Chemical Engineering Journal 431 (2022) 134116

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Chemical Engineering Journal

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Novel antibacterial and antifouling PES nanofiltration membrane

incorporated with green synthesized nickel-bentonite nanoparticles for
heavy metal ions removal
Soheil Dadari a, Masoud Rahimi a, *, Sirus Zinadini b
a
Department of Chemical Engineering, Faculty of Engineering, Razi University, Kermanshah, Iran
b
Environmental Research Center, Department of Applied Chemistry, Razi University, Kermanshah, Iran

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

Keywords: Lack of water resources and water pollution by heavy metal ions and microorganisms has made it necessary to
Green synthesis utilize efficient water treatment methods. In this study, for the first time, nickel-bentonite nanoparticles (NBNPs)
Nickel-bentonite were synthesized using Scrophularia striata extract. NBNPs were used as novel nanofillers to fabricate antifouling
Nanofiltration membrane
and antibacterial NBNPs/polyethersulfone (PES) nanofiltration membranes via the phase inversion method for
Antifouling
Antibacterial
heavy metal ions rejection. NBNPs were characterized by FT-IR, XRD, zeta potential, EDS, FESEM, and TEM. The
Heavy metal ions removal fabricated membranes were characterized using FT-IR, XRD, EDS, SEM, water contact angle, zeta potential, and
porosity analyses. The results showed improvement of hydrophilicity, surface charge, and porosity for the
modified membranes.
The blended membranes had substantially less fouling and higher heavy metal ions rejection than the un­
modified membrane. Pure water flux of the unfilled PES membrane was enhanced from 15 to 34.4 and 58.8 kg/
m2h for 0.1 and 0.5 wt% of NBNPs, respectively. The flux recovery ratio was increased from 38.3% for the
unmodified membrane to 98.2% for 0.5 wt% NBNPs/PES membrane. Also, 0.5 wt% NBNPs/PES membrane
exhibited the best rejection performance (Zn2+: 98.62%, Cu2+: 97.88% and Pb2+: 97.03%). Evaluation of
antibacterial properties of the membranes against Escherichia coli and Staphylococcus aureus was performed. The
modified membranes had significant antibacterial capability and 1 wt% NBNPs/PES membrane exhibited the
highest antibacterial rate. According to the findings, NBNPs could be used as nanofillers to fabricate modified
nanofiltration membranes for heavy metal ions rejection and antibacterial ability.

1. Introduction worldwide needs is to use a water and wastewater treatment method to

Rising industrial activities, rapid population growth, and climate
change are the most important reasons for water pollution and lack of
access to safe drinking water resources worldwide, especially in less
developed and developing regions [1]. Heavy metal ions ,such as Fe2+ ,
Mn2+ ,Zn2+ ,Cu2+,Pb2+ ,Ni2+ ,Cd2+, Cr3+,6 and Hg1+,2+ in aqueous
media are the most toxic water pollutants [2]. These ions are introduced
into the environment and natural cycle, and due to their toxicity, non-
biodegradability, low solubility, and high stability affect human
health and the environment [3]. Pathogens are another kind of
contamination of water sources posing a great risk to human health,
including viruses, bacteria, and pillows that can cause diseases like
cholera and diarrhea [4]. Therefore, one of the urgent and essential
deal with pathogenic bacteria and heavy metal ions simultaneously.
Membrane technology, chemical leaching, bioremediation, photo­
electrocatalysis, adsorption, ion exchange, and electrochemical removal
are common methods for water and wastewater treatment [5].
Affordability, low energy demand, scalability, easy fabrication, and
being eco-friendly are the main advantages of using a membrane as a
highly effective and promising method for water treatment [6]. In recent
years, in comparison with other filtration membranes, nanofiltration
(NF) has attracted much attention for usage in various sciences due to its
high permeation flux, low-pressure drive, relatively high retention, and
low relative cost [7]. One of the most often used materials for NF
fabrication is polyethersulfone (PES), owing to its thermal and me­
chanical resistance, low cost, chemical persistence, and favorable

* Corresponding author.
E-mail address: m.rahimi@razi.ac.ir (M. Rahimi).

