from wastewater. Although several
specimens and cause severe health problems by interaction with living physico-chemical techniques have been studied for efficient dye elimi­
organisms through the food chain (Godiya et al., 2019). For instance, nation, some defects such as nonspecific interactions, limited reus­
lead (II) ions are toxic heavy metal ions which accumulate and retain in ability, and high preparation cost restrict wide industrial application of
the body and indicate mutagenic and carcinogenic properties. These these traditional method (Donkadokula et al., 2020; Mohan et al., 2007).
ions simply bind by nucleic acids, proteins, and small metabolites to Nowadays, membrane-based process as a significant solution for
block their biological roles and cause serious harm to liver, kidneys and advanced physical wastewater treatment is playing sufficiently
the reproductive and nervous system (Jones, 2012). On the other hand, remarkable role in water industry due to its advantages including
release of untreated synthetic dye wastes into the environment can lead modular nature, which provide flexibility in designing, application

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (A. Asghari), [email protected] (V. Vatanpour).

https://doi.org/10.1016/j.jenvman.2021.112918
Received 11 December 2020; Received in revised form 20 April 2021; Accepted 10 May 2021
Available online 15 June 2021
0301-4797/© 2021 Elsevier Ltd. All rights reserved.
S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

possibility at very large or small scale, high quality of the filtered water, 2011). Hydrogel modified membranes via photo-initiated grafting of
the almost slight footprint and in some cases less energy consumption polyethylene glycol methylether methacrylates (PEGMEMA) based
(Zioui et al., 2015). Different membrane types from finely porous hydrogel layer on polyamide composite membranes indicated higher
structures to nonporous with a different separation ranges including hydrophilicity and fouling resistance compared to the unmodified
microfiltration (MF), ultrafiltration (Fu et al., 2020), nanofiltration membranes (Lei and Ulbricht, 2014).
(Zhang et al., 2015) and RO are available and used in membranes pro­ Incorporation of hydrogel compatible nanoparticle such as graphene
cess to eliminate contaminants such as bacteria and protozoa down to oxide (GO) nanosheets in hydrogel polymeric network not only lead to
dyes and ions (Doménech et al., 2020). NF with membranes properties in mechanical reinforcement, but also due to presence of a large surface
between range of UF and RO has made a lot of progress since it was first area with abundant oxygen containing reactive groups, could increase
introduced during the late 80’s and has attracted growing importance in hydrogel adsorption capacity (Yu et al., 2018). Blending some bio-based
water softening and wastewater purification by many researchers nanocomposite hydrogels with adsorptive polymers was utilized to
(Mohammad et al., 2015). NF separation process is considered as utili­ prepare composite membranes with improved separation properties in
zation of a high pressure-driven method with 0.5–10 nm of membrane treatment of heavy metals and dyes wastewater (Bahram et al., 2016). In
pore size and 5–40 bar of operating pressures in order to separation of our previous work, we fabricated hydrophilic PVA-GO-SA hydrogel
pesticides, herbicides, sugars, proteins, liquid droplets, dyes, heavy (HG) and then studied the blending effects of this additive on the
metal ions and microorganisms (Doménech et al., 2020). In addition of modified PES based NF membranes filtration performance. High hy­
important properties belonging to NF membranes such as higher flux drophilicity and permeability and also superior antifouling character­
than RO membranes, high permeation to monovalent ions and low istics was reported for PES/HG blended NF membranes in comparison
permeation to divalent ions, these types of membranes due to providing with the pristine PES membranes (Amiri et al., 2020).
longer cycle times and therefore lower operation costs offer advantages Chitosan (CS) is a linear cationic polysaccharide, the second most
over other membranes and increased process reliability and accuracy nature accessible biopolymer that produced commercially by deacety­
(Mohammad et al., 2015). lation of chitin, which is existed in crustacean’s exoskeleton and fungi
Membrane fouling is one of the most significant concerns for mem­ cell walls (Konwar et al., 2015). CS-based hydrogels applicability in
brane technology, which generally occurs in forms of foulant adhesion/ composite membranes for the elimination of toxic components, heavy
deposition (Wu et al., 2020; Long et al., 2020; Li et al., 2020; Liu et al., metals and dyes removal from different effluents is related to existence
2020). As with all membrane-based separation processes, fouling phe­ of multiple amino (NH2) and hydroxyl (OH) reactive functional groups
nomenon which is the accumulative deposition of the typical foulants (Nangia et al., 2018). The combination of CS-based hydrogels with
including inorganic solutes, organic solutes, colloids, or biological solids suitable substances such as aminosilanes, amino acid esters, ethylene
onto membrane surface and inside the membrane pores can hinder the diamine, aromatic polyimides, various nanomaterials such as Ag, ZnO,
broader implementation of NF and results in the permeate flux decline, CNT, GO nanomaterials and so on have found remarkable attention in
selectivity change, shorter membrane lifespan and drop in membrane order to improved their adsorption performances and mechanical
productivity (Zahid et al., 2018). Due to hydrophobic nature of the resistance (Wang et al., 2013).
traditional membrane materials such as polysulfone (PSf) and poly­ Combination of nanocomposite hydrogel adsorbent with membrane
ethersulfone (PES), the polyarylsulfone membranes are more susceptible filtration method with the aim of nanocomposite membrane preparation
to fouling. So various appropriate studies on membrane preparation offers dual functionality of filtrating and adsorbing in water contami­
have been dedicated to solve these problems and mitigate fouling phe­ nant removal and application of the nanocomposite hydrogel in the
nomenon by using innovative modification techniques in order to polymeric membrane modification brought a new insight in water pu­
fabrication of fouling resistant membranes (Ganjali et al., 2020). Much rification (Nasir et al., 2019).
efforts have been done in case of polyarylsulfone membranes surface Cross-linked chitosan hydrogel grafted with APSGO adsorbent was
modification via following strategies: (1) coating (Xia et al., 2020), (2) exhibited efficient function for Pb(II) adsorption in aqueous medium due
grafting (Zhang et al., 2020), (3) chemical (Yalcinkaya et al., 2020), (4) to existence of high surface concentration of active-sites (-NH2/ = NH)
blending (Bai et al., 2020), (5) composite (Wang et al., 2020), or (6) which was responsible for the adsorption (Sharma et al., 2018). On the
combined methods (Shah et al., 2021). When appropriate conditions are other hand, addition of CS-APSGO to the membranes casting solution as
applied, all mentioned methods make membranes surface modification a nanocomposite hydrogel possess hydrophilic nature was expected to
possible without affecting the bulk properties extremely. It should be improve membrane hydrophilicity and consequently permeation and
mentioned that perfect and apparently permanent hydrophilic modifi­ antifouling properties of the blended PES membranes (Amiri et al.,
cation of polyarylsulfone membranes are available by photoinduced 2020). These are two main reasons for synthesizing and using CS-APSGO
grafting and blending through reducing foulants adsorption at the ob­ nanocomposite hydrogel as a hydrophilic additive in modification of
tained hydrophilic surfaces (Nady et al., 2011; Zahid et al., 2018). PES membranes.
Hydrogels are known as a water-swollen three-dimensional (3D) To the best of our knowledge, expect our previous work (Amiri et al.,
network of hydrophilic polymers chains which can hold a large amount 2020), which PVA and sodium alginate coated GO was used for pre­
of water in aqueous media with structure preservation due to presence of paring PES membrane for dye removal, there isn’t any study about
chemical crosslinks or physical junction and entanglements (Yuan et al., blending method of nanocomposite hydrogel in PES membrane matrix
2019). Because of the particular hydration nature of the hydrogel, they and bio-based CS-APSGO nanocomposite hydrogel has not been used in
can improve the antifouling property and tune barrier properties of modification of PES NF as a hydrophilic additive.
membranes (e.g., permeation, rejection and selectivity) via filling or In the present study, first GO nanosheets were synthesized via
narrowing the membranes pores. Investigation of hydrogel usage in the improved Hummer’s method and then functionalized with synthesizing
preparation of polymeric membranes with the aim of wastewater aminopropylsilane graphene oxide (APSGO) through condensation re­
treatment has been done in several literatures (Ji et al., 2018). The 3D action. Cross-linked CS hydrogel grafted with APSGO was formed with
GO-based nanostructure hydrogel membranes have been fabricated sol-gel stratagem in acidic medium in attendance of glutaraldehyde
through vacuum filtration method and remarkable water stability and crosslinker agent (Sharma et al., 2018). The resulted
efficiency in diverse pollutants separation were reported (Chen et al., chitosan-aminopropylsilane GO nanocomposite hydrogel (CS-APSGO)
2019). was added into a PES membrane matrix as a hydrophilic nanofiller and
Due to hydrophilicity and sieving properties of polymeric hydrogels, PES/CS-APSGO blended NF membranes were prepared via the
the membranes via combinations of these substances with adsorptive non-solvent induced phase separation (NIPS) technique. It was predicted
polymers indicated improved separation performance (Yang et al., that hydrophilic nanocomposite hydrogel blending with PES membrane

