Separation and Purification Technology 241 (2020) 116735

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Separation and Purification Technology

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

Novel polyethersulfone-functionalized graphene oxide (PES-fGO) mixed T

matrix membranes for wastewater treatment
⁎ ⁎
Adewale Giwa , Shadi W. Hasan
Center for Membranes and Advanced Water Technology (CMAT), Department of Chemical Engineering, Khalifa University of Science and Technology, P.O. Box 127788,
Abu Dhabi, United Arab Emirates

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

Keywords: In this study, three routes of nucleophilic substitution of graphene oxide (GO) were compared for the fabrication
Nucleophilic-substituted graphene oxide of novel polyethersulfone-functionalized GO (PES-fGO) mixed matrix membranes. These routes were: cross-
Maleic acid linking of GO with maleic acid containing nucleophilic dicarboxyl groups (M1); co-polymerization of GO with
Hyperbranched polyethylenimine hyperbranched polyethyleneimine (HPEI) with excess amino group (M2); and nucleophilic modification of GO
Chitosan
with naturally-derived chitosan containing amino and hydroxyl groups (M3). These membranes were then
Mixed matrix membranes
characterized and tested for the treatment of electrokinetically remediated wastewater. Membrane properties
such as mechanical strength, morphology, chemical functionalities, hydrophilicity and pore structures were
measured to assess the membranes in relation to their performance. M2 membrane displayed the least open and
densest structure due to the abundance of nucleophilic amino groups on HPEI. The flexible NeH chains in-
creased the resistance of the active layer to water and contributed to the lowest water fluxes provided by M2
membrane. Regardless of viscous hindrance, intermolecular bonds with higher energies (CeO in M1 and OeH in
M2) promoted thermodynamic instability which increased the pore sizes and water fluxes through M1 and M3.
Therefore, the highest tensile strength and allowable load were exhibited by M2 membrane. The COeNH lin-
kages in M2 contributed to the highest overall pollutant removal efficiencies: 97.1% Fe2+, 95.3% Zn2+, 92.7%
Cd2+, 99.9% Cr6+, 99.9% bacteria, and 98% chemical oxygen demand (COD) due to stronger repulsive elec-
trostatic force and nano-sized membrane pores.

1. Introduction
The United Nations (UN) has proposed wide-scale wastewater reuse
as a sustainable approach for tackling freshwater stress. In fact, the
theme of the UN’s 2017 World Water Day was focused on wastewater
reuse [1]. However, many contaminants in significant quantities might
still be present in the treated effluents from traditional sewage treat-
ment such as activated sludge treatment, sand filtration, membrane
bioreactors (MBRs), etc. When exposed to the environment, these
contaminants are oftentimes harmful to humans and aquatic life. The
impacts of these contaminants can lead to the contamination of potable
water aquifers. Therefore, efficient removal of hazardous materials in
wastewater, such as toxic heavy metal ions and pathogenic bateria, is
essential for the realization of this proposal.
As a recently developed treatment method, electrically-enhanced
membrane bioreactor (eMBR) has been shown to provide effluents of
highly quality at lower cost than the traditional approaches [2,3]. The
eMBR system provides higher removal efficiencies for organics, water
hardness, and bacteria from raw sewage. The cocepct of eMBR has also
driven other researchers to investigate potential alternatives to reduce
its energy requirements [4]. eMBR consists of electrodes inserted in a
MBR to induce electrokinetics for higher pollutant removal efficiency.
The presence of electrokinetics has led to significant changes in the
physico-chemical and biological characteristics of the sludge. For ex-
ample, processes such as electrocoagulation, electroosmosis, electro-
settling among others have generated a mixed liquor suspended solids
(MLSS) with denser flocs, less bound water and highly settled [2,3]. The
electrodes can be inserted in cylindrical or rectangular configurations.
eMBR has also demonstrated less susceptibility to membrane fouling
when compared with the conventional MBR system [4]. However, the
residual contaminants in eMBR effluent are still beyond levels of gen-
eral applications.
In recent times, due to advances in nanomaterial synthesis and as-
sembly, nanomaterials are now being incorporated as fillers to poly-
meric matrix to fabricate mixed matrix membranes for wastewater post-
treatment [6]. These nanomaterials impart properties such as nano-