https://doi.org/10.1016/j.cej.2021.134116

Available online 14 December 2021

1385-8947/© 2021 Elsevier B.V. All rights reserved.
S. Dadari et al.
membrane fabrication flexibility [8]. Despite the convenient advantages
of PES, it is inherently hydrophobic, which is its main drawback and has
resulted in increment of membrane fouling and decrement of perme­
ation and lifetime of the membrane [9]. Membrane fouling is classified
as organic, inorganic, and biofouling and may occur due to foulants
adsorbing or adhering to the membrane surface and pores or as a result
of cake layer compression. One of the severe problems in using mem­
branes for bacterial effluents is biofouling caused by deposition, stick­
ing, and growth of microorganisms on internal and external surfaces of
the membrane [10,11]. Since many compounds causing fouling are
organic and hydrophobic, membrane modification is necessary to
overcome fouling, especially for some inherent properties of the mem­
brane strongly influenced by materials and fabrication methods,
including surface roughness, pore size, hydrophilicity, and surface
charge [12]. Grafting, surface coating, plasma treatment are some
known approaches for membrane modification [13]. Recently, incor­
porating nanofillers into polymeric structures has received great atten­
tion as a simple and effective modifying approach. This method has been
able to overcome some challenges related to permeation flux, fouling,
mechanical and chemical stability, and rejection.
Various nanostructures, including carbon-based nanomaterials,
metal and metal oxide nanoparticles, water channel proteins, and met­
al–organic frameworks, have been used to modify membranes [14]. A
large number of nanoparticles, such as silver [15] adipate ferroxane
[16], Fumarate alumoxane [17], peroxopolyoxometalate [18],
lanthanum vanadate [19], copper zinc tin sulfide [20], cysteine-
functionalized graphene oxide [21], and Zirconium dioxide [22], are
among the nanostructures that have been used as a filler for modifying
PES membrane. The presence of adsorption sites inside the membrane
structure, particularly in the surface layers, is critical for reducing heavy
metal ions in the membrane’s output stream. In 2013, Taurozzi et al.
[23] fabricated a novel polymeric membrane with p-xylylene-peraza
[2.2.2]cryptand (Aza222) that showed high performance for Hg2+
removal from aqueous solutions. Zinadini et al. [24] prepared PES/tet­
rathioterephthalate (TTTP) nanocomposite membrane. The results
demonstrated a flux recovery ratio (FRR) of 98.2% for 0.1 wt% TTTP
(3.1 times higher than bare PES) and 99.2, 98.5, and 97.4% of rejection
for Zn2+, Cu2+ and Pb2+, respectively. A PES membrane was fabricated
in another study by incorporating boehmite nanostructures functional­
ized with curcumin [25]. The modified membranes’ pure water flux was
enhanced. The rejection of heavy metals ions of 0.5 wt% boehmite-
curcumin-PES membrane was reported as 99.88, 98.72, 99.61, 99.31,
99.11, and 99.51% for Fe2+, Cu2+, pb2+, Mn2+, Zn2+, and Ni2+
respectively. The PES nanocomposite membrane modified by graphene
oxide-metformin showed 92 and 99% rejection for copper ions and dye
removal, respectively [26]. The membrane modified with TTTP coating
on aniline oligomers-grafted PES showed 90% rejection of Cu2+ and
Pb2+ for different concentrations of feed in comparison with bare PES
membrane, which showed maximum rejection of Cu2+ and Pb2+ by
32.20 and 32.10%, respectively [27].
Bentonite is a kind of clay that is typically formed after the change of
volcanic ash. It is composed mainly of montmorillonite. The structure of
bentonite is composed of two significant blocks; the octahedral
aluminum sheet is surrounded and squeezed between two tetrahedral
silica sheets. A weak negative charge of the silicate layers has created the
potential of interaction with cation ions from accommodated space
through intermediate layers. Bentonite has significant swelling, viscos­
ity characteristics. All of these properties are highly appreciated in in­
dustrial settings. Bentonite is an excellent binder for foundry mud and
suspending agent in oil well drilling fluids. Also, bentonite is used in
many other industries, including catalysts, Pharmaceuticals, paints,
rubber, paper, civil construction, and agriculture [28]. Recently,
bentonite clay has been considered a natural and low-cost alternative
adsorbent and membrane modifier agent due to its intrinsic attributes,
including high surface area, high thermal resistance, hydrophilicity, and
surface negative charge [29]. Dutta et al. [30] functionalized bentonite
2
Chemical Engineering Journal 431 (2022) 134116
particles using EDTA as an improving filler for polysulfone membrane
and used the membrane for heavy metal ions removal from industrial
effluent. The prepared mixed-matrix membranes showed a more hy­
drophilic surface and better antifouling properties due to the presence of
functionalized bentonite particles. The highest permeability was 7.4 ×
10-11 m/Pa.s, and the rejection of Ni2+, Cu2+, Zn2+, and Pb2+ ions was
92–98 %. Kumar et al. [31] prepared and characterized polysulfone/
bentonite ultrafiltration membranes to treat oily produced water. They
compared the characteristics and performance of the polysulfone/
bentonite membrane with the polysulfone/silica membrane. The results
exhibited a more efficient rejection performance of the polysulfone/
bentonite membrane than the polysulfone/silica membrane. Ahmad
et al. [32] reported in 2018 the utilizing of bentonite to fabric PVC ul­
trafiltration membrane.
The results proved that bentonite enhanced the membrane surface
porosity and pore density and improved the antifouling capability (flux
recovery ratio: 81.97%) and oil rejection performance (97.0%). In 2018,
Ahmad et al. [33] investigated the fabrication of the low-cost PVC/
bentonite ultrafiltration membranes via phase inversion method with
different solutions in the coagulation bath, including NH4Cl NaCl, KCl,
MgCl2, and CaCl2 and used for the filtration of oilfield water produced.
The formed membrane in the KCl coagulation bath with the 5 wt% of
bentonite exhibited the highest pure water flux of 467.5 L m-2h− 1 atm− 1.
At the same time, the best rejection performance (98.6%) was related to
the membranes with 18.0 g and 0.0 g bentonite. In another study,
Ahmad et al. [34] used different loading of the inorganic salts and N-
methyl-pyrrolidone to fabricate high-performance PVC/Pluronic F127/
salt/bentonite ultrafiltration membranes. The addition of bentonite
nanoclay to the casting solution, including Pluronic F127 and KCl-
induced PVC, significantly enhanced membranes surface hydrophilici­
ty, water permeate, and oilfield produced water flux. Also, they reported
the optimal preparation of PF127/polyacrylonitrile/bentonite-blended
PVC ultrafiltration membranes for oilfield wastewater treatment [35].
The optimally fabricated membrane exhibited the enhancement and
stability of water flux, antifouling performance for the long-time test.
Some other studies have reported using bentonite as an inorganic agent
combined with membrane to improve overall performance [36–38]. One
of the inherent weaknesses of bentonite is its low antibacterial capa­
bility. Kamyar et al. [39], using the inhibition zone method, demon­
strated that montmorillonite has no antibacterial properties against
Escherichia coli and Staphylococcus aureus. They revealed that adding
chitosan and synthesizing silver nanoparticles in the lamellar space of
montmorillonite resulted in intense antibacterial activity for Ag-
montmorillonite/chitosan compound. Santos et al. [40] investigated
the antibacterial activity of raw bentonite and bentonite treated with
acid. They expressed the absence of antibacterial activity for raw
bentonite against Escherichia coli and Staphylococcus aureus bacteria. In
2017, Bama et al. [41] enhanced the antibacterial activity of pristine Na-
bentonite by using Ag and TiO2 against Escherichia coli and Staphylo­
coccus aureus. Several metallic nanoparticles, such as Au, Ag, Ni, Cu, and
Zn, have been introduced in the form of nanostructures with antibac­
terial activity [42]. Chaudhary et al. [43] synthesized Ni nanoparticles
via the chemical reduction method with an average crystalline size of 30
nm. They investigated the antibacterial capability of the nanoparticles
with different concentrations (20, 40, and 60 µg) against four types of
bacteria. The results indicated the highest antibacterial activity of Ni
nanoparticles at the concentration of 60 µg against Pseudomonas aeru­
ginosa. Ezhilarasi et al. [44] used Solanum trilobatum extract to synthe­