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

matrix resulted to membrane’s performance improvement through hy­ followed by chemical crosslinking in attendance of glutaraldehyde.
drophilicity reinforcement of the modified membranes. Filtration per­ Under stirred condition, a 2 w/w% viscous solution of chitosan in
formance of the membranes was examined by separation of Lead (II) and deionized water comprising acetic acid (2 v/v%) was prepared. The
Reactive Blue 50 and Reactive Green 19 dyes solutions. Antifouling synthesized APSGO (0.5%, w/w) from previous step was added to the
characteristics of the modified PES/CS-APSGO membranes were inves­ mentioned solution and ultrasonicated for 30 min to assure the good
tigated with bovine serum albumin (BSA) solution filtration. homogeneity and then were kept under continuous stirring condition at
30 ◦ C for 24 h. The obtained CS-APSGO solution was suspended in a 200
2. Materials and methods mL mixture of chlorobenzene: Span-80: toluene (3:1:1) below vigorous
stirred condition for a period of 8 h at 30 ◦ C. Then, the reaction mixture
2.1. Materials heated up to 90 ◦ C for next 8 h under stirring. After cooling the mixture
to room temperature, glutaraldehyde (2 w/w%) was added to the
Graphite powder (powder, 99% carbon basis, − 325 mesh particle mentioned solution and stirred at 30 ◦ C for 8 h. The resulted cross-linked
size (>99%), natural), phosphoric acid (H3PO4, 85%), sulfuric acid CS-APSGO hydrogel was separated by filtration and rinsed multiple
(H2SO4, 98%), hydrogen peroxide (H2O2, 30% (w/w) in H2O, contains times with acetone continued by DI water, and eventually neutralized by
stabilizer), potassium permanganate (KMnO4), hydrogen chloride ® NaOH solution. The synthesis steps of CS-APSGO nanocomposite
(HCl, 37%), ethanol (C2H5OH), chitosan (powder, medium molecular hydrogel is depicted in Fig. S1. (Sharma et al., 2018).
weight, high purity, 99% degree of deacetylation), 3-amino-propyltri­
methoxysilane 97% (APTMS), tetrahydrofuran (THF, anhydrous, 2.3. Synthesis of PES/CS-APSGO blended NF membranes
≥99.9%, inhibitor-free), acetic acid (CH3COOH, 96%), Span-80
(C64H124O26), toluene (anhydrous, 99.8%), chlorobenzene (anhydrous, Pure and CS-APSGO hydrogel filled PES membranes were prepared
99.8%), glutaraldehyde (25% (w/w) in H2O), lead nitrate and BSA (96% using the NIPS method. As shown in Fig. 1, the doping solutions were
electrophoresis, pH = 7, lyophilized powder) were obtained from Sigma- obtained with dissolving 20 wt% PES polymer at various amounts of CS-
Aldrich company (McGregor et al.). polyethersulfone (Ultrason® S PES, APSGO (0.5, 1.0, 2.0 and 5.0 wt%) as a modifying agent in N, N-dime­
E6020 P, Mw: 58,000 g/mol) from BASF Company (Germany) were thylacetamide (DMAc) solvent at the attendance of 1 wt% PVP pore
obtained. Polyvinylpyrrolidone (PVP, average Mw: 25,000 g/mol) and former. In doing so, CS-APSGO nanocomposite hydrogel with different
dimethylacetamide (DMAc, Reagent Plus® >99%) were supplied by ratios related to PES weight was added to DMAc, 10 min stirred and
Merck Company (Germany). Two azo dyes, C.I. Reactive Blue 50 subjected to bath ultrasonication for 30 min to reach homogeneous
(Lanasol blue 3 R) and C.I. Reactive Green 19 with molecular weight of dispersions. Next, the precise amount of PVP (1 wt%) was added to the
789.4 and 1418.9 g/mol, respectively were purchased from Azar Co., solutions. Lastly, 20 wt% PES were mixed and dissolved in the solutions
Iran. Distilled water was used in the preparation of all solutions and also by stirring at 400 rpm at ambient temperature for 24 h. To degas the
as the non-solvent agent in the membrane preparation. All the chemicals obtained casting solutions, bath sonication process was applied for 15
were employed with the highest commercially available purity. min. In the following, the prepared doping solutions were cast over a flat
glass plate by 170 μm thickness using a Dr. Blade and rapidly dipped in
2.2. Fabrication of CS-APSGO nanocomposite hydrogel distilled water bath as a coagulant nonsolvent. After 10 min, the pre­
pared membranes were transferred to a fresh distilled water bath and
2.2.1. Preparation of GO nanoplates kept for 24 h to guarantee phase inversion completeness and next,
According to our previous work (Amiri et al., 2020), GO nanosheets reserved in distilled water until usage in membrane tests.
were prepared via oxidizing the graphite powder via improved Hum­
mer’s technique (Gholami and Mahdavi, 2018). A mixture of 1.50 g
2.4. Characterization of CS-APSGO nanocomposite hydrogel
graphite powder and 200 mL H2SO4/H3PO4 (9:1 (V/V)%) was prepared
and subjected to magnetic stirring for 2 h. Afterwards, KMnO4 (9.0 g)
Fourier transform infrared spectra (FTIR) of the GO and CS-APSGO
under agitated condition was added to the obtained mixture and sub­
nanocomposite hydrogel were recorded from 4000 to 400 cm− 1 with
jected to stirring for a period of 24 h at 50 ◦ C. By adding 150 mL chilly
an Elmer FT Spectrum RX1 FTIR spectrometer using potassium bromide
distilled water after addition of 5 mL H2O2 (30 w/w%) at 25 ◦ C to
(KBr), in order to determination their functional groups (McGregor
remove surplus of KMnO4, oxidation reaction brings to an end. After
et al., 1992). The X-ray diffraction (XRD) patterns were recorded via a
several washing of the resulted product, it was suspended in water
X-ray diffraction spectrometer (Philips-PW 17C diffractometer) over a
during 1 h ultrasounicating. After separation of the obtained brown
range of 2θ = 5–80◦ . Bragg equation was used to calculate GO nano­
product through continuous centrifuging, the washing with distilled
sheets d-spacing as following (Liu et al., 2018):
water was performed for up to 3 times to eliminate extant impurities and
get to the neutral pH. In order to remove the moisture, the produced GO 2d sin θ = nλ (1)
powder was heated in a vacuum oven at 70 ◦ C for 4 h followed by
overnight drying in the air (Marcano et al., 2010). where θ is the diffraction angle, n is diffraction order and λ is the incident
wave length.
2.2.2. Preparation of aminopropylsilane graphene oxide (APSGO) Morphologies of the fabricated nanocomposite hydrogel was iden­
APSGO was synthesized through condensation reaction of APTMS tified through scanning electron microscopy (SEM) imaging using
and GO. The suspension of GO (0.5 g) and THF (350 mL) subjected to Cambridge SEM, Model CAM-MV2300 (England) under 15 kV of oper­
bath ultrasonic dispersion for 30 min at room temperature. Then, 3-ami­ ating voltage.
nopropyl-trimethoxysilane (APMS, 1 mL) was poured and the resulted
solution was refluxed overnight at 105 ◦ C. By cooling the solution to 2.5. Characterization of PES/CS-APSGO nanofiltration membranes
30 ◦ C, the obtained APSGO was precipitated and next, filtered and
rinsed by distilled water. Lastly, the resulted APSGO was dried in a Surface wettability and hydrophilicity property of the pure and
vacuum oven at 70 ◦ C for 24 h (Sharma et al., 2018; Pandey and Shahi, hydrogel embedded PES modified membranes were determined through
2014). contact angle analysis. For this purpose, the images of 3 μL DI water
droplets on the membranes surface were captured at room temperature
2.2.3. Fabrication of CS-APSGO nanocomposite hydrogel and relative humidity of 50% via OCA20, obtained images were
CS-APSGO nanocomposite hydrogel was prepared via sol-gel process analyzed via Dataphysics Instruments, Germany and ImageJ software. In

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 1. Fabrication of PES/CS-APSG blended NF membrane.