⁎
Corresponding authors.
E-mail addresses: adewale.giwa@ku.ac.ae (A. Giwa), shadi.hasan@ku.ac.ae (S.W. Hasan).

https://doi.org/10.1016/j.seppur.2020.116735
Received 31 December 2019; Received in revised form 17 February 2020; Accepted 17 February 2020
Available online 17 February 2020
1383-5866/ © 2020 Elsevier B.V. All rights reserved.
A. Giwa and S.W. Hasan
sized pores and enhanced membrane performance. Although a nano-
porous membrane with the desirable properties might be fabricated but
the propensity of the membrane to withstand fouling or leaching of the
active layer during long-term operations is a key requirement. Gra-
phene oxide (GO) is one of the materials at the heart of current ad-
vances in mixed matrix membrane fabrication because of its unique
properties [7]. GO contains abundant oxygen groups on its surface
which support its interaction with water. GO contains hydroxyl, car-
boxyl and epoxy functional groups in the carbon lattice across the basal
plane and on the edges. The number of hydroxyl group in GO depends
on the extent of oxidation of graphene. Water permeates through the
inter-sheet distance or interconnected nanocapillaries ensured by the
stacking of GO nanosheets with relatively intrinsic low mass transfer
resistance [8]. However, the reactions at GO surface are further ex-
panded to non-covalent due to the sp2 and sp3 domains on the surface.
van der Waals bonding and π–π stacking are the primarily non-covalent
reactions [8]. π–π stacking is the attractive interactions between aro-
matic rings. This staking arises from the π bonds in the rings. A π bond
is formed from two p-orbitals. π interactions are more pronounced in
GO as a result of the transformation of sp2 carbon to sp3 carbon caused
by defects or distortions during its production from graphene [10].
Hence, ensuring adequate adhesion between GO in GO-assisted
mixed matrix membranes is critical for the long-term performance of
these membranes. A poor interaction could cause rapid decline in the
selectivity of the membrane due to leaching and formation of non-se-
lective voids at the interfacial region [11]. The incorporation of an
external adhesive layer between GO and polymer phases is a common
strategy used to address adhesion but this layer-by-layer self-assembly
approach provides non-covalent bonding [12]. With such a concern,
choosing linkers that can provide intrinsic and integral chemical lin-
kages between the polymer and GO is essential. Therefore, in this paper,
mixed matrix membranes consisting of GO integrally linked with ad-
hesive functional groups were studied for the removal of residual heavy
metal ions in eMBR effluent. Polyethersulfone (PES) was used as the
polymer in the mixed matrix membrane and integral adhesion between
GO and PES was achieved via nucleophilic substitution of GO. The
carboxyl, hydroxyl and epoxy groups of GO have electrophilic carbon
centers that can be attacked by nucleophiles [11,12]. On the other
hand, PES is composed of two repeating functional groups: sulfonyl and
ether groups (Fig. 1(a)) that may be involved in polycondensation re-
actions.
In these reactions, new polymer derivatives might be formed from
the attack of the sulfonyl and ether groups, as shown in Fig. 1(b) and
1(c) [13]. Crosslinking might occur during these reactions via pheny-
lation of the CeS and CeO bond cleavages [14]. The phenyl rings and
oxygen moieties in the functional groups might also be attacked by
nucleophiles via addition polymerization to form co-polymers and
conjugates (Fig. 1(d–f)). The electrophilic carbon of the phenyl rings
might be attacked by the nucleophilic terminal groups of another
polymer to form co-polymers (Fig. 1(d)) and reactions with additional
reagents might produce conjugates of these co-polymers (Fig. 1(e))
[15,16]. Also, addition polymerization might occur via the coordina-
tion of the ether bond and the oxygen moieties of sulfone group to
oxides (Fig. 1(f)) [17]. Meanwhile, coordination reaction without the
use of nucleophilic modifiers would not ensure that the PES and GO
phases are covalently bonded.
The most nucleophilic modifiers are compounds bearing donate-
able electrons such as organic amines and charged molecules.
Therefore, three routes of GO functionalization by nucleophilic sub-
stitution were compared in this study, using three modifiers: Chitosan,