size NiO nanoparticles. In this study, the highest inhibition zone (21
mm) was obtained against Staphylococcus aureus using 150 µg/mL of NiO
nanoparticle. In another study, the findings exhibited obtained inhibi­
tion zone (6 and 4 mm) against Staphylococcus aureus and Escherichia coli
with 0.01 g of Ni nanoparticles at 37 ◦ C [45]. The presence of nickel ions
as heavy metals in the environment and natural water currents could be
hazardous. Nevertheless, in addition to its antibacterial properties,
nickel also has some valuable properties, including biocompatibility,
S. Dadari et al.
cost-effectiveness, abundance, reactivity, and anti-inflammatory activ­
ity, which have increased its usage in various industries [46]. Due to
these characteristics, controlled usage of nickel can be more advanta­
geous than uncontrolled release into the environment, and it can be
utilized even in the environmental process. Nickel-bentonite is a hybrid
compound that is ideal for use as a catalyst due to its availability, low
cost, and ability to rupture C–H and –C bonds [47]. There are several
chemical and physical approaches for the synthesis of nanoparticles.
These methods have limitations, such as high pressure, high tempera­
ture, toxic solvents, and hazardous reagents. In recent years, the green
synthesis of nanostructures using plant extracts due to biocompatibility,
large-scale synthesis potential, simplicity, safety, availability, and cost-
effectiveness has attracted a great deal of interest. The green synthesis
processes use a large number of biomolecules. Plant extracts include a
variety of biomolecules, including polyphenols (phenolic acids, flavo­
noids, and non-flavonoids), polyphenylene, iridoids, vitamins, enzymes,
amino acids, carbohydrates, proteins, and alcoholic compounds. How­
ever, the synthesis of nanoparticles using plant extracts is complicated
and yet little known; numerous studies have shown the function and
impact of these biomolecules in reducing and stabilizing the nano­
particles throughout their green production [48,49]. Scrophularia
striata is a flowering plant growing naturally in mountainous areas of
western and northwestern Iran. Chemical analysis of Scrophularia
striata with chromatographic and phytochemical methods has proved
the existence of the polyphenol and polyphenylene compounds with
various functional groups, including high levels of flavonoids (quercetin
and Isorhamnetin-3-O-rutinoside), phenolic acids, phenylpropanoid
glycoside, and iridoids in the plant extract [50–52]. According to the
studies, these biomolecules could act as reducing agents for metal ions.
Additionally, they serve as a capping agent, preventing nanoparticles
accumulation [49]. Some quantitative studies investigated the antibac­
terial activity of Scrophularia striata against different bacteria
[51,53,54]. Also, Scrophularia striata possess anti-cancer, antioxidant,
and anti-inflammatory effects [55].
As mentioned, heavy metal ions and pathogenic bacteria in water
sources can be dangerous to human health and the environment. As a
result, it is critical to use appropriate water and wastewater treatment
method that prevents the introduction of heavy metal ions and bacteria
into natural water sources. According to these challenges, the antibac­
terial and antifouling modified nanofiltration PES membranes were
fabricated in this study. In this way, we used an utterly eco-friendly
method to synthesis the membrane modifier agents (nickel-bentonite
nanoparticles) using Scrophularia striata extract. We utilized the anti­
bacterial property of Scrophularia striata extract and nickel and the
excellent absorption property of bentonite in one unit of the nano­
particle to modify the PES membranes. The main novelties of this study
are:
• The green synthesis of nickel-bentonite nanoparticles using Scro­
phularia striata extract.
• Using nickel-bentonite nanoparticles to modify the overall charac­
teristics of PES membranes.
• Enhancement of the antibacterial and heavy metal ions removal
performance of the PES membranes by using the green synthesized
nickel-bentonite nanoparticles.
To the best of our knowledge, in this study, for the first time, the
nickel-bentonite nanoparticles (NBNPs) have been synthesis by the
green method and used to modify a PES membrane for improving
antibacterial capability and heavy metal ions rejection. The modified
membranes can be considered a significant candidate for the treatment
of effluents containing heavy metal ions in various industries such as
paint, paper, petroleum, and bacterially contaminated effluents such as
hospital effluents in one membrane-treatment process instead of using
two or more processes for removing bacteria and heavy metal ions.
Based on the nanoparticle green synthesis process and membranes’
3
Chemical Engineering Journal 431 (2022) 134116
ability to simultaneously treat contaminated wastewater from heavy
metals and bacteria, it could be attractive for membrane manufacturing
companies from an economic and environmental point of view.
Aqueous extract of Scrophularia striata was prepared and character­
ized by Fourier transform infrared (FT-IR) analysis. The NBNPs were
synthesized using Scrophularia striata extract and characterized by FT-
IR, zeta potential, X-ray diffraction (XRD), energy-dispersive X-ray
spectroscopy (EDS), field-emission scanning electron microscopy
(FESEM), transmission electron microscopy (TEM) analyses. The bare
and modified nanofiltration membranes were prepared via the phase
inversion method. FTIR, EDS, and XRD analyses were conducted to
verify the formation of NBNPs/PES membranes. FESEM was used to
evaluate the membranes’ cross-sectional and surface morphology. The
water contact angle, overall porosity, surface pore size distribution,
mean pore radius, and zeta potential measurements were done to
characterize the prepared membranes’ hydrophilicity, porosity, and
surface charge. The roughness of the surface of the membrane was
determined using atomic force microscopy (AFM). The membranes’
pure water flux and antifouling parameters (reversible fouling ratio,
irreversible fouling ratio, total fouling ratio, and flux recovery ratio)
were evaluated via long-term cyclic filtration of pure water and milk
powder solution. The elimination of heavy metal ions was investigated
using ionic solutions containing Pb2+, Cu2+, and Zn+2. The antibacterial
capability of the membranes against Escherichia coli (Gram-negative
bacterium) and Staphylococcus aureus (Gram-positive bacterium) was
also investigated using inhibition zone and colony-forming count
methods.
2. Experimental
Fig. 1 states the steps of the research method in order. At first, NBNPs
were synthesized and characterized. Next, the membranes were fabri­
cated via phase inversion procedure and characterized. Following that,
the performance of the membranes was evaluated using flux and anti­
fouling, heavy metal ions rejection, and antibacterial analyses.
2.1. Materials
All chemicals were reagent grade. Polyvinylpyrrolidone (PVP, Mw =
25000 g/mol), Ni (NO3) 2.6 H2O (290.81 g/mol, 99.999% trace metals
basis), Zn(NO3)2⋅6H2O (297.49 g/mol, 98% reagent grade), Cu
(NO3)2⋅2.5H2O (232.59 g/mol, 98 %ACS reagent), Pb(NO3)2 (331.21 g/
mol, ≥99.0% ACS reagent) and Ethanol (46.07 g/mol, 96%) were pur­
chased from Merck.
Dimethylacetamide (DMAc) (87.12 g/mol, 98%) as a solvent and
Polyethersulfone (Ultrason E 6020P, Mw = 58,000 g/mol) were pro­
vided by BASF Co.
Bentonite clay nanopowder (Purity: 99%, APS: <80 nm) was ob­
tained from Nanoshel. Phosphate buffered saline(PBS) was supplied by
Sigma-Aldrich. Luria-Bertani (LB) broth miller (LBL407.500) was pur­
chased from BioShop lnc., Canada. Agar was obtained from Daejung
Chemical Co. Aerial parts of Scrophularia striata were collected from the
north-eastern mountains (1440 m above sea level) of Ilam province.
Deionized water (DI) was provided by the Millipore Milli-Q purification
system (18.2 MΩ cm). Kermanshah University of medical science pro­
vided staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC
25922).
2.2. Green synthesis of NBNPs
The biological conversion of a metal salt to metal nanoparticles using
plant extracts is a straightforward and ecologically benign method that
utilizes oxidation–reduction processes.
Fig. 2 illustrates a schematic of a green synthesis process using plant
extracts. These responses occur within a few minutes. When aqueous
extracts of plants are combined with aqueous solutions of metal salts, the
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig.1. Steps of the experimental method.