order to lessen the experimental errors, contact angle measuring was permeated water volume per unit of time (m3/s), and ΔP is the operation
repeated at six distinct points on each membrane surface and the pressure (0.3 MP (
average value of measuring was reported. Average of contact angle Atomic force microscopy (AFM) was applied to investigate surface
values of prepared membranes were compared with each other and on roughness properties of the membranes by use of a DME scanning probe
the other hand contact angle measuring were repeated six time, so microscope Park XE-100 (Germany).
experimental errors or any interference of the surface roughness were In order to determine the surface charge of prepared membranes, an
spread between data and made CA results convincing. outer surface streaming potential measurements were done at 25 C in
As is well known, apparent contact angle of a rough surface is related KCl solution (0.001 M) by employing Electro Kinetic Analyzer instru­
to the ideal contact angle by the Wenzel equation as follows (Dong et al., ment (EKA 1.00, Anton-Paar, Swiss) and zeta potential of membranes
2015): were reported at pH range of 3–10 based on the Helmholtz–Smo­
luchowski equation (Susanto and Ulbricht, 2009).
r(γSV − γSL )
cos θw = = r cos θi (2)
γ LV
In this equation, θW is the Wenzel contact angle, i.e., the apparent 2.6. Permeability, antifouling and separation performance examination
contact angle of a water droplet upon a rough surface, γ SL, γSV, and γLV
are the interfacial free energy per unit area of the solid-liquid, solid-gas, Permeation, antifouling properties and nanofiltration performance
and liquid-gas interfaces, respectively. The θi is the ideal contact angle, of the membranes were studied by a dead-end stirred setup containing
and r is the roughness ratio, equal to ratio of the surface area to its flat three parallel cells. Each cell has 200 mL of capacity and an effective
projected area. area of 19.6 cm2 connected to a 5 L feed reservoir. After putting the
Pure PES and PES/CSAPSGO membranes surface spectroscopic membranes in the cells, they were set to stirring with fixed speed of 400
investigation was performed with attenuated total reflection rpm and pre-compaction of membranes were done by pure water at 4
(Luque-Alled et al., 2020) technique using Bruker-IFS 48 FTIR spec­ bar for 20 min. After compacting, filtration of first pure water perme­
trometer (Ettlingen, Germany). Membrane’s morphology was studied ation test was done for 60 min at steady pressure of 3 bar and room
through surface and cross-sectional SEM imaging using Hitachi SU3500 temperature. The pure water flux, Jw,1 (L/m2h) was estimated every 10
(Japan). The modified membranes in small pieces were broken by min by Eq. (5) (Haghighat and Vatanpour, 2020).
immersing in liquid nitrogen and gold-coated before cross-sectional V
imaging and viewed with the microscope at 15 kV at different Jw,1 = (5)
AΔt
magnifications.
The porosity of membranes was calculated based on gravimetric , where V (L) is the collected permeated volume, A (m2) is the membrane
technique via Eq. (3) (Jalali et al., 2016). surface area, and Δt (h) is the testing time. The membrane tests were
repeated at least six times for each membrane and the average of results
W1 − W2
ε= (3) was reported.
A × l × dw
Then, in order to investigate the membrane performance in Pb (II)
In this equation, W1 and W2 (g) are the weight of wet and dry removal from water, the cells will refill with 50 mg/L of Pb(NO3)2 so­
membrane, respectively. A (cm2), dw (g/cm3) and l (cm) are the effective lutions and the tests were repeated six times at 3 bar and 25 ◦ C tem­
area of membrane, the water density (0.998 g/cm3) and the membranes perature. Lead ions concentration in feed solution and permeate were
thickness. measured with atomic absorption spectrophotometer PG-990 (In­
Membranes mean pore radius (rm), was obtained by the filtration struments Limited, UK). Eq. (6) was employed to determine lead ion
velocity method using Guerout-Elford-Ferry equation shown by Eq. (4) rejection:
(Haghighat and Vatanpour, 2020). ( )
CP
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ R (%) = 1 − × 100 (6)
(2.9 − 1.75ε) × 8ηlQ Cf
rm = (4)
ε × A × ΔP
In this equation, CP and Cf (mg/L) were lead ion concentration in
In this equation, η is the water viscosity (8.9 × 10-4 Pa s), Q is the permeate and feed, respectively (Abdi et al., 2018).

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

The optimum membrane reusability in lead ion removal experiments (UV–Vis 3600i Plus) was used to determine dye concentrations in the
was studied by evaluating removal efficiency of the selected membrane feed and permeate streams at λmax of 626 nm and 630 nm for Reactive
during five cycles of filtration. Each cycle of filtration was carried out Blue 50 and Reactive Green 19, respectively. Flux of dye solutions was
under the same condition of 50 mg/L concentration of Pb(NO3)2 determined using Eq. (5) and the removal efficiency of the dyes is ob­
aqueous solutions and 3 bar of pressure for 60 min and lead ions removal tained by Eq. (6) where Cp and CF (ppm) denote dye concentration in the
efficiency of optimum membrane was reported via Eq. (6) at the end of permeate and feed streams.
each cycle. Then, the membrane was mixed in 25 mL of 10 mM EDTA In addition, long term filtration performance of optimum PES/CS-
solution as a chelating agent for 60 min and then washed with distilled APSGO blended membrane was evaluated through 12 h continuous
water (Kamari and Shahbazi, 2020). filtration of C.I. Reactive Green 19 dye solutions under the same con­
In the following, the membranes were subjected to a solution of BSA dition of the primary tests (Kamari and Shahbazi, 2020). Permeated flux
protein with concentration of 200 mg/L, as a model foulant in purpose of and dye rejection were measured every 90 min by using Eqs. (5) and (6),
assessing the antifouling performance of membranes in term of BSA flux respectively.
and rejection. Membranes antifouling experiment was performed at 3
bar for 60 min. BSA permeation flux Jp (L/m2 h) was calculated based on 2.7. Stability examination
the permeated solution volume and the average value of six times
repeated tests was reported for each membrane. Eq. (6) was used to The stability of CS-APSGO nanocomposite hydrogel in matrix of PES
calculated BSA rejection of the membranes. BSA concentration was membrane were investigated through immersing optimum PES/CS-
determined via UV–Vis spectrophotometric method (UV–Vis 3600i Plus) APSGO membrane in water for up to 10 days. After 10 days of water
at λmax of 260 and 280 nm (Haghighat and Vatanpour, 2020). After immersing, surface chemistry of mentioned membrane was studied via
washing of the fouled membranes and keeping them in distilled water ATR-FTIR analyze to evaluate any changes in membrane characteriza­
for 20 min, the second pure water filtration was measured under the tion. Pure water flux and contact angle measuring were done to study
same condition. The second pure water flux (Jw,2, L/m2h) was recorded water flux and hydrophilicity stability. For this purpose, the pure water
and flux recovery ratio (FRR) was obtained according to following flux and contact angle of optimum PES/CS-APSGO membrane were
expression (Eq. (7)). firstly measured before immersing and then after immersing in a closed
( ) container of DI water for a certain number of days in order to compare
Jw, 2
FRR(%) = × 100 (7) the obtained results (Nikooe and Saljoughi, 2017; Susanto and Ulbricht,
Jw, 1
2009).
In general, the higher value of FRR indicated more flux recovery and
antifouling improvement of the modified membranes. 3. Results and discussion
Equation (8)–(10), were applied respectively to determine total (Rt),
reversible (Rr), and irreversible (Lafreniere et al., 1987) fouling ratios. 3.1. Characterization of CS-APSGO nanocomposite hydrogel
( )
Jp
Rt = 1 − × 100 (8) 3.1.1. Chemical structure and composition
Jw,1
Functionalization of the prepared GO nanosheets produced by
( ) improved Hummer’s method was achieved by condensation reaction
Jw,2 − Jp
Rt = × 100 (9) with APMS. In fact, covalent bond was formed by–OH groups of GO
Jw,1
nanosheets through nucleophilic substitution and elimination of CH3OH
( ) which produced APSGO (Sharma et al., 2018). The sol-gel process in
Jw,1 − Jw,2
Rir = × 100 (10) acidic medium was applied for the fabrication of CS-APSGO nano­
Jw,1
composite hydrogel and crosslinking of CS was performed by reaction
The reversible fouling ratio (Rr) refers to a type of fouling resulted by between glutaraldehyde crosslinker agent and –OH groups of CS chain.
the concentration polarization on membranes surface, while the irre­ The structural characterization of synthesized GO including presence
versible fouling ratio (Lafreniere et al.) is the consequence of the foulant of oxygen containing functional groups on the surface of its nanoplates
adsorption/desorption and pore blocking on membranes surface due to and also its interaction with CS chains in polymeric network of CS-
its constant connection. The total fouling (Rt) is the summation of Rr and APSGO nanocomposite hydrogel were presented by FTIR spectra, as
Rir and displays total flux reduction degree (Zinadini et al., 2017). showed in Fig. 2a. For the GO nanosheets, the strong absorption band at
Fouling resistance parameters of the PES/CS-APSGO NF membranes 3421 cm− 1 was related to hydroxyl group stretching vibration. The
including intrinsic resistance (Rm), pore resistance (Wong et al.), cake 1720 cm− 1 characteristic absorption band was assigned to the acidic
resistance (Rc) and total filtration resistance (Rt) were calculated via Eqs. carbonyl group (–COOH) and stretching vibrations of and the 1623 cm− 1
(11)-(14) (Zhao et al., 2011). band corresponded to carbon-carbon double bond (C– – C). The 1237
− 1
( ) cm absorption band was ascribed to stretching vibrations of C–OH
ΔP
Rm = (11) group and 1032 cm− 1 band attributed to epoxy rings (C–O–C) stretching
μJw,1
vibrations (Zinadini et al., 2017).
( ) In FTIR spectrum of CS-APSGO nanocomposite hydrogel, the band at
ΔP
Rf = − Rm (12) 3411 cm− 1 was attributed to –NH stretching. The bands at 2923 and
μJw,2
2811 cm− 1 were observed due to symmetric and asymmetric stretching
( ) vibrations of–CH2, which authenticated crosslinking of chitosan chains.
ΔP
Rc = − Rm − Rf (13) The O–H stretch of carboxylic acid groups could be detected at 2721
μJ p
cm− 1. The band positioned at 1603 cm− 1 is imputed to –NH bending.
Rt = R c + R m + R f (14) The bands at 1320, 1380 and 1127 cm− 1 were related to stretching of
C–O and Si–O–C, respectively that showed desirable compatibility be­
Finally, the solution reservoir was refilled with 100 mg/L C.I. tween CS and APSGO. The 762 cm− 1 absorption band was assigned to
Reactive Blue 50 (Lanasol blue 3 R) and C.I. Reactive Green 19 dye aliphatic amine –NH wag and the 620 cm− 1 absorption band was related
solutions as two model azo dyes with different molecular weights. The to OH bend (out of plane) (Marcano et al., 2010).
membrane performance in removal of dye as flux and rejection of the XRD plots of GO nanoplates and CS-APSGO nanocomposite hydrogel
dyes were recorded during 90 min. The UV–Vis spectrophotometer are presented in Fig. 2b. As shown, a sharp characteristic peak at 2θ =