hyperbranched PEI (HPEI), and maleic acid. The studied routes were:
crosslinking of GO with naturally-derived chitosan containing nucleo-
philic amino and hydroxyl groups; co-polymerization with HPEI with
excess amino group; and crosslinking of GO with maleic acid containing
nucleophilic dicarboxyl groups. The comparison was carried out by
investigating the influence of the reactive terminal groups of the
2
Separation and Purification Technology 241 (2020) 116735
nucleophilic modifiers on the properties, stability, and filtration per-
formance of PES-fGO membranes. This is the first study on the com-
parison of the influence of nucleophilic modifiers on PES-GO mem-
branes at the molecular level. All nucleophilic-substituted PES-GO
membranes were employed in this study for the treatment of electro-
kinetically remediated wastewater effluent obtained after the eMBR.
Therefore, the novelty of this research study relies on: (1) the com-
parison of the influence of nucleophilic modifiers (maleic acid, hyper-
branched polyethylenimine, and chitosan) on the performance of GO-
assisted mixed matrix membranes at the molecular level, and (2) the
combination of eMBR with nucleophilic-functionalized graphene oxide
(GO) mixed matrix membrane filtration for treatment of raw waste-
water.
2. Material and methods
2.1. Raw wastewater and treated effluent after eMBR
Raw wastewater (Table 1) from a municipal MBR wastewater
treatment plant at Masdar City, Abu Dhabi, United Arab Emirates was
obtained. It was then fed into a 31.5 L rectangular polycarbonate eMBR
operated at a hydraulic retention time of 13 ½ h and sludge retention
time of 240 days. A current density of 1.5 mA/cm2 was applied to the
configuration at an intermittent cycle of 5 min ON and 5 min OFF for
120 days. Full details on the design of eMBR can be found in our pre-
vious research studies [2,3,5]. The effluent from the eMBR (Table 1)
was used as an input for the performance tests of the PES-fGO mixed
matrix membranes developed in this study.
2.2. Nucleophilic-functionalized graphene oxide-incorporated mixed matrix
membranes
The materials used for the fabrication of the nucleophilic-functio-
nalized GO-incorporated membranes include: (i) 99.5% pure tetra-
hydrofuran (THF), bought from LOBA Chemie Pvt Ltd; (ii) the materials
purchased from Sigma Aldrich, i.e. GO (4 mg/mL dispersion in water,
greater than95% purity); branched PEI with average molecular weight
of ~25,000; 99% pure maleic acid powder; ≥99.8% pure acetic acid;
99.8% pure anhydrous N,N-dimethyl formamide (DMF); chitosan
powder with molecular weight of 50,000–190,000 Da; 99.8% pure
ethanol; 99% pure sodium chloride; 99% pure N-methyl-2-pyrrolidone
(NMP); 99.5% pure anhydrous citric acid; and sodium hypochlorite;
(iii) the materials purchased from VWR International LLC, i.e. anhy-
drous sodium phosphate monobasic and sodium phosphate dibasic; and
(iv) PES with molecular weight of ~75,000, bought from Prakash
Chemicals Pvt. Limited.
Solutions of the nucleophilic modifiers were first prepared by dis-
solving them in appropriate solvents. 5 wt% aqueous solution of maleic
acid was mixed with 5 wt% sodium dihydrogen phosphate used as
catalyst. 10 wt% HPEI was dissolved in THF:DMF solution (1:1 wt ratio)
at 70 °C. 10 wt% chitosan was dissolved in 0.1 M acetic acid at room
temperature. These solutions were then used to prepare functionalized
GO (fGO) suspensions. 1 L solution of pH 7.0 tris-H3PO4 buffer was
prepared by mixing 0.477 mol of sodium dihydrogen phosphate
monohydrate and 0.523 mol of sodium phosphate dibasic in 950 mL of
DI water. The pH of the buffer solution was adjusted to 7.0 by adding
0.1 M sodium hydroxide. Once pH 7.0 was reached, deionized water
was added to bring the total volume of phosphoric acid buffer to 1 L.
The resistivity of the deionized water used throughout this study was
15 MΩ cm. Then, three samples of 4 mg/mL GO solution were diluted
by adding 20 mL of the prepared tris-H3PO4 buffer solution in tightly
sealed sample vials to ensure that the maximum charge of GO was
maintained. Each solution of nucleophilic modifier was added dropwise
to a buffered GO solution in the ratio 8:1 vol/vol. The resulting sus-
pensions were stirred continuously with a magnetic stirrer for 24 h at
60 °C. The suspensions were then centrifuged using HERMLE
A. Giwa and S.W. Hasan Separation and Purification Technology 241 (2020) 116735