Fig. 2. Schematic of NBNPs green synthesis procedure. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

4
S. Dadari et al.
solution changes color, indicating the formation of nanoparticles [56].
Extraction of Scrophularia striata was the initial step for the synthesis of
NBNPs. The dried powder of Scrophularia striata was added to DI water
at 80 ◦ C while stirring. After 20 min, the mixture was filtered and
centrifuged to get the final extract. Following that, 100 ml of the final
extract was freeze-dried for FT-IR analysis, and the remaining was stored
at 4 ◦ C for further use. For the synthesis of NBNPs, bentonite powder was
added to the extract at 80 ◦ C while stirring. After a time, the Ni2+ so­
lution was added to the mixture, and After centrifuging the mixture and
heating it in the oven, green synthesized NBNPs were obtained.
2.3. Preparation of the NBNPs/PES membranes
According to our earlier research, The phase inversion method was
used to fabricate NBNPs/PES membranes [57]. NBNPs were dispersed in
DMAc in different concentrations by sonication (DT 102H Bandelin
Ultrasonic, Germany) for 30 min. Then, PES and PVP were added to the
suspension and stirred for 24 h (400 rpm). The solution was sonicated to
bubble releasing for 20 min and cast on a glass plate using a metallic film
applicator thickness of 150 µm. The glass plates were immediately
submerged in a DI water coagulation bath for 2 min. For 24 h, the
produced membranes were put in a container filled with DI water to
remove any remaining solvent. The membranes were then sandwiched
between two sheets of filter paper to dry thoroughly. Table 1 lists the
compositions of the prepared membranes.
2.4. Characterization
Fourier transform infrared (FT-IR) is a method for identifying
chemical bonds and properties of organic, polymeric, and, in certain
situations, inorganic materials. In FT-IR analysis, infrared light is
used to scan samples and determine their chemical characteristics. The
chemical bonds and functional groups of Scrophularia striata, NBNPs,
and the prepared membranes were evaluated by FT-IR spectra according
to the ASTM standards (E168 and E1252) using a spectrophotometer
(PerkinElmer, Spectrum Two, USA). XRD is a method used to determine
the crystallinity or amorphous nature of materials. Additionally, it
contains information on the structure, the average grain size, the phases,
and other relevant characteristics. The nanoparticles’ XRD patterns were
identified using the Panalytical X’ Pert Pro diffractometer (Cu Kα, λ =
1.54055 A◦ radiation) according to the joint committee on powder
diffraction standards(JCPDS). The morphology of NBNPs and the pre­
pared membranes were evaluated with field emission scanning electron
microscopy (FESEM, Sigma VP, ZEISS, Germany) based on the Inter­
national Organization for Standardization (ISO) standards (19749:2021,
and 9220:1988).
Energy-dispersive X-ray spectroscopy (EDS) was used to explore the
element composition of the membranes and nanoparticles (FESEM,
Sigma VP, ZEISS, Germany) according to the ASTM E1508 − 12a. A
transmission electron microscope (TEM) was used for a closer look at the
morphology, including shape and size distribution of NBNPs (EM10C,
100 KV, ZEISS, Germany) based on ISO 21363:2020 standard. The study
of the zeta potential of the nanoparticles for evaluating surface charge
related to the functional groups was carried out using a zeta sizer (Ultra,
Malvern, Netherland) according to the ISO 13099–2:2012. Roughness
and topology of the surface of the membranes were analyzed at different
amounts of NBNPs by atomic force microscopy (AFM, TMDS 95–200/50,
Table 1
composition of the prepared membrane.
Membrane PES(wt.%) PVP(wt.%) DMAc(wt.%) NBNPs(wt.%)
M− 0(PES) 20.0 1.0 70.0 0.0
M− 1 20.0 1.0 69.9 0.1
M− 2 20.0 1.0 69.5 0.5
M− 3 20.0 1.0 69.0 1.0
5
Chemical Engineering Journal 431 (2022) 134116
DME, Denmark). The surface charge of the membranes (with 0.01 M KCl
solution in PH = 6) was measured using Electro Kinetic Analyzer (EKE,
Anton Paar, Austria). Measurement of the static contact angle was car­
ried out by Drop Shape Analyzer (DSA100E, KRUSS, Germany). An
atomic absorption spectrometer (AA500FG, PG Instruments Limited,
United Kingdom) determined heavy metal ions concentration according
to ASTM D4691 − 17.
The overall porosity (ε) was determined by the gravimetric method,
and the average value of 4 times measurements was reported:
( )
W1 − W2
ε(%) = × 100 (1)
ρAl
Where W1 and W2 are the wet and dry membrane weights. A, ρ and l
refer to the membrane surface area (cm2), water density (0.998 gr/cm3),
and the thickness of the membranes (using a digital micrometer, Mito­
toyo, Japan).
2.5. Pure water flux
The pure water flux of the prepared membranes was analyzed using
the dead-end filtration cell we used in our previous study [16]. Soaking
in deionized water for 1 h, pressurizing at 6 bar for 30 min with nitrogen,
and eventually, reduce pressure to 4 bar were carried out for all the
prepared membranes before taking any test. Pure water flux was
calculated every 10 min during 1 h according to the following equation:
M
J= (2)
At
Where M, A, and t, are the weight of permeated water (kg), the
membrane area (m2), and permeation time (h), respectively.
2.6. Evaluation of antifouling performance
The capability of the membranes to resist fouling was assessed using
reversible fouling ratio (Rr), irreversible fouling ratio (Rir), and total
fouling ratio (Rt), and flux recovery ratio (FRR). Reversible fouling is
caused by the weak attachment of fouling agents on the membrane
surface and is generally cleaned with regular washing, and Rr refers to
the membrane resistance against reversible fouling. Pore plugging and
adsorption on the membrane surface, which is more challenging to
overcome and, in most cases, must be removed chemically, is called
irreversible fouling. Rir evaluates the membrane resistance against
irreversible fouling. Rt exhibits membranes resistance against both
reversible and irreversible fouling. FRR refers to the membrane’s ability
to recover its initial flux after filtering a solution containing foulants
[58,59]. After the pure water flux test during the first 60 min, milk
powder solution (8000 mg/L) was replaced in the dead-end cell and
filtered (150 min). Then, the membrane was removed from the filtration
cell, washed with DI water for 15 min, and replaced in the dead-end cell
to determine pure water flux for the final 60 min.
Antifouling capability test was performed at a pressure of 4 bar and
under stirring conditions. Following equations were used to calculate
FRR, Rr, Rir, and Rt:
( )
Jc
FRR(%) = × 100 (3)
Jw
( )
Jc − Jp
Rr (%) = × 100 (4)
Jw
( )
Jw − Jc
Rir (%) = × 100 (5)
Jw
( )
Jw − Jp
Rt = (6)
Jw
Jw, Jc, and Jp refer to pure water flux, water flux after cleaning the
S. Dadari et al.
membrane, and the milk powder solution flux in kg/m2h.
2.7. Heavy metal ions filtration