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 2. (a) FTIR spectrum and (b) XRD plots and (c) SEMs of GO nanoplates and CS-APSGO nanocomposite hydrogel.

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

12.4◦ in the diffraction pattern of GO was corresponding to the internal Original contact angle data of prepared membranes related to one
planar distance (d001) of about 0.716 nm between GO nanoplates measuring was presented in Fig. S3. In addition to functional groups of
calculated by Bragg equation (Amiri et al., 2020). XRD patterns of membrane surface, membranes contact angle is influenced by the sur­
CS-APSGO exhibited a diffraction peak at 11.5◦ , indicating silane mol­ face porosity and roughness. In fact, by surface porosity increasement
ecules inserting in GO nanoplates via nucleophilic substitution. Appar­ because of the capillary forces, the water drops might slowly diffuse in
ently, a sharp diffraction peak appeared at 18.6◦ implying CS chain and membrane pores which resulted to decrement in contact angle value due
APSGO hydrogen bonding interactions and crosslinking of CS chain to water molecules surface adhesion force (Etemadi et al., 2017). Similar
decreased the crystallinity and resulted to greater structural heteroge­ results have been obtained in the literature when O-carboxymethyl
neity in the obtained nanocomposite hydrogel (Sharma et al., 2018). chitosan–Fe3O4 was incorporated in the doping solution of PES NF
membranes (Zinadini et al., 2014). Membrane’s wettability was
3.1.2. Morphology enhanced by adding membranes surface roughness caused by the surface
SEMs of the synthesized GO nanosheets and CS-APSGO nano­ chemistry, too. For instance, chemically hydrophobic membranes sur­
composite hydrogel are exhibited in Fig. 2c. Functionalization of GO face become more hydrophilic when surface roughness is reduced
nanosheets and applying them in crosslinked hydrogel network as a (Etemadi et al., 2017). In order to calibrate the water contact angle of
scaffold, demolished their orderly structure. As shown, a porous 3D the membranes to eliminate the interference of the surface roughness,
dense structure of nanocomposite hydrogel was formed after cross­ the measured apparent contact angles of each prepared membrane came
linking due to desirable compatibility between APSGO and CS which out to be practically identical with calculated contact angle values by the
resulted to uniform distribution of APSGO in CS matrix (Marcano et al., Wenzel equation (Eq. (2)) as shown in Table S1 and slight difference
2010; Singh et al., 2017). The formation of hydrogel on the surface of were within the range of the standard deviation of six replicates which
GO nanosheets could be observed. was ignorable (Dong et al., 2015; Meiron et al., 2004).
In the fabricated hydrogel embedded membranes, by increasing CS-
3.2. Characterization of CS-APSGO/PES modified membranes APSGO nanocomposite hydrogel dosages up to 1 wt% in the PES
membranes casting solution, porosity enlargement caused to mem­
3.2.1. Surface wettability branes contact angle reduction and in 2 and 5% membranes although
The measured contact angles between deionized water droplets and porosity reduction was achieved due to increasing membrane casting
membranes surface can reflect the natural surface wettability of the solution viscosity but hydrophilic functional groups on the top mem­
membrane material. The less contact angle value demonstrates the more branes surface caused to membranes wettability increasement. In these
wettability and subsequently more hydrophilic nature of the membranes modified CS-APSGO hydrogel embedded membranes, surface roughness
surface. The static water contact angle for the pure PES membrane and parameters were reduced compared by the bare PES membrane which
CS-APSGO or/and PVP containing PES membranes are presented in indicated improving wettability properties of modified membranes.
Table 1. As shown, the pure PES membranes showed the highest contact
angle value of 63.1◦ and therefore the lowest hydrophilicity. The 3.2.2. Porosity and mean pore radius
decreasing trend of measured contact angle were visible and the mini­ The overall porosity results of the PES/CS-APSGO NF membranes are
mum contact angle value of 48.7◦ by blending of 5 wt% CS-APSGO was presented in Table 1. For all of the membranes, an appropriate porosity
achieved. This reducing water contact angle trend of the hydrogel in the range between 61.2% and 74.8% was obtained and the overall
modified membranes could be described by the migration of hydrophilic porosity of the CS-APSGO nanocomposite hydrogel blended PES mem­
CS-APSGO nanocomposite hydrogel near the surface of membrane branes was more than that of the unfilled PES membrane. Due to the
through the phase inversion preparation and decoration of their hy­ hydrophilicity effect of CS-APSGO nanocomposite hydrogel in the
drophilic groups on the top surface of the modified membrane which casting solution of hydrogel containing membranes, solvent/non-
causes them more hydrophilic (Vatanpour et al., 2011). Contact angle solvent exchange become faster and result in porosity increment dur­
comparing of the PES/CS-APSGO 1 wt% and PES/PVP 1 wt% blended ing the phase inversion preparation (Koulivand et al., 2019). On the
membranes showed that the CS-APSGO hydrogel has induced better other hand, diffusion of solvent molecules from the polymer matrix to
hydrophilicity to PES matrix rather than the PVP additive and conse­ the nonsolvent bath occurred more simply due to the nanocomposite
quently resulted to superior antifouling properties in the PES/CS-APSGO hydrogels hindrance in the doping solution which reduced the in­
blended membrane (Amiri et al., 2020). teractions between polymer and solvent molecules (Zinadini et al.,
2014). Accordingly, by increment the loading content of CS-APSGO in
Table 1
the doping solution up to 1 wt%, the porosity value of membranes
Contact angle, mean pore radius, overall porosity and roughness parameters of increased as it shown. However, in 2 and 5 wt% CS-APSGO blended
the hydrogel blended PES membranes. membranes the viscosity of the casting solutions increased due to total
solid content increment (approved by our previous works (Shahabi
Membranes Contact Porosity Mean Roughness parameters
angle (◦ ) (%) pore et al., 2020; Vatanpour et al., 2020)) and resulted in porosity reduction.
Sa Sq Sz The porosity of PES/PVP 1 wt% membrane was higher than that of
radius
(nm) (nm) (nm)
(nm) the PES/CS-APSGO 1 wt% membrane, confirming the better pore
Bare PES 20% 63.1 ± 61.2 ± 1.28 ± 14.6 17.8 192.1 forming role of PVP additive than the CS-APSGO hydrogel and showed
2.0 1.8 0.2 higher tendency of PVP additive to leach out of the membranes casting
PVP 1% 61.1 ± 65.0 ± 2.53 ± 13.7 16.9 165.3 solution to form pores. On the other words, the CS-APSGO nano­
2.2 1.9 0.5
composite hydrogel as a large network of polymeric chain trapped be­
CS-APSGO 1% 57.8 ± 63.3 ± 1.94 ± 11.2 14.3 151.3
3.2 2.3 0.4 tween the chains of PES polymer during membrane formation process,
PVP 1% + CS- 56.0 ± 69.4 ± 5.54 ± 10.4 13.6 137.8 so it didn’t indicate pore forming role. However, according to the con­
APSGO 3.3 1.8 0.9 tact angle results, CS-APSGO additive could induce better hydrophilicity
0.5% and consequently superior antifouling properties to the modified
PVP 1% + CS- 54.4 ± 74.8 ± 6.13 ± 9.1 11.1 112.4
APSGO 1% 1.6 2.1 1.2
membranes (Amiri et al., 2020).
PVP 1% + CS- 50.6 ± 72.3 ± 5.25 ± 13.5 15.8 173.7 Consistent with the mean pore radius results illustrated in Table 1,
APSGO 2% 1.4 1.7 0.8 the mean pore radius of the membranes enlarged by CS-APSGO nano­
PVP 1% + CS- 48.7 ± 71.3 ± 5.08 ± 14.1 16.9 181.2 filler content up to 1 wt% (due to fast exchange of solvent-nonsolvent)
APSGO 5% 2.5 2.4 0.7
and then declined. Reduction in the mean pore radius in the high