Fig. 1. Schematic of molecular interactions of PES showing (a) the chemical structure of PES with the functional groups and phenyl ring; phenyl radical formation by
the cleavage of (b) CeS and (c) CeO bond; (d) co-polymer formation by the nucleophilic attack of the phenyl ring; (e) conjugation of the co-polymers by addition
reaction; (f) polycondensation reaction between PES and an oxygenated material represented by AO, such as GO.

Table 1 respectively. Each exfoliated fGO in NMP was mixed with PES using
Pollutant concentrations in raw wastewater and eMBR effluent. 18:82 PES:NMP weight ratio. The weight ratio of fGO in the mixture
Contaminant Raw wastewater eMBR effluent was kept at 0.5 wt% of PES. The mixtures or dope solutions containing
fGO prepared from maleic acid, HPEI, and chitosan were denoted as
Fe2+ (µg/L) 281 28 M1, M2, and M3, respectively. Continuous magnetic stirring of the PES-
Zn2+ (µg/L) 2250 476 NMP-fGO dope solutions was ensured at 70 °C and 120 rpm for 6 h.
Cd2+ (µg/L) 63 13
Cr6+ (µg/L) 1400 14
After stirring at 70 °C, clear dope solutions were ensured by allowing
Chemical oxygen demand (COD) (mg/L) 880 36.9 stirring to continue at room temperature for additional 12 h. Then,
Biological oxygen demand (BOD) (mg/L) 640 26.8 stirring was discontinued for the next 6 h to ensure air bubble removal.
Bacteria (CFU/100 mL) 3,900,000 18,300 The procedure for fabricating the membranes is shown in Fig. 2.
The dope solutions were then used to laminate non-woven PES
support, such that flat sheet PES-fGO mixed matrix membranes were
Labortechnik Z 326 K centrifuge at 9000 rpm for 30 min to recover the
fabricated. The PES substrate was initially positioned on a glass plate.
fGO while the supernatant was decanted away. Each fGO was washed
Then an active layer containing each dope solution was uniformly cast
many times with 10 wt% dilute solution of ethanol and deionized water
on the substrate at a casting thickness of 100 µm and traverse speed of
to remove residual unreacted chemicals. Each fGO was then dried in the
60 cm/min using MSK-AFA-III Compact Tape Casting Coater. Non-sol-
oven at 35 °C and the % yield was computed using Eq. (1).
vent induced coagulation was first achieved by, drying the as-coated
wfGO − wGO membranes for 15 min in the oven to ensure uniform phase separation
%yield = × 100
wGO (1) and then by, immersing the dried membranes in deionized water for
24 h. The membranes were then washed with additional deionized
where wfGO is the weight of fGO and wGO is the initial weight of GO water to remove impurities on the membrane surface and dried by air at
before the nucleophilic modification. room temperature.