The low-concentration solutions (20 mg/L based on anhydrous
weight) of Zn(NO3)2⋅6H2O, Cu(NO3)2⋅2.5H2O, and Pb(NO3)2 were
used to examine the capability of the membranes to eliminate heavy
metal ions (Pb2+, Cu2+, Zn2+). The rejection percentage was determined
using the following equation:
( )
Cp
R(%) = 1 − × 100 (7)
Cf
Cf and Cp are the concentration of heavy metal ions in the feed and
permeate, measured by atomic absorption spectrometer.
2.8. Pore size analysis
The surface pore size distribution of the prepared membranes was
evaluated using AFM images. The surface area of 4 µm2 of each sample
was scanned using DME software to determine pore size distribution
[60].
Guerout-Elford-Ferry equation (Eq. (8)) was used to compute the
mean pore radius of the membranes [61] :
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(2.9 − 1.75ε)8ηlQ
rm = (8)
εAΔP
ε, η, l, Q, A, and ΔP are overall porosity (%), the viscosity of water
(8.9 × 10–4 Pa s), pure water flow as a permeate (m3/s), area of the
membrane surface (m2) and operation pressure (0.3 MPa), respectively.
2.9. Antibacterial activity
2.9.1. Preparation of bacteria
At first, a single colony of bacteria was cultured in Luria-Bertani (LB)
broth (sterilized at 120 ◦ C for 20 min in an autoclave) at 37 ◦ C and 200
rpm for 24 h. Afterwards, 2 ml of the bacterial culture was inoculated
into a flask containing 200 ml fresh and sterilized LB and placed in a
shaking incubator at 37 ◦ C and 120 rpm for 24 h. Then, the culture was
centrifuged (at 3500 rpm for 20 min) and washed several times with
phosphate-buffered saline(PBS) solution. The separated bacteria were
suspended in PBS solution (pH = 7.4) and diluted to 104 colony forming
units (CFU)/ml concentrations [62].
2.9.2. Inhibition zone analysis
3 ml of the prepared bacterial suspension (104 CFU/ml) was
dispersed on LB-agar plates uniformly. Then sterilized pieces of the
membranes were put on the top of plates in contact with LB-agar me­
dium. The plates were placed in an incubator at 37 ◦ C. After 48 h, the
halo zone was formed, and observation of the transparent locations on
the disk where the bacteria could not be grown indicated the modified
membranes antibacterial properties. Digital photos were recorded to
analyze the halo zones formation [63].
2.9.3. Quantitative method
The quantitative study of the prepared membranes’ antibacterial
properties was evaluated by the colony-forming count method. Pieces of
the membranes were sterilized by autoclaving and UV irradiation. Then,
the samples were soaked into the bacterial suspension (100 ml, 104
CFU/ml) and incubated at 37◦ C and 120 rpm for 12 h. after that, the
membranes were removed from the bacterial suspension and washed
with PBS. The treated solution was diluted with deionized water, and 1
ml of the diluted solution was spread on LB-agar plates and incubated at
37◦C.
After 24 h, the antibacterial rate was calculated by counting the
viable bacteria colonies. Equation (9) express the percentage of
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Chemical Engineering Journal 431 (2022) 134116
antibacterial rate [64] :
( ) ( )
A CFU CFU
ml
− B ml
Antibacterialrate(%) = ( ) *100 (9)
A CFUml
A and B are the colony counts of the bacterial cultures contacted with
the unfilled PES membrane and NBNPs/PES membranes, respectively.
3. Results and discussion
3.1. Characterization of the NBNPs
FT-IR analysis detects the various functional groups bonds associated
with nanostructures. It is the most necessary analysis in the green syn­
thesis used in many research types as a primary identifying method for
recognizing biomolecules and related functional groups responsible for
reducing metal ions and forming nanoparticles [49,65,66]. The results
of FT-IR analysis of Scrophularia striata extract and NBNPs are shown in
Fig. 3. The peaks at 3402 and 3428 cm− 1 are related to the O–H stretch
band of carboxylic acids. Peaks for saturated hydrocarbons (-C–H-SP3)
were observed at 2930 cm− 1 and 2925 cm− 1. Carbonyl groups were
detected in the peaks at 1646 cm− 1 and 1605 cm− 1.
The peak of aromatic rings was specified at 1385 cm− 1.
Some peaks at 1300 cm− 1 to 1000 cm− 1 confirmed C-OH stretching
vibrations. The broadband appeared at about 500 cm− 1, corresponds to
metallic nanoparticles. The results showed that the presence of func­
tional groups related to polyphenols, such as flavonoids and phenolic
acids, in the plant extract is probably the reason for forming NBNPs. The
primary function of these biomolecules found in the plant extracts is to
reduce metallic ions and stabilize the resultant nanostructures. The
п-electron interaction of the functional groups and surface of the metal
ions resulted in functionalized NBNPs [67,68]. In addition, functional
groups played a role as ligating agents between nickel nanoparticles and
bentonite structure. In fact, without the interaction of biomolecules and
nanoparticles surface, observation of the peaks related to functional
groups is not possible in FTIR analysis [69]. According to the related
studies, the proposed mechanism for the formation of NBNPs is shown in
Fig. 4 [70–73].
Along with FT-IR analysis, zeta potential measurements were used to
analyze the effect of biomolecules present in the plant extracts and their
associated functional groups on the structure of green synthesized
nanoparticles (Fig. 5). Zeta potential could be advantageous for deter­
mining the functionalities of nanostructures[49]. As the findings indi­
cated, NBNPs had a higher zeta potential than bentonite nanostructures,
implying the existence of functionalities on their surfaces linked to
biomolecules from the plant extracts. The change in zeta potential value
after the green synthesis method verifies the plant extract’s influence in
the synthesis procedure, leading to functionalized nanoparticles for­
mation. Generally, high zeta potential levels, either positive or negative,
must be obtained to preserve particle stability and prevent particle ag­
gregation [49,74].
The XRD patterns confirmed the formation of NBNPs (Fig. 6). The
analysis showed that the main compounds of the bentonite structure are
montmorillonite and quartz. Diffraction peaks at 2θ = 19.84◦
(0 2 0),35.21◦ (1 3 0) and 61.84◦ (0 6 0) are related to planes of mont­
morillonite (JCPDS 29–1498), and the peaks attributed to quartz were
located at 2θ = 26.81◦ (1 0 1),36.25◦ (1 1 0) according to JCPDS 05–0490
card. Impurities corresponding to illite, cristobalite, and feldspar are
shown in other peaks [75]. Diffraction peaks of nickel appeared at 2θ =
44.4◦ (1 1 1),52.1◦ (2 0 0), and 76.4◦ (2 2 0) according to JCPDS 87–0712
card. These peaks confirmed desirable dispersion and crystalline size
[76].
The elemental composition of the bentonite and NBNPs were deter­
mined by EDS analysis (Fig. 7). The signal showed the presence of Al, O,
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 3. FT-IR spectrum of the plant extract (a) and NBNPs (b).