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 3. Cross-sectional SEMs of membranes CS-APSGO embedded membranes.

loading content of nanocomposite hydrogel additive may be related to indicated lesser surface pores density in compare to 1 wt% PVP con­
viscosity increasement of blended solutions by addition of more amount taining membranes (compare Fig. S2c and S2b). This comparison
of the nanocomposite hydrogel additive. showed that CS-APSGO nanocomposite hydrogel didn’t leach out of the
membranes doping solution to form pores during NIPS process.
3.2.3. Membranes morphology The cross-sectional SEMs of membranes indicated a usual asym­
Top surface and cross-sectional SEM images of the hydrogel blended metric finger-like structure consist of a condensed thin-skin up layer, a
PES mixed matrix membranes have been shown in Fig. S2 and Fig. 3. porous sub-layer and a bottom layer with a lot of narrow voids. The
There are no substantial differences between the surface morphology of dense thin-skin top layer limits pure water permeation flux because of
the membranes. All the surface of membranes is comparatively smooth existence of the nanoscale pore channels, but progresses separation ef­
and without any CS-APSGO hydrogel nanocomposite mass or lump. ficiency and selectivity by barricading the solutes to cross through this
Because of the carbon-based structure of GO nanosheets and CS-based layer (Shen et al., 2012). Bottom-layer as a supporting layer is respon­
nanocomposite hydrogel, good dispersion of this CS-APSGO nano­ sible for maintenance of membrane strength through filtration tests and
composite hydrogel in PES membranes matrix was resulted without any supporting higher permeability, it is more effective to have microscale
agglomeration on the membrane surface (Safarpour et al., 2016). In porosity (Vatanpour et al., 2018). The cross-sectional images of mem­
addition, there aren’t any cracks on the surfaces, which confirm that by branes indicated the irregular finger-like designs with lower and shorter
the addition of nanocomposite hydrogel, the resulted membranes pores for the pure PES membranes but in CS-APSGO nanocomposite
maintained their stability and did not become fragile. In addition, all hydrogel blended PES membranes, this structure formed with a longer
modified membranes have more surface pores density in comparison to finger-like design and regular pore wall decoration which enhanced the
the bare PES membrane. In fixed content of 1 wt% PVP pore former rate of permeation of these modified membranes. In fact, the thermo­
agent, the surface of 1 wt% CS-APSGO blended PES membranes showed dynamic characteristics of the solvent and nonsolvent mostly deter­
the highest pore density but in 2 wt% and 5 wt% membranes, it lessened mined the total structure of membranes during phase separation step.
due to the kinetic hindrance resulting from enhancement in dope solu­ Because of greater affinity of DMAc to the PES, a delay in demixing
tion viscosity of the membranes with increasing of CS-APSGO nano­ resulted to formation the unequal finger-like plans in the pure PES
composite content [46]. Furthermore, the membranes containing 1 wt% membrane. However, in hydrogel blended membranes, CS-APSGO
PVP compared with those without addition of this pore former agent nanocomposite hydrogel additive caused solvent-nonsolvent exchange
indicated more membranes surface pores density (compare Fig. S2e and rate enhancement during the membranes fabrication process (Shen
S2c). This is confirmed pore forming properties of the PVP additive et al., 2012). Consequently, this phenomenon base on compatibility of
(Lafreniere et al., 1987). The 1 wt% CS-APSGO blended PES membranes the PES matrix and CS-APSGO nanocomposite hydrogel can intensify the

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 3. (continued).

instantaneous demixing mechanism and resulted to more and extended according to Fig. 3e. Pore size enlargement by hydrophilicity improve­
length finger-like pores with regular design in the modified membranes. ment of the casting solution through increasing CS-APSGO amount can
This structure in 1 wt% CS-APSGO blended PES membranes formed with be related to thermodynamic and kinetic effects. However, increasing
reduced thickness skin of top layer and extended length finger-like CS-APSGO content up to 2 wt% caused to enhancement in thickness of
pores. As shown in Fig. 3c combined addition of 1 wt% PVP and 0.5 upper layer and this thickness increasing were more evident in upper
wt% CS-APSGO to the PES doping solution caused to increment in size layer of 5 wt% CS-APSGO containing membranes (compare Fig. 3f and
and number of finger-like macrovoids in the membrane sub-layer. The g). In fact, with raised addition of CS-APSGO nanocomposite hydrogel to
PES/CS-APSGO 1 wt% blended membrane showed the most pore size membranes doping solution, the viscosity of the polymer casting

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 3. (continued).

solution increases and accumulation of this hydrogel on membranes both spectra, two absorption bands related to the PES structure at 1297
pore surface occurred (Vatanpour et al., 2011). and 1150 cm− 1 imputed to the sulfone groups asymmetrical and sym­
metrical vibrations, respectively (Madaeni et al., 2013). The diphenyl
3.2.4. ATR-FTIR C–O–C bond stretching vibration of PES polymer could be seen at 1011
Fig. 4 presented the ATR-FTIR spectra of the pure PES and PES/CS- and 1240 cm− 1. The strong absorption bands appeared in 1480–1580
APSGO 5 wt% nanocomposite hydrogel embedded membranes. In cm− 1 region were related to the stretching mode of the benzene rings
(Ghaemi et al., 2012). These bands were revealed in the spectrum of
CS-APSGO/PES blended NF membranes, too. The ATR-FTIR spectrum of
CS-APSGO blended PES membrane is dissimilar from the pure PES
membrane. Fig. 2a showed that the FTIR spectrum of the CS-APSGO
nanocomposite hydrogel presented absorption bands at 3411, 2923
and 2811, 2721, 1603 cm− 1 for (–NH), symmetric and asymmetric
(–CH2) stretching vibrations, (OH) stretch of (–COOH) groups and (–NH)
bending and also the characteristic absorption band at 1380 and 1320,
1127, 762 and 620 cm− 1 which assigned to (C–O) stretching, (Si–O–C)
stretching, (–NH) wag of aliphatic amine and OH out of plane bending.
Similar characteristic bands emerged in the spectrum of CS-APSGO
containing membranes, too. These observations confirming the exis­
tence of CS-APSGO nanocomposite hydrogel on the membranes surface
which improved membranes hydrophilicity. Based on this explanation,
the highest surface hydrophilicity was resulted in the membranes with 5
wt% CS-APSGO nanocomposite hydrogel. The bands at 1400 and 1600
cm− 1 are related to vibration of (C–N) and (N–H) stretching of PVP
structure.
Fig. 4. ATR-FTIR spectra of the pure PES and the PES/CS-APSGO 5 wt%
modified membranes.