2.3. Fabrication of PES-fGO membranes 2.4. Characterization of fGO suspensions, dope solutions and membranes

NMP solvent was used to disperse each fGO sample. Branson 1510 fGO and PES-fGO membrane characteristics such as average fGO
Ultrasonic Cleaner was then used to exfoliate each fGO sample by ul- particle sizes in fGO suspensions, isoelectric point of fGO particles in
trasonication at a frequency and duration of 40 KHz and 60 min, fGO suspensions, viscosity of dope solutions, mechanical strength of

3
A. Giwa and S.W. Hasan
Addition of nucleophilic
Preparation of
crosslinkers to GO
functionalized GO
(a) (b) (c)
Lamination of
dopes as active
layer on PES
support
Fig. 2. Fabrication procedure for M1, M2, and M3 containing nucleophilic-substituted GO. fGOa, fGOb, and fGOc are GO functionalized with maleic acid, HPEI, and
chitosan, respectively.
membranes, membrane morphology, chemical functionalities on
membranes, membrane hydrophilicity and pore structures were mea-
sured to assess the properties of the dope solutions and membranes, in
relation to the performance of the two-stage treatment system. All
measurements were performed at room temperature, i.e. 21 ± 1 °C.
HORIBA LA 950V2 Particle Size Analyzer (PSA) was used to measure
the mean sizes of fGO particles. The PSA was fitted with red and blue
laser diodes, such as the absorbance or transmittance of emitted lights
by the particles was converted to particle sizes. NanoBrook ZetaPALS
potential analyzer was used to measure the isoelectric point of the fGO
particles in the suspensions. The zeta potentials of the particles were
measured via light scattering technique at a scattering angle of 15° and
for each fGO sample, the pH at which zero potential occurred was de-
noted as the isoelectric point. HAAKE RheoStress 6000 rheometer was
used to measure the viscosity of the dope solutions. Viscosity was
measured by shearing the dope solutions for 120 s at a rate of 240 1/s.
The mechanical strength of the membranes was determined from the
tensile strength and maximum allowable load. Blue hill mechanical
compression device was used to deform the membrane at a rate of
1 mm/min and measure the maximum stress on each membrane before
break (i.e. tensile strength). Nova NanoSEM 650 Scanning Electron
Microscopy (SEM) device was used to observe the surface morphology
of the membranes. Membrane morphology was observed at an electron
beam energy of 5 kV and spot size of 4.0. Before SEM analysis, mem-
brane samples were coated with gold and platinum (at a thickness of
10 nm) to make them become electrically conductive. Bruker’s Vertex
80v Fourier Transform InfraRed (FT-IR) spectrometer was used to ob-
serve the chemical functionalities on the membranes. FT-IR analysis
was carried out at a wavenumber range of 400–4000 cm−1 and 4 cm−1
resolution. Alpha 300R confocal micro-Raman imaging spectrometer
was further used to observe the Raman signals from the membranes and
study the vibrational characteristics of the chemical bonds. Raman
spectroscopy was performed using a 532-nm visible laser source. The
sessile drop technique in Krüss GmbH Drop Shape Analyzer (DSA) was
used to measure the hydrophilicity of the membranes in terms of the
water contact angle. By dropping 1 µL deionized water onto each
membrane sample, the intersection point between the drop contour and
Separation and Purification Technology 241 (2020) 116735
Washing and
Recovery of
removal of
functionalized GO impurities
M1 M2 M3
Preparation of Exfoliation of
functionalized functionalized GO
GO-incorporated
dopes
projection of the membrane surface was used to obtain the water
contact angle. PMI Capillary Flow Porometer was used to measure the
mean pore sizes of the membranes. Membrane porosity was determined
using the gravimetric method. In this approach, the membranes were
dipped inside a wetting liquid, Silwick™ in the membrane pores was
displaced by the wetting liquid in order to displace the air in the
membrane pores by the wetting liquid. For each membrane, the volume
of the air displaced by Silwick™ was considered as the membrane pore
volume. The ratio of the measured pore volume to the total membrane
volume was then estimated and considered as the membrane porosity,
as shown in Eq. (2).
Vp (mF − mI )/ ρ
Membrane porosity = =
VT Axδ (2)