Fig. 4. Proposed mechanism for NBNPs green synthesis. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

Mg, Si, Au, and Ca in the bentonite structure. The results confirmed the
existence of nickel in the NBNPs. The signal corresponding to carbon
indicated the presence of biomolecules of the plant extract, which led to
the formation of nickel nanoparticles.
Fig. 8 shows the FESEM and TEM images and size distribution of
NBNPs. The conditions of the green synthesized process led to the for­
mation of spherical NBNPs, with an average size of 64 nm. It has been
observed in previous studies in which the final shape of nanostructures
containing bentonites such as Fe3O4/bentonite, chitosan-coated
Bentonite clay composite capsules-Cr(VI), and ash-bentonite was
spherical [77–79], similar to our study. As mentioned, the higher zeta
potential of nanoparticles leads to a decrease in aggregation and
agglomeration [49,74]. The green synthesized NBNPs exhibited signif­
icantly high zeta potential, and according to the results, the SEM images
exhibit the minimum agglomeration obviously, as similar study results
show [80].TEM was used to characterize the shape and size of NBNPs.
The deposition of nickel nanoparticles on the bentonite structure was
observed clearly.

7
S. Dadari et al.
Fig. 5. Zeta potential analysis of bentonite (a) and NBNPs (b).
Fig. 6. XRD patterns of the bentonite and NBNPs.
3.2. Characterization of the fabricated membranes
3.2.1. FTIR and EDS analysis of the unfilled PES and NBNPs/PES
membranes
Fig. 9 (a) shows the FTIR spectra of the bare PES and nanocomposite
membranes. The absorption bands at 1145 and 1315 cm− 1 are ascribed
to symmetric and asymmetric stretching of sulfone groups in the struc­
ture of PES [25]. Asymmetric stretching of C–O is represented at 1106
cm− 1 [81]. The peaks at about 1485 and 1578 cm− 1 are related to
benzene rings [82]. Two peaks around 1478 and 1575 cm− 1 are asso­
ciated with the intrinsic characteristic of the PES matrix [83]. Due to the
low amount of NBNPs in the polymer matrix, the FTIR spectra results
exhibited a similar chemical structure of the bare PES and 1 wt%
NBNPs/PES membrane.
The nanocomposite membrane showed more substantial absorption
peaks around 3445, 1660, and1020 cm-1 corresponding to the poly­
phenol hydroxyl group, stretching of carbonyl groups, and C-OH
stretching vibrations. These peaks confirmed the presence of functional
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Chemical Engineering Journal 431 (2022) 134116
groups related to NBNPs on the surface of 1 wt% NBNPs/PES membrane.
Fig. 9 (b) shows a comparison of the XRD patterns of the 1 wt% NBNPs/
PES membrane and the bare PES membranes. The characteristic peaks of
both NBNPs and polyethersulfone were detected in the XRD pattern.
Although, due to the low amount of nanoparticles in the polymer
matrix, the characteristic peaks of NBNPs were not more intense. In
order to confirm the presence of NBNPs in the structure of the modified
membranes, EDS analysis was performed (Fig. 9 (c)). The results illus­
trated the presence of NBNPs in the polymer matrix.
3.2.2. The morphology of the bare and modified membranes
The top-surface, cross-section, and matrix morphology of the mem­
branes are shown in Fig. 10. The top-surface SEM images indicated the
modified membranes’ smooth and crack-free surface with no agglom­
eration of NBNPs on the surface. The surface of the nanocomposite
membranes is darker than the bare PES membrane, and it can be
attributed to the hydrophilicity of the nanoparticles, resulting in
migration to membranes surface during the phase inversion process
S. Dadari et al.
Fig. 7. EDS spectrum of the bentonite (a) and NBNPs (b).
[84]. Solvent and nanofillers used are two key parameters influencing
the cross-section morphology of polymeric membranes [85]. As ex­
pected, SEM images of the cross-section illustrated that all the mem­
branes have typical asymmetric morphology, including a dense thin top-
layer and thick sponge-like sub-layer with finger-like cavities. The dense
structure of the top layer enhances filtration efficiency, and the porous
sub-layer structure improves membrane stability [86].
The nanocomposite membranes’ porosity has increased along with
increasing NBNPs loading in the casting solution; it is mainly due to the
presence of hydrophilic NBNPs in the polymer matrix and intrinsic
swelling property of the bentonite in water, resulting in a rapid ex­
change rate between solvent and non-solvent in coagulation bath [87].
Consequently, the porosity and pore size of the modified membranes has
been improved. The SEM images of polymer matrix related to M− 2 and
M− 3 membranes indicated dispersion of NBNPs.
3.2.3. Hydrophicility, mean pore radius, and zeta potential
Hydrophilicity is one of the most important parameters influencing
properties of polymeric membranes, including flux and antifouling
performance [88]. Water contact angle analysis was used to determine
the surface hydrophilicity of the pristine and blended membranes
(Fig. 11 (a)). As can be observed, the NBNPs/PES membranes had a
lower water contact angle than the bare PES membrane. The findings
indicated that a higher concentration of nanoparticles in the polymer
matrix resulted in increased hydrophilicity, wettability, and contact
angle reduction. The decreasing trend in water contact angles may be
attributed to hydrophilic NBNPs migrating to the water/membrane
interface during the phase inversion process [84]. Hydrophilic func­
tional groups (e.g., carbonyl, carboxyl, and hydroxyl groups) in the
structure of NBNPs led to the increase in nanoparticles affinity to water
molecules via hydrogen bonding [89]. Also, favored and selective
adsorption of water molecules by bentonite could be another reason for
the decrement in water contact angle [90]. The color difference between
the top and bottom surfaces of the blended membrane indicated the
presence of NBNPs on the top surfaces. (Fig. 11 (b)).
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Chemical Engineering Journal 431 (2022) 134116
The surface pore size distribution of the prepared membranes is
shown in Fig. 12. A Gaussian curve fitted the distribution histograms.
The results illustrate that introducing NBNPs at 0.1, 0.5, and 1 wt% to
the polymer matrix improved pore sizes. By increasing the amount of the
nanoparticles, the maximum point of the Gaussian curves moved to the
larger pore sizes.
The data of Fig. 12 and Table 2 prove that the overall porosity and
mean pore radius of NBNPs/PES membranes are higher than the bare
PES membrane. The overall porosity and mean pore radius were
improved from 67.9 to 75.8% and 5.88 to 7.67 nm, respectively, by
adding
0.1 wt% of NBNPs. This trend continued up to 0.5 wt% of NBNPs. In
general, introducing hydrophilic nanofillers enhances or decreases
polymeric membranes’ porosity and pore radius (depending on the
dose) by affecting the thermodynamic and kinetic parameters during the
phase inversion process [91]. Thermodynamic instability could cause
phase separation in polymeric solutions. Changes in the composition of
components, phase equilibrium, and temperature fluctuations could
result in phase separations, change demixing rate and shift polymeric
solution condition from homogeneous to heterogeneous conditions. So,
the thermodynamic stability of the components is a critical factor in
influencing the formation of membrane structure during the phase
inversion method. By introducing additives, the thermodynamic phase
equilibrium of non-solvent/solvent/polymer is disrupted. Additives
such as nanoparticles could reduce the miscibility of casting solutions in
interaction with the non-solvent in the coagulation bath and affect the
demixing rate [92,93]. The first reason for the porosity increment is the
thermodynamic instability condition of the casting solution at low doses
of NBNPs. Hydrophilic NBNPs in the casting solution and their tendency
to water molecules broke the thermodynamic stability, speeding up the
demixing rate of solvent and non-solvent and making more and bigger
pores in the membrane structure during phase inversion procedure in
the coagulation bath [94]. The barrier effect of NBNPs in the casting
solution, which limited the interactions between polymer chain and
solvent, leading to easier penetration from the polymer matrix to
S. Dadari et al.
Fig. 8. FESEM (a), TEM (b), and size distribution (c) of NBNPs.
coagulation bath for solvent, could be considered a second reason for the
enhancement of porosity and pore radius [95].
Another reason is favorable osmotic and crystalline swelling of
bentonite with the solvent that provided the appropriate capability of
solvent-holding, which improved porosity and mean pore radius of the
blended membranes [90]. At a high amount of NBNPs (beyond 0.5 wt
%), the viscosity of the solution was increased, and the kinetic condition
was dominant, resulting in the decrement of pore radius and porosity
[96]. In addition, pore-blocking at higher concentrations caused by
aggregation of nanoparticles could decrease porosity and pore radius
[97].
The surface charge of the prepared membranes was investigated by
measuring zeta potential at a pH of 6 (with 1 mM KCL). According to the
results (Table 2), all the membranes had a negative surface charge. Zeta
potential became more negative and changed from − 10.62 to-17.33 mV
by the addition of 0.1 wt% NBNPs to PES.
As mentioned earlier, the surface charge of NBNPs is more negative
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Chemical Engineering Journal 431 (2022) 134116
than bentonite as a result of the existence of functional groups related to
polyphenolic compounds of the plant extract. Hydrophilic functional
groups and the intrinsic tendency of bentonite to water molecules cause
NBNPs to be distributed on the top surface of the blended membranes in
coagulation bath and, ultimately, formation of the negatively charged
surface. Typically at a higher amount of nanofillers, membrane surface
charge becomes more negative [95]. Accordingly, the surface charge of
1 wt% NBNPs/PES was more negative among all the prepared
membranes.
AFM images and results regarding measuring roughness parameters
of the bare PES and NBNPs/PES membranes are shown in Fig. 13. The
peaks and valleys (pores) of the membrane’s surface are presented in
bright and dark areas. The average surface roughness of the bare PES
membrane was higher than the modified membranes. Hight and depth of
the peaks and valleys were decreased by introducing a low amount (up
to 0.5 wt%) of NBNPs into the polymer matrix, which led to the creation
of a smoother surface. It could be assigned to the growth of dope solution
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 9. FT-IR spectra (a), XRD patterns (b), and EDS analysis (c) of the PES and 1 wt% NBNPs/PES membranes.

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S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 10. Surface, cross-section, and matrix SEM images of the prepared membranes.

12
S. Dadari et al.
Fig. 11. the contact angle of the prepared membrane (a), and digital photographs of the top and bottom surface of the nanocomposite membranes (b).
viscosity and hydrophilic characteristics of NBNPs, which led to their
migration towards the water/membrane interface in coagulation bath
during phase inversion process and covering valleys of the surface of the
membrane [98]. There was a slight increase in surface roughness by
further loading, and also, as listed in Table 2, mean pore radius and
overall porosity were decreased. This is probably due to a large number
of functional groups of NBNPs, which promoted the tendency of the
nanoparticles to agglomerate in the polymer matrix and surface of the
membranes and led to the decrement of pore radius and porosity and
increment surface roughness. These findings support the data provided
in Table 2.
In most cases, the decrease in surface roughness of the polymeric
membranes improves permeation flux and antifouling performance by
reducing the number of areas where pollutants tend to be absorbed or
adhered [99].
3.2.4. Pure water flux and antifouling performance
The effect of NBNPs with different doses on the pure water flux of the
prepared membranes was evaluated, and the results are represented in
Fig. 14 (a). The pure water flux was greater compared to the pure PES
membrane in all NBNP/PES membranes. Pure water flux was increased
from 15 to 34.4 kg/m2h by adding 0.1 wt% NBNPs. The 0.5 wt% NBNPs/
PES membrane showed the highest pure water flux (about 59 kg/m2h)
among all the prepared membranes.Generally, enhancement of porosity,
mean pore radius, hydrophilicity, and diminution of surface roughness
are the essential key factors resulting in improved permeability and pure
water flux [89]. As mentioned before, migration of hydrophilic NBNPs
boosted surface hydrophilicity and decreased surface roughness. Also,
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Chemical Engineering Journal 431 (2022) 134116
the increment of pore radius and overall porosity, confirmed by SEM
images and the data presented in Table 2, led to increased water
permeation. However, the pure water flux of the nanocomposite mem­
branes declined in 1 wt% loading of NBNPs. This slight decrement is
probably due to the aggregation of NBNPs, causing pore blocking and
reduction of overall porosity [100]. The overall performance of poly­
meric membranes was substantially influenced by fouling. Limiting
permeation flux, deforming and destroying the membrane surface,
increasing operation and maintenance costs, and declining membrane
lifetime are the most significant difficulties caused by the fouling phe­
nomenon. The long-term cycling filtration of water and milk powder
solution utilizing the membranes was conducted over 1200 min, and the
results are shown in Fig. 14 (b) [25,101]. The results reveal that 0.5 and
1 wt% NBNPs/membranes almost equally during 1260 min, with a
slight decline in performance for 1 wt% NBNPs/membrane. Among the
modified membranes, the 0.1 wt% NBNPs/PES membrane had the
sharpest decrease in time-dependent flux, and after 700 min of filtration,
the flux declined continuously without recovery. The flux decrement of
the unfilled PES is greater than that of the modified membranes during
the test, and its water flux recovery after 200 min of filtration was weak.
Additionally, the flux decreased to near zero after 480 min. According to
the cycling filtration test results, the flux values did not reach the initial
flux values after washing due to irreversible fouling caused by severe
deposition of fouling agents on the membrane’s surface or entrapment of
foulant molecules in pores of the structure of the membranes. The
membranes FRR (Fig. 14 (c)) was 98.2, 95.6, 79.9, and 38.3 % in the first
cycle for 0.5, 1, and 0.1 wt% NBNPs/PES and the bare PES membranes,
respectively.
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 12. Surface pore size distribution of the prepared membranes.