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

3.2.5. Zeta potential 5 wt% had remodeled the reducing trend of the roughness parameters
Based on Zeta potential data of the prepared bare PES and the CS- owing to the evident formation of valleys on the membrane surface. In
APSGO blended PES membranes at the pH range of 3–10 presented in fact, due to enhancement of ionic interaction among surface polymeric
Fig. 5, the bare PES membrane display negative charge in the range of chain by agglomeration of CS-APSGO nanocomposite hydrogel on the
the examined pH values due to existence of sulfonyl (O– – S–
– O) func­ membranes surface at high concentrations, polymeric chains wrinkling
tional groups of PES and negative surface charge of the modified on the membranes surface resulted to the surface roughness enhance­
membrane was increased by blending CS-APSGO in PES membrane ment in 2 and 5 wt% nanocomposite hydrogel embedded membranes.
matrix as the pH increased. This negative charge increasement in PES/ The changes in trend of roughness parameters indicated that blending of
CS-APSGO membrane might be due to dissociation of amide, carboxyl CS-APSGO has reduced the mean roughness (Sa) of the fabricated PES-
and hydroxyl and epoxy hydrophilic functional groups of CS-APSGO on based modified membrane compared to the pure membrane due to
the membrane surface. Since the potential of the most fouling agents decoration of the CS-APSGO nanocomposite hydrogel onto the surface of
seem to be negative at neutral pH, the negative surface charge of these blended membranes. However, the surface roughness initiates
membranes has induced a repulsive force against foulants which become improving trend in high concentration of CS-APSGO additive and
stronger with increasing CS-APSGO blended concentration and resulted enhanced Sa from 9.1 nm for 1 wt% to 13.5 and 14.1 nm for 2 and 5 wt%
to superior anti-fouling performance in the blended membranes (Bar­ membrane, respectively. Enhancement in number of amide, carboxyl,
zegar et al., 2020). hydroxyl and epoxy active groups on the surface which increased the
ionic interaction among surface chains and caused surface wrinkling
3.2.6. AFM was the reason. Therefore, according to surface roughness data and with
The surface roughness of membranes can control the membrane regard to surface hydrophilicity of prepared membrane, the 1 wt% CS-
fouling by affecting the adsorption/desorption of foulants on the surface APSGO blended membrane should be the best prepared antifouling
of membrane and the smoother membranes surface indicated superior membrane and negative surface charge confirmed this (Vatanpour et al.,
antifouling characteristics (Sun et al., 2010). Blending of CS-APSGO 2014).
additive to the membranes doping solution affects the roughness of
the resulted membranes. Fig. 6 displays the AFM images taken from the 3.3. Membrane performance
membrane surface of the pure and hydrogel mixed PES membranes (5
μm × 5 μm). DME/SPM software (version 2.1.1.2) was used to calculate 3.3.1. Pure water flux
the roughness factors of the membrane surface comprising average Existences of a direct correlation between the pure water permeation
roughness (Sa), the root mean square of the Z data (Sq), and the differ­ and hydrophilicity properties of membranes surface have been approved
ence of the highest peak and the lowest valley (Sz) (Arnett et al., 2013) in the several reports in the literature (Zhang et al., 2014). Hydrophilic
and obtained value of these parameters have been gathered in Table 1. nature of nanocomposite hydrogel arising from their surficial functional
The pure PES membrane has the maximum value of surface rough­ groups makes them an applied category of additive with the aim of
ness and the blending of CS-APSGO hydrogel to PES matrix led to hydrophilicity reinforcement of polymeric membranes in wastewater
reduction in value of the roughness parameters. Incorporation of CS- treatment application (Amiri et al., 2020). Incorporating of CS-APSGO
APSGO nanocomposite hydrogel onto the membranes surface PES additive into the membranes doping solution enlarged hydrophilicity
were occurred by self-assembly. This manner of CS-APSGO nano­ and accordingly pure water flux permeation of the modified membranes.
composite hydrogel on the PES membrane surface by ether bond and The hydrophilic nature of CS-APSGO additive in PES matrix and its
terminal functional groups (carbocyclic acid, sulfonic acid and sulfone higher tendency to water increased transport velocity between solvent
groups) can be explained by interactions between these groups and and water nonsolvent during the NIPS method resulted to mean pore
nanocomposite hydrogel functional groups (amide, carboxyl, hydroxyl, radius enlargement. But in higher than optimum concentration of
epoxy and aromatic rings) via π-π stacking interactions or hydrogen CS-APSGO, increasement in total solid content of membrane casting
bonding. solution resulted to mean pore radius reduction. Comparing
The minimum values of roughness parameters were recorded for cross-sectional SEMs of the prepared membranes confirmed pore size
PES/CS-APSGO 1 wt%+ PVP 1 wt% optimized membrane compared to trend, which are compatible with values of pure water fluxes (Amiri
the other blended membranes. The Sa, Sq and Sz values are reduced as et al., 2020).
the of CS-APSGO nanocomposite hydrogel content is increased up to 1 As presented in Fig. 7a, the pure water flux of all CS-APSGO blended
wt%, and additional increase of nanocomposite hydrogel amount up to PES membranes was higher than that of the pure PES. The pure water
flux for the 1 wt% PVP containing membranes were obtained to be 15.5
(L/m2 h) and for membranes with 1 wt% CS-APSGO decrease to 10.1 (L/
m2 h), indicating that the CS-APSGO additive does not leach out of
membranes doping solution in order to pores producing and does not
show pore former role. In modified membranes containing fixed content
of 1 wt% PVP, increment of the CS-APSGO additive amount in the
membranes doping solution caused to membranes pure water flux
increasement until attained its utmost value of 123.8 (L/m2 h) in 1 wt%
CS-APSGO optimum membrane, while corresponding value was re­
ported 3.7 L/m2 h for the pure PES membranes. The observed increment
in pure water permeation could be justified by noticing to the contact
angle trend and porosity improvement, see Table 1. Accordingly, the
hydrophilicity of PES/CS-APSGO 1 wt%+ PVP 1 wt% embedded mem­
branes is higher than that of the pure PES and consequently showed the
most permeability. Besides, by increasing CS-APSGO content in the
casting solution higher solvent-nonsolvent exchange rate during phase
inversion process resulted to the formation of the hydrogel blended
modified membranes by higher porosity and mean pore radius in com­
parison to pure PES membranes. However, pure water flux reduction
Fig. 5. Zeta potential of the fabricated membranes versus pH. observed in membranes with 2 and 5 wt% CS-APSGO compared to

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 6. Surface AFM images of the hydrogel blended PES membranes.

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

membranes with 1 wt% of this additive could be related to their lesser

pore radius and also pores blockage caused by possible agglomeration of
the nanocomposite hydrogel (Zinadini et al., 2017).

3.3.2. Antifouling behavior

Antifouling properties of membranes are considered as a key factor
in practical application of membranes process. Therefore, membranes
antifouling ability improvement is the main purpose which attracted the
attention of many researchers (Zinadini et al., 2017). Among various
approaches devoted to the preparation of antifouling membranes
through membranes hydrophilicity enhancement, addition of a com­
posite of hydrogel 3D networks with inorganic nanoparticles to the
casting solution improves the membranes performance in terms of per­
meance efficiency and fouling resistance (Amiri et al., 2020).
With the purpose of investigate antifouling properties of the mem­
branes, obtained results of membranes performance after explosion to
200 mg/L BSA feed solution in term of BSA solution flux and BSA
rejection were shown at Fig. 7b. The obtained results reveal that all the
CS-APSGO/PES blended membranes in compared to pure PES mem­
branes indicated more BSA rejection and rejected the BSA protein more
than 97%. As shown PES/CS-APSGO 1 wt% blended membranes in
comparison with PES/PVP 1 wt% and PES/CS-APSGO 0.5 wt% + PVP 1
wt% membranes rejected more BSA solution confirmed that CS-PSGO
additive in compared to PVP has more effect on membranes BSA
rejection reinforcement due to antifouling improvement in membranes
modification. Therefore, slight enlargement in the rejections of BSA
solution with CS-APSGO content increment in the doping solution of
membranes could be justified by membranes hydrophilicity improve­
ment. As shown in Fig. 7b by incorporation of CS-APSGO nanocomposite
hydrogel, the BSA flux of the membranes increased compared with the
pure PES membranes. This can be explained by refer to the hydrophilic
nature of CS-APSGO nanocomposite hydrogel which resulted to hydro­
philicity reinforcement of the hydrogel blended modified membranes,
see Table 1. However, more concentrations of CS-APSGO resulted to
agglomeration and due to membranes pores blockage reduce of mem­
branes efficiency occurred. As presented in Fig. 7a and b, imputed to
membrane pure water and BSA protein flux, the membranes with 2 and
5 wt% CS-APSGO indicated less flux rather than 1 wt% membranes.
Fig. 7c presented first pure water flux, BSA solution flux, and second
pure water flux after water washing of the membranes versus time. All
the CS-APSGO blended membranes showed higher water and BSA fluxes
in comparison with unfilled PES membrane indicated the effective role
of CS-APSGO nanocomposite hydrogel additive in membranes hydro­
philicity and permeability improvement. In the case of CS-APSGO 1 wt
% + PVP 1 wt% blended PES membranes topmost pure water perme­
ation fluxes before and after BSA filtration were reported and pure water
flux reduction in 2 and 5 wt% CS-APSGO blended membranes may be
attributed to membranes pores blockage by the aggregated CS-APSGO
nanocomposite hydrogel. BSA solution flux approximately indicated
similar trend in all membranes and a significant BSA permeability
reduction was visible due to concentration polarization caused by BSA
molecules adsorption on the membranes surface (Vatanpour et al.,
2014).
With the aim of study antifouling characteristics of membranes, the
percentage of flux recovery ratio (FRR) is the most useful index intro­
ducing antifouling performance of the membrane and the best anti­
fouling performance was obtained by the membrane possess the highest
FRR. The results of FRR for all the unfilled and CS-APSGO blended PES
membranes are shown in Table 2. As it obvious, the FRR of CS-APSGO/
PES blended membranes is higher than that of pure PES membranes
Fig. 7. (a) Pure water flux of the membranes at 3 bar, (b) BSA solution flux and indicating the antifouling improvement of blended membranes in
rejection through the membranes, (c) membranes flux versus time in three expose to BSA solution. The FRR value of pure PES membranes were
stages: first pure water, BSA solution and second pure water filtration after 57.4 signifying a poor antifouling property for this membrane. In the
membranes washing (at 3 bar) in time duration of 60 min for each test. case of membrane with the best antifouling property, i.e. PES/CS-
APSGO 1 wt% +PVP 1 wt%, 96.6% FRR value was achieved. Change
trend of FRR is coordinated by water contact angle and pure water flux

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Table 2
Calculated percentage of flux recovery ratio, fouling ratio and resistance parameters of the CS-APSGO/PES membranes.
Membranes FRR (%) Fouling ratio parameters (%) Fouling resistance parameters