Vp is estimated pore volume; VT is membrane’s total volume; mF is
membrane’s weight after dipping in Silwick™; mI is membrane’s initial
weight before dipping in Silwick™; ρ is density of Silwick™ (0.7031 g/
cm3); A is membrane’s effective area; and δ is thickness of the mem-
brane.
2.5. PES-fGO membrane performance tests
Membrane performance was assessed in terms of the permeate flux
and pollutant removal efficiency. To evaluate membrane performance,
each PES-fGO mixed matrix membrane was placed in a module, pres-
surized for 6 h at 0.6 MPa, through which the effluent from the eMBR
was made to flow through as shown in the schematic illustration in
Fig. 3.
The module contained two opposite channels that were structured
equally. Each channel had dimensions: 4 cm × 9 cm × 3 mm. Nitrile
rubber gasket was used to cover these halves to prevent leakage and
provide structural support. Membrane permeability and permeate flux
were estimated from the volume of the eMBR effluent that passed
through each membrane at 0.6 MPa. The volume of the permeate was
measured periodically for 5 h. Membrane permeability and permeate
flux were estimated using Eqs. (3) and (4), respectively.
4
A. Giwa and S.W. Hasan
Fig. 3. The integrated system of eMBR and PES-fGO mixed matrix membrane. The streams and units in the system include: (1) raw wastewater; (2) eMBR recycled
sludge; (3) eMBR influent; (4) drained sludge from eMBR; (5) stored sludge for possible end uses; (6) eMBR effluent; (7) concentrate from module; (8) influent to PES-
fGO membrane; (9) final product water; (10) the module in cross flow or dead-end configuration.
Jw
Permeability =
ΔP
Pv
Permeate flux, Jw =
A×t
Pv is permeate volume; t is time of permeate collection; ΔP is
transmembrane pressure. The effective area of the membrane in the
module was 36 cm2.
DR3900 UV/Vis spectrophotometer was used to measure the con-
centrations of pollutants including heavy metals (Cd2+, Fe2+, Zn2+ and
Cr6+) and organics (measured as biological oxygen demand (BOD) and
chemical oxygen demand (COD)). The spectrophotometer used radio-
frequency identification to identify the maximum UV/Vis wavelength
absorbable by the pollutant. UV/Vis light absorption was then con-
verted to concentration parameter by the spectrophotometer, for each
pollutant measured. Pathogenic bacteria (measured as total colony
forming units; CFU) was measured by preparing Luria Broth agar
medium consisting of 10 g/L tryptone, 20 g/L agar powder, 5 g/L NaCl,
and 5 g/L yeast extract in deionized water. The autoclaving of the
medium was carried out at 121 °C for 20 min. The autoclaved medium
was then poured into agar plates at room temperature and used for the
measurement of total bacterial count (TBC).
The removal efficiencies were estimated from the % rejection. The
% rejection of each pollutant was calculated using Eq. (5).
Cf − Cp ⎞
%rejection = 100 × ⎛⎜ ⎟ in GO [9].
⎝ Cf ⎠
Cf and Cp are feed and permeate concentrations of a pollutant, re-
spectively.
The membranes were physically and chemically cleaned after fil-
tration. The module was backwashed with deionized water at 0.6 MPa
to ensure physical cleaning. For chemical cleaning, the module was
washed with an aqueous solution containing 3 wt% citric acid and 1 wt
% NaOCl. The membranes were reused after cleaning in order to assess
the reusability of the membranes and estimate the flux recovery. The
ratio of the permeate flux obtained after cleaning to the flux before
cleaning was considered as the flux recovery ratio.
Separation and Purification Technology 241 (2020) 116735
3. Results and discussions
(3)
3.1. Nucleophilic linkage mechanisms
(4)
The introduction of carbonyl and carboxyl groups along the edges,
and hydroxyl and epoxy groups on the basal plane of GO during gra-
phene oxidation leads to the defects in the sheet. These functional
groups equally present reactive sites for the chemical modification of
the sheets. As a cis-isomer, maleic acid was able to form a cyclic an-
hydride and covalent ester linkage with the hydroxyl groups on the
basal plane of GO sheets in M1, as shown in Fig. 4(a).
The crosslinking of the GO maleate formed was also enhanced by
the NaH2PO2 catalyst, as HePeH bonds of NaH2PO2 would react with
the MA moieties esterified with GO to form a cross-linkage. In M2, the
amino groups of HPEI undergo amidation by forming covalent COeNH