could be ascribed to the following reasons :

Table 2
Overall porosity, mean pore radius, and zeta potential of the prepared
• Enhancement of surface hydrophilicity.
membranes.
• Increment of negative surface charge.
Membrane Overall porosity Mean pore radius Zeta potential (at pH = 6 • Reduction of surface roughness.
(%) (nm) mV)

M− 0(PES) 67.9 (±1.5) 5.88 (±0.55) − 10.62 (±0.21) Enhancement of membrane hydrophilicity rejects foulants by a thin
M− 1 75.8 (±2.5) 7.67 (±0.33) − 17.33 (±0.38)
layer of water molecules adsorbed on the hydrophilic surface of the
M− 2 82.3 (±1.2) 9.85 (±0.28) − 20.87 (±0.42)
M− 3 80.2 (±1.1) 8.72 (±0.61) –22.46 (±0.71) membrane [102]. Besides, fouling agents are negatively charged natu­
rally, and the increment of negative surface charge of NBNPs/PES
membranes intensifies charge repulsion between membrane surface and
The flux recovery ratio of the 0.5 and 1 wt% NBNPs/PES membranes negatively charged foulants [103]. Also, as mentioned in earlier sec­
remained more than 94% throughout the long-term filtration test. tions, the smoother surface of the blended membranes declined
Compared to the preceding cycle, the FRR of the 0.1 wt% NBNPs/PES adsorption areas for fouling agents and improved antifouling properties.
and bare membranes decreased sharper with each cycle. Results
regarding measuring antifouling parameters, including Rr, and Rir, are 3.2.5. Heavy metal rejection
indicated in Fig. 14 (d). As can be seen, the Rr, Rir, and Rt were decreased Fig. 15 (a) shows the results regarding the rejection of heavy metal
for all the NBNPs/PES membranes compared to the bare PES membrane. ions of the prepared membranes at 4 bar and room temperatures, and
The bare PES membrane indicated the highest irreversible fouling of the pH of the feed (ionic solution) was adjusted to 6 due to suitable
69.6%. The results showed that introducing a low amount (0.1 wt%) of solubility [24]. Three separated and low concentration ionic solutions
NBNPs into dope solution decreased Rir from 69.6% to 22.1%. The were prepared. Each ionic solution contained just one type of Zn2+,
measurements demonstrated the significant improvements of Rir and Rt Cu2+, and Pb2+ ions. The results were obtained as average values of 5
for 0.5 wt% NBNPs/PES membrane, from 69.6% to 3.14% and from 82% cycles of filtration of each solution. After each cycle of filtration, the
to 64% , respectively. however, further increment of NBNPs concen­ membrane was removed from the dead-end cell and was washed with
tration up to 1 wt% declined FRR, Rr, and Rir. It could be owing to a EDTA solution and DI water, then was replaced in the dead-end cell
slight increment in surface roughness, as confirmed by AFM analysis. filled with a fresh ionic solution at the same concentration. All the
Improvement of antifouling properties of the composite membranes nanocomposite membranes indicated higher rejection of heavy metal

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S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

the bare PES membrane owing to the inclusion of NBNPs with different
functional groups. The negatively charged membrane surface rejects
nitrate (NO3–) ions from the utilized ionic solutions through the Donnan
mechanism, consequently reducing the related heavy metal ions
[104,105]. As shown in Fig. 16, the complicated chelation interaction
between oxygen atoms of functional groups related to polyphenolic
compounds in the NBNPs structure and metal ions is a second possible
explanation for the improved rejection performance of the modified
membranes. This complex chelation interaction resulted in the adsorp­
tion of copper, lead, and zinc ions on the surface of the modified
membranes [106]. The results (see Table 2) showed that although the
NBNPs/PES membranes had a higher overall porosity and pore size than
the unmodified membrane, their efficacy in rejecting heavy metal ions
was more efficient. This contrast between the structure and performance
of the NBNPs/PES membranes demonstrates that the dominant mecha­
nism of heavy metal ion rejection is electrostatic expulsion [25].
Although, a slight decrement in rejection performance was observed for
1 wt% NBNPs/PES membrane, which could be assigned to agglomera­
tion of NBNPs at high concentration [107]. Next, the rejection of heavy
metal ions by the prepared membranes using a solution containing all
ions including Zn2+, Cu2+, and Pb2+ was investigated, and the results are
shown in Fig. 15 (b). As can be seen, the rejection performance of all the
membranes decreased by using a mixture solution of all ions. For
example, the rejection performance of 0.5 wt% NBNPs/PES when
separated ionic solutions of Zn2+, Cu2+, and Pb2+ used was 98.62%,
97.88%, 97.03% , respectively.
However, by using mixture ionic solutions, these values decreased to
76.21%, 74.78%, and 74.22% for Zn2+, Cu2+, and Pb2+respectively. This
was attributable to the presence of divalent metal ions limiting the
mobility of the examined metal ions to the surface of the prepared
membranes. Additionally, complexing ions with the prepared mem­
branes surface functionalities decreases the active functionalities avail­
able to each ion for binding [25,108]. In blended polymeric membranes
modified with nanoparticles because nano-additives are not grafted into
the polymer matrix, It is always possible that the nanoparticles leached
after prolonged use of the membranes with the permeated stream,
reducing the membrane efficiency or contaminating the permeate
stream. To evaluate the leaching possibility of NBNPs from the mem­
branes, the 1.0 wt% NBNPs/PES membrane was not replaced during the
antifouling and heavy metal ions removal test, and only one piece of the
membrane was used for over 1260 min. The cross-section EDS mapping
images (Fig. 17) of the 1.0 wt% NBNPs/PES membrane before and after
using for a long time exhibited that NBNPs are well embedded into the
polyethersulfone matrix, and there was no sign that they were leached
out of the membrane. For a closer look, the existence of nickel ions was
investigated using an atomic absorption spectrometer in the permeate
during heavy metal ions rejection test and analyzing Zn2+, Pb2+, and
Cu2+ ions. The results showed no Ni2+ ions in the membrane’s permeate,
indicating that NBNPs were firmly interacted with the polymer during
the phase inversion process and could not leave the membrane structure
and contaminated permeate flow. Also, Fig. 17 illustrates that the
dispersion of NBNPs in the polymer matrix is entirely uniform.