Rr Rir Rt Rm Rp Rc Rt

Bare PES 20% 57.4 ± 2.5 9.7 63.8 73.5 91.1 149.7 103.2 343.9
PVP 1% 68.2 ± 3.1 3.7 31.7 35.5 21.7 10.1 1.8 33.7
CS-APSGO 1% 80.6 ± 2.4 16.2 19.4 35.6 33.4 8.0 10.4 51.86
PVP 1%+ CS-APSGO 0.5% 87.8 ± 1.9 39.0 12.2 51.2 4.0 0.6 3.7 8.28
PVP 1%+ CS-APSGO 1% 96.6 ± 1.8 27.4 3.4 30.8 2.7 0.1 1.1 3.94
PVP 1%+ CS-APSGO 2% 91.2 ± 2.2 20.2 8.8 51.4 3.0 0.3 3.2 6.48
PVP 1%+ CS-APSGO 5% 89.6 ± 2.8 41.0 10.4 73.5 3.5 0.4 3.4 7.36

of the membranes. This remark could be explained with the hydrophi­ blockage of membranes, respectively (Vatanpour and Haghighat, 2019).
licity enhancement of the modified membranes which resulted to water
molecules adsorption to the hydrophilic surface of the modified mem­ 3.3.3. Lead ion removal
branes and prevented the adsorption of foulants by creation a thin layer Fig. 8a presents the results of Pb(II) ions rejection of the PES mem­
of water between the membrane surface and BSA molecules (Kumar branes with different CS-APSGO nanocomposite hydrogel concentra­
et al., 2019). The FRR value of the PES/CS-APSGO 1 wt% embedded tions. As it shown, the lowest lead rejection was reported for the pure
membranes is greater than the PES/PVP 1 wt% membrane, confirming PES membrane and lead ion rejection has improved by increasing CS-
their improved antifouling performance. The CS-APSGO additive is a APSGO content, and the PES blended membranes with 5 wt% CS-
chemical crosslinked network of polymeric chains possessing hydro­ APSGO (92.2%) indicated higher lead ions rejection than 2 wt% CS-
philic nature that leached out to the nonsolvent water bath thru the APSGO (87.9%), 1 wt% CS-APSGO (82.3%) and 0.5 wt% CS-APSGO
phase separation step and induces better hydrophilic properties to (73%) membranes compared to the pure PES membrane (29.1%) after
blended membranes by tarring between PES chains. Nevertheless, the 60 min filtration time. This may be mainly due to the superior adsorp­
PVP is a pore former agent and addition of this additive to membrane tion characteristics of CS-APSGO nanocomposite hydrogel related to
casting solution resulted to membrane porosity increase by leaching out attendance of oxygen containing functional groups which causing more
the polymer structure. So, the hydrophilicity of PES/CS-APSGO 1 wt% is interaction of Pb(II) with the blended membranes surface. On the other
more than the PES/PVP 1 wt%, which causes better antifouling per­ hand, high surface concentration of active adsorption sites (-NH2/ =
formance. From Table 2, when the CS-APSGO weight fraction related to NH) possessed lone pairs of electrons in CS-APSGO nanocomposite
the PES weight in the doping solution enlarged from 1 to 2 and 5 wt%, hydrogel caused considerable hydrogen bonds forming in combination
the FRR value indicated reduced trend. This could be explained by the with heavy metal ions and confirmed Pb(II) ions anchoring on mem­
surface roughness alteration of the blended membranes. From Table 1, branes surface (Sharma et al., 2018). Moreover, the hydrophilic nature
by addition of low content of CS-APSGO nanocomposite hydrogel, the of CS-APSGO nanocomposite hydrogel resulted to membrane surface
roughness parameters of obtained membranes reduced. However, the hydrophilicity improvement and increased membranes surface area
blended membranes roughness increased in 2 and 5 wt% CS-APSGO which provides more active sites on the membrane surface for lead ions
additive and resulted to the FRR diminishment. adsorption (Han et al., 2012).
In order to more evaluate the antifouling properties of membranes, With attention to above explanation, filtrating and adsorbing resul­
the calculated fouling resistance parameters including total (Rt), ted to Pb(II) removal from aqueous solution and the separation mech­
reversible (Rr) and, irreversible (Lafreniere et al.) fouling ratio of the anism of fabricated membranes for Pb(II) removal seem to be
membranes were calculated and the results were gathered in Table. 3. adsorption. In fact, in the structure of CS-APSGO nanocomposite
Better membranes performance against fouling phenomenon was ob­ hydrogel additive with active adsorption sites (-NH2/ = NH) along with
tained by increasing the reversible fouling ratio and decreasing the oxygenated functional groups, lone pair(s) of electrons sharing with Pb
irreversible fouling ratio (Vatanpour and Haghighat, 2019). As specified (II) ions resulted to formation of Pb(II) metal complex (Sharma et al.,
in diagram, CS-APSGO blended membranes indicated more reversible 2018). According to zeta potential data, negative surface charge of
fouling ratio, as well as less irreversible fouling ratio. The total and PES/CS-APSGO in neutral pH caused to intensify Pb(II) cation adsorp­
irreversible fouling parameters of membranes were decreased from 73.5 tion onto membrane and increase interaction between Pb(II) cations and
to 68.8% to 30.8 and 3.4% for the pure PES membranes and membranes active adsorption sites (-NH2/ = NH) of membraned which resulted to
with 1 wt% PVP and CS-APSGO additive, respectively. higher lead ions removal. (Kamari and Shahbazi, 2020).
In fact, incorporation of CS-APSGO nanocomposite hydrogel to PES Theoretically, the addition of CS-APSGO into PES matrix enlarged
matrix resulted to membranes hydrophilicity reinforcement and decre­ the membrane pore size, and it hence should reduce the rejection rate
ment in membranes surface roughness, therefore by reducing adhesion against lead during filtration, but as shown in Fig. 8a, obtained results
of foulant to the membranes surface resulted to antifouling properties indicated that the lead ion rejection has improved by increasing CS-
improvement in the hydrogel blended membranes (Zhang et al., 2015). APSGO content in membranes casting solution due to superior adsorp­
In the purpose of studying fouling phenomenon in the membranes, tion characteristics of CS-APSGO nanocomposite hydrogel additive.
total resistance (Rt), intrinsic resistance (Rm), pore resistance (Rp) and Based on the results of the zeta potential analysis in Fig. 4, negative
cake resistance (Rc) were also commutated and the values are presented surface charge of the modified membrane was increased by blending CS-
in Table 2. As shown, intrinsic resistance as a main part of PES mem­ APSGO in PES membrane matrix due to dissociation of amide, carboxyl
branes resistance is causes the flux reduction in the pure membrane. and hydroxyl and epoxy hydrophilic functional groups of CS-APSGO on
Modification of PES membranes by blending CS-APSGO nanocomposite the membrane surface which is favorable for the lead ion pollutant’s
hydrogel could be able to diminish intrinsic resistance due to hydro­ adsorption during filtration (Kamari and Shahbazi, 2020).
philicity enhancement in the blended membranes. The results confirmed In order to investigate performance of modified membrane after the
that, incorporation of CS-APSGO nanocomposite hydrogel in the mem­ adsorption saturation, lead removal efficiency of the prepared PES/PVP
branes doping solution not only reduced intrinsic resistance, but also 1 wt% and PES/PVP 1 wt% + CS-APSGO 1 wt% optimum membranes
lessen the cake resistance (Rc), and pore resistance (Rp) which were were tested after saturation in 50 mg/L of Pb(NO3)2 for 24 h. In com­
created by the cake layer posited on the surface of membrane and pores parison with the original membranes, lead removal of PES/PVP 1 wt%

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

Fig. 8. (a) Lead ion removal (3 bar, pH = 7.0 ± 0.1, 50 mg/L Pb (NO3)2, after 60 min filtration). (b) Reusability of PVP 1% + CS-APSGO 1% membrane during five
cyclic filtrations.

was constant after the saturated adsorption and 3% reduction was ob­
tained for PES/PVP 1 wt% + CS-APSGO 1 wt% membrane related to
slight reduction in adsorption capacity of CS-APSGO nanocomposite
hydrogel additive in membrane structure. These results imply that op­
timum modified membrane can be efficiently used after membrane
saturation with negligible reduction in Pb(II) removal (Jie et al., 2015).
The evaluation of prepared blended membranes reusability in lead
removal as an indicator of adsorption capacity of CS-APSGO additive
was conducted. For this purpose, reusability of the PES/CS-APSGO 1 wt
% optimum membrane was studied during five continuous filtration
cycles. Each cycle involved 60 min filtration of Pb(NO3)2 aqueous so­
lution under the same condition of 50 mg/L concentration of Pb(NO3)2
solution and 3 bar of pressure followed by 20 min of membranes
washing. As shown in Fig. 8b, the CS-APSGO optimum membrane
indicated Pb(II) ions removal of 82.3, 81, 80.2, 78.5, 78% for 1st to the
5th cycle, respectively, by reduction efficiency of 5.2% from the 1st
cycle to the 5th cycle due to Pb(II) ions adsorption onto surface of
membrane during continuous filtration cycles. The obtained results
imply that prepared PES/CS-APSGO blended membrane had the Fig. 9. Dyes (RB50 and RG19) rejection of the PES/CS-APSGO modified
adequate potential for several time usage without a sensible efficiency membranes (after filtration of 100 ppm dye solution for 90 min at 3 bar, pH =
reduction. 7.0 ± 0.1).