3.2.6. Membrane antibacterial activity

Fig. 13. AFM images and roughness parameters of the fabricated membranes. Fig. 18 (a) indicates the significant antibacterial capability of the
NBNPs/PES nanocomposite membranes against staphylococcus aureus
and Escherichia coli. A weak zone of inhibition was observed for 0.1 wt%
ions than the bare PES membrane. The 0.5 wt% NBNPs/PES membrane
NBNPs/PES membrane and diameter of zone inhibition was increased
showed the best performance regarding removal of heavy metal ions
by increasing load of NBNPs. Obviously, the result of the zone inhibition
with rejections of Zn2+: 98.62%, Cu2+: 97.88%, and Pb2+: 97.03%.
test was almost equal for both types of bacteria. The results of the
Three critical factors, including Donnan exclusion, chelation reaction,
colony-forming count method are shown in Fig. 18 (b) and (c). Fig. 18
and membrane structure filtration performance, influence the rejection
(b) shows the plates, which had been in contact with the prepared
of heavy metal ions. The Donnan exclusion mechanism is the first pro­
membranes. After exposing bacterial solutions with the nanocomposite
bable explanation for the modified membranes’ effective rejection of
membranes, the number of colonies formed was decreased, and a dra­
heavy metal ions. As shown by the zeta potential analysis (Table 2), the
matic decrement was observed for 0.5 wt% NBNPs/PES membrane and
surface charges of the modified membranes were higher than those of
the best antibacterial capability was related to 1 wt% NBNPs/PES

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S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 14. (a) pure water flux (kg/m2h), (b) time-dependent flux (kg/m2h), (c) flux recovery ratio (%) and (d) fouling resistance ratio.

16
S. Dadari et al.
Fig. 15. Heavy metal ions rejection of the prepared membranes; separately ionic solutions (a) and the mixture of ionic solutions (b).
membrane. The quantitative analysis of the antibacterial capability of
the blended membranes was carried out to determine the antibacterial
rate, and the results are shown in Fig. 18 (c). The 0.1 wt% NBNPs/PES
membrane showed 20.3 and 18.7% of antibacterial rates for staphylo­
coccus aureus and Escherichia coli, respectively. The antibacterial rate
reached 68.1 and 66.9% for staphylococcus aureus and Escherichia coli,
respectively, by adding NBNPs up to 0.5 wt%. At 1 wt% concentration,
the maximum antibacterial rate was observed about 90 and 88 % for
staphylococcus aureus and Escherichia coli, respectively. Hydrophilicity
and surface roughness are two critical factors in the enhancement of
antibacterial capabilities in membranes [109]. The water contact angle
measurements verified the higher hydrophilicity of the NBNPs/PES
membranes. When water molecules are in a close atmosphere to the
surface of the membranes, they prefer to interact with the hydrophilic
surfaces, resulting in a thin coating of water molecules covering the
membrane’s whole surface. Because microorganisms have an organic
structure, the water layer prevents them from adhering to the surface.
Additionally, the smoother surface with modest roughness reduced the
probability of microorganisms finding ideal attachment sites. The anti­
bacterial efficacy of 1 wt% NANPs/PES membrane is higher despite its
greater roughness characteristics compared to the 0.5 wt% NANPs/PES
membrane. On the other hand, the membrane containing 1 wt% of
NANPs exhibited the maximum surface hydrophilicity. It seems that
17
Chemical Engineering Journal 431 (2022) 134116
surface hydrophilicity has a more significant influence on antibacterial
characteristics than surface roughness. Another critical aspect of the
modified membranes’ antibacterial resistance is the presence of NBNPs
in the PES structure.
As mentioned before, studies have shown that bentonite does not
have antibacterial properties. So, the antibacterial capability of the
nanocomposite membranes is related to NBNPs. According to the liter­
ature, nickel nanoparticles showed good antibacterial properties against
various types of bacteria [43–45]. The antibacterial mechanism of nickel
nanoparticles has not been known entirely yet, but the probable mech­
anism includes the effect of nickel on the membrane structure of bacteria
disrupting regular and proper transport through the plasma membrane
and eventually causing the death of microorganisms [43]. Another
possible reason for the antibacterial performance of the membranes is
the high affinity of nickel nanoparticles to interact with phosphorous
and sulfur, which are in DNA structure resulting in inhibition of cell
activity [110]. In addition, various studies have shown the significant
antibacterial performance of Scrophularia striata [111–113].The hy­
droxyl groups related to polyphenol compounds of the extract in the
structure of the NBNPs and blended membranes confirmed by FTIR form
hydrogen bonds leading to dissipation of pH gradient of the cytoplasmic
membrane of the bacteria and disruption of proton motive force (PMF)
and intracellular adenosine triphosphate (ATP) (ATPin) in
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 16. Chelation interaction of NBNPs functional groups on the modified membrane surface with heavy metal ions.

Fig. 17. Cross-section EDS mapping images of the 1.0 wt% NBNPs/PES membrane (a) before and (b) after using in antifouling and heavy metal ions
removal analyses.

18
S. Dadari et al. Chemical Engineering Journal 431 (2022) 134116

Fig. 18. (a) photographs of the results of inhibition zone method, (b) results of colony-forming count method, and (c) antibacterial rate of the nanocomposite
membranes (%).

19
S. Dadari et al.
microorganism’s cell [114]. Therefore, these nanocomposite mem­
branes would have significant potential to treat water polluted by
bacteria.
4. Conclusions
Green-synthesized NBNPs were used as a novel nanofiller to enhance
the antifouling property, remove heavy metal ions, and antibacterial
performance of the PES nanocomposite membranes. NBNPs were syn­
thesized using Scrophularia striata extract and were characterized by
FTIR, zeta potential, XRD, EDS, FESEM, and TEM analysis techniques to
investigate the Physico-chemical properties of the NBNPs. FTIR and EDS
analyses of the blended membranes confirmed the presence of NBNPs in
the polymer matrix structure. FESEM results and measurements of
overall porosity and mean pore radius illustrated that the addition of
NBNPs resulted in the increment of porosity and pore radius size of the
nanocomposite membranes. The water contact angle analysis showed
that the hydrophilicity of the NBNPs/PES membranes was higher than
the bare PES membrane due to the existence of NBNPs with various
functional groups on the surface of the membrane. The 0.5 wt% NBNPs/
PES membrane possessed a water contact angle of 50.3◦ while the water
contact angle was equal to 64.6◦ for the bare PES membrane. All the
modified membranes exhibited higher pure water flux compared to the
bare PES membrane. The highest pure water flux was about 59 kg/m2h,
which was related to 0.5 wt% NBNPs/PES membrane while PES mem­
brane showed the lowest pure water flux of 16 kg/m2h. AFM images
showed a smooth surface for the blended membrane, resulting in higher
antifouling performance than the PES membrane. The irreversible
fouling reached 3.14 %, while the flux recovery ratio was increased to
98.2 % upon introducing 0.5 wt% of NBNPs. Rejection of heavy metal
ions was carried out using 20 mg/L of ionic solutions and 0.5 wt%
NBNPs/PES membrane exhibited the maximum rejection as follows :
Pb2+ , 97%; Cu2+ , 97.8%; Zn2+ , 98.6%. The antibacterial capability of
NBNPs/PES membranes against staphylococcus aureus and Escherichia
coli were investigated through the inhibition zone and colony-forming
count method. The results showed a great average antibacterial rate
for the nanocomposite membranes. The antibacterial rate of the 0.5 and
1 wt% NBNPs/PES membrane against staphylococcus aureus and
Escherichia coli was measured as 68.1, 90; 66.9, and 88%, respectively. It
could be due to the presence of nickel nanoparticles and hydroxyl groups
in the NBNPs structure.
NBNPs/PES membranes exhibited significant performance, and thus,
they would be considered for removal of heavy metal ions and bacteria
from wastewater in the real world.
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.
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