3.3.4. Dye removal APSGO to the membranes doping solution amplify RB50 dye rejection of
Two types of azo dyes i.e. C.I. Reactive Blue 50 (RB50) and C.I. obtained membranes to 88.4%, 90.5%, 92.1%, 92.3% because of pore
Reactive Green 19 (RG19) with molecular weight of MW = 789.4 and forming property of PVP additive and hydrophilic nature of CS-APSGO
MW = 1418.9 g/mol, respectively were applied to assess the nano­ nanocomposite hydrogel.
filtration performance of the modified nanocomposite hydrogel blended In the case of RG19, the CS-APSGO blended PES membranes showed
PES membranes in removal of low and high molecular weight dyes. a higher dye rejection capacity and all the modified membranes rejected
RG19 as an anionic sulphonated diazo dye with superior fastness char­ RG19 dye more than 98%. Similar trend of the RB50 dye rejection was
acteristics and cost effectiveness is wildly applied in textile industry reported for the rejection of RG19 dye in the prepared membranes.
(Ghulam et al., 2020). RB50 is an acidic dye with negative charge in Accordingly, RG19 dye rejection of the blended membranes was
natural pH which is commonly used in the leather and textile industry enhanced compared to the bare PES membrane and the maximum ob­
(Vatanpour et al., 2019). Molecular structures of reactive Green 19 and tained rejection efficiency was reported 98.8% provided by the mem­
reactive Blue 50 are shown in Fig. S4. brane containing 5 wt% CS-APSGO/1 wt% PVP. This may be related to
Fig. 9 indicates the membrane rejection results for both azo dyes. The the higher surface hydrophilicity of the CS-APSGO blended PES mem­
RB50 rejection for all of the modified hydrogel blended PES membrane branes, CS-APSGO nanocomposite hydrogel could improve membranes
was obtained higher than 86%. However, the highest rejection for both surface hydrophilicity, as the water contact angle measuring of fabricate
azo dyes was provided by 5 wt% CS-APSGO containing membrane. The membranes confirmed this result (Table 1). The higher hydrophilic
RB50 dye rejection of the pure PES membrane was 80.7% and for the 1 membranes surface adsorbed more volume of dye aqueous solution
wt% CS-APSGO/1 wt% PVP modified membranes reached to 83.2% and during dye removal test and dye molecules could permeate into 3D
86.3%, respectively. Addition of 1 wt% PVP with 0.5, 1, 2 and 5 wt% CS- network of hydrogels nanocomposite and immobilize between hydrogel

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

chains on membranes surface and consequently prevent passing through RG19 dye aqueous solution. As shown in Fig. 10a, premier performance
PES/CS-APSGO membranes. The dye rejection performance of the PES/ of optimum membrane in term of RG19 dye rejection and permeate flux
CS-APSGO embedded membranes could be justified conforming to was maintained during long-term filtration test. The dye rejection of
Donnan exclusion mechanism by negative surface charge (Sarkar et al., optimum membrane during long-term filtration was approximately
2010). Negative charge of both RB50 and RG19 dyes in the neutral pH constant value of 98.5%, while the dye solution flux was reduced from
are related to dissociation of their sulfonic group as shown in Fig. 8c. 123.5 to 118 L/m2 h (4.4% reduction) during the long–term filtration
Moreover, the PES/CS-APSGO modified membranes are negatively experiments due to polarization of the solution concentration raised
surface charged in the presence of an aqueous dye solution through from dye molecules aggregation on membrane surface during long-term
dissociation of membranes surface functional groups, which repels the filtration process. These obtained results indicated that CS-APSGO ad­
negatives dyes and resulted in higher dye rejection efficiency (Kumar ditive improved anti-pollution property of blended membranes which
et al., 2019). Accordingly, the result of dye elimination performance of restricted rapid flux reduction in prolonged filtration application of the
the membranes could be contributed to negative charge electrostatic prepared membranes (Kamari and Shahbazi, 2020).
repulsion of mentioned azo dyes and CS-APSGO nanocomposite
hydrogel. Furthermore, the surface pore sizes of the blended membranes 3.3.6. Stability test study
can amplify modified membranes dye removal (Safarpour et al., 2016). Additive stability in the membrane’s polymer matrix is an important
According to zeta potential measurement the modified PES/CS- factor in the practical application of modified membranes. In our study,
APSGO membrane indicated negative charge in neutral condition and stability of CS-APSGO in PES matrix as a hydrophilic additive was
also RG19 and RB50 as two azo dyes have negative charge in neutral pH, investigated and evaluated via ATR-FTIR analyze, pure water flux and
too. Physical rejection through repulsion effect between negatively contact angle measuring. For this purpose, PES/CS-APSGO 1 wt% op­
charged modified membranes and the anionic dyes is effective mecha­ timum membrane was immersed in water for up to 10 days, then surface
nism for higher dye rejection of CS-APSGO blended membranes (Kou­ chemistry of mentioned membrane after water soaking was studied via
livand et al., 2020). ATR-FTIR analyze. As shown in Fig. S5, similar absorption bands related
to CS-APSGO functional groups were observed after water soaking (see
3.3.5. Long-term filtration experiments for RG19 dye removal section 3.2.4) which approved that CS-APSGO nanocomposite additives
According to prepared membranes separation performance and ef­ was completely stable in the PES matrix of prepared membrane. Other
ficiency results, long-term filtration of PES/CS-APSGO 1 wt% as opti­ than surface chemistry investigation, stability of CS-APSGO in PES
mum membrane was evaluated through 12 h continuous filtration of matrix of prepared membrane was studied in case of surface hydrophi­
licity and transport property by contact angle and water flux measuring
before water soaking and then after a certain number of days during the
period of water soaking.
Fig. 10b presents the stability of water flux permeability and surface
hydrophilicity property of the prepared membranes during water
immersing. Pure water flux of optimum membrane did not change
during 10 days of immersing and sight flux reduction were still within
the range of experimental error which was ignorable. Obtained contact
angle data of optimum membrane during water immersing indicated
that hydrophilicity property of prepared membrane did not change
which proved the stability of CS-APSGO additive in the membrane
polymer matrix (Nikooe and Saljoughi, 2017; Susanto and Ulbricht,
2009).

3.3.7. Comparison with literature data

Table S2 presented a comparison of our work with the other studies
which have applied graphene oxide contained composite additive for
modification of PES membranes in order to improved waste water
treatment. So far, one another report have been embedded biopolymer
based - GO contained nanocomposite hydrogel to modify polymeric
membrane. The mentioned study has been used PVA-GO-SA nano­
composite hydrogel additives with the purpose of enhancing perme­
ability and antifouling properties and better dye removal. The
comparison of data in Table S2 highlights that CS-APSGO hydrogel as a
novel nanocomposite biopolymeric additive is highly effective to
improve the membrane characteristics specifically dye and heavy metal
rejection, fouling mitigation, and permeability improvement.

4. Conclusion

The CS-APSGO nanocomposite hydrogel was firstly synthesized, and

then utilized as an additive in the preparation of PES/CS-APSGO
embedded membranes by the phase separation method. The SEMs of
membranes indicated that blending of the CS-APSGO to the PES casting
solution caused to the creation of asymmetric membranes by reduced
thickness skin of top layer at lower concentration. The effect of distinct
Fig. 10. (a) Long–term filtration results for RG19 dye removal and (b) contact weight percentages of CS-APSGO hydrogel on the PES/CS-APSGO
angle and pure water flux as a function of immersing time of 1 wt% PES/ blended membranes performance revealed that all the PES/CS-APSGO
CS-APSGO. membranes indicated greater water permeability in comparison to the

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S. Amiri et al. Journal of Environmental Management 294 (2021) 112918

unfilled membranes and for the optimum modified PES membrane by 1 Cui, L., Wang, Y., Gao, L., Hu, L., Yan, L., Wei, Q., Du, B., 2015. EDTA functionalized
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The authors declare that they have no known competing financial Jalali, A., Shockravi, A., Vatanpour, V., Hajibeygi, M., 2016. Preparation and
interests or personal relationships that could have appeared to influence characterization of novel microporous ultrafiltration PES membranes using
synthesized hydrophilic polysulfide-amide copolymer as an additive in the casting
the work reported in this paper.
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Acknowledgment inspired hydrogel microspheres with high dimensional stability and anion-exchange
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The authors thankfully acknowledge the Semnan University Preparation and characterization of carboxyl multi-walled carbon nanotubes/
(Semnan, Iran) and the Kharazmi University (Tehran, Iran) for all of the calcium alginate composite hydrogel nano-filtration membrane. Mater. Lett. 157,
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lead-based paint hazards and the prevalence of childhood lead poisoning. J. Urban
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Appendix A. Supplementary data
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green nanofiller embedded in PES–nanofiltration membrane matrix for salts, heavy
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