linkages with the carboxyl groups on the edges of GO sheets, as shown
in Fig. 4(b). The excess amino groups are protonated and impart posi-
tive charge to the fGO. The amino groups of chitosan solution are also
protonated and take the form of chitosanium. Amide covalent linkages
between the carboxyl groups of GO nanosheets and amino groups of
chitosan chains, which follow nucleophilic substitution mechanism, are
formed in M3 and shown in Fig. 4(c) [18]. The amino groups in chit-
osan can also react by forming hydrogen bonding with the epoxy groups
in GO [11]. Aside from the amino groups, chitosan contains hydroxyl
groups which can interact to form hydrogen bonding with the moieties
(5) The Raman signals of the membranes further revealed the nucleo-
philic effect of the modifiers. The Raman spectra of graphene normally
show three distinct peaks: (i) a strong G band close to 1580 cm−1,
corresponding to the first-order scattering of the graphene lattice; (ii) D
band around 1350 cm−1, corresponding to out-of-plane breathing
mode of the sp2 atoms associated with internal structural defects; and
(iii) 2D band in the region of 2700 cm−1, corresponding to the second-
order processes of the vibrational mode [8]. However, in the Raman
signals obtained (Fig. 5(a)), a shift and broadening of the D and G bands
resulting from the covalent interaction of the nucleophilic functional
groups to the GO sheet was noticed. The most noticeable changes in
5
A. Giwa and S.W. Hasan
Fig. 4. Schematic of the proposed research showing the nucleophilic routes and links for membranes fabricated from GO (a) functionalized with MA (M1), (b)
functionalized with HPEI (M2), (c) functionalized with chitosan. The hydroxyl groups in chitosan might also form hydrogen bonds with the epoxy groups on the basal
plane of GO.
Fig. 5. The nucleophilic action of the modifiers as evident in the (a) Raman
signals of the virgin mixed matrix membranes; (b) disparity in the mean particle
sizes of fGO in the fGO suspensions used to fabricate the membranes; (c) color
changes imparted to GO as a result of the nucleophilic functionalization. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
Raman spectra were observed in the 2D band, relating to the hydro-
philic interactions between the GO sheets and nucleophilic modifiers.
Meanwhile, the amino groups in HPEI and chitosan showed higher
nucleophilic crosslinking degree to GO, as observed in fGO mean par-
ticle sizes (Fig. 5(b)). The mean particle sizes of fGOb and fGOc were
2.1 µm and 43.7 nm, respectively while that of fGOa was 11.4 nm. The
extent of nucleophilic interactions was also evident in the yield of the
fGO. The yields of fGOa, fGOb, and fGOc were 20, 122.8, and 82%,
6
Separation and Purification Technology 241 (2020) 116735
respectively. The casting (dope) solutions for M1 and M2 appeared as
dark grey and light grey while that of M3 appeared as very dark sus-
pension (Fig. 5(c)).
3.2. PES-fGO membrane properties
M1 and M3 membranes exhibited spongy layers with grooves and
wrinkles (Fig. 6(a) and 6(c)) while a dense structure is exhibited by M2
membrane (Fig. 6(b)). Of all three membranes, the surface of M2
membrane showed the least open structure and minimum heterogeneity
in morphology. Due to the abundance of nucleophilic amino groups on
HPEI, NeH molecular chains tend to aggregate at GO edges to form
COeNH intermolecular linkages on M2 membrane surface. M3 dis-
played a more open structure than M2 due to the presence of less
COeNH linkages in the fGO. On the other hand, the attack of the hy-
droxyl groups on the basal plane of GO by the terminal ester (eCOO)
groups of maleic acid might have caused more open structure for M1
membrane. M2 membrane surface had relatively minimal protrusions,
as observed from the SEM scan. This observation might be due to the
flexible chains exhibited by HPEI. These flexible chains also contributed
to the lowest water fluxes provided by M2 membrane because the
flexible chains increased the resistance of the active layer to water by
creating a denser membrane surface [19]. The energy of the CeN bond
in M2 is 305 kJ/mol. This energy is lower than the energy of the CeO
linkage in M1, i.e. 358 kJ/mol and OeH linkage partly formed in M3 by
the interaction of epoxy group in GO and chitosan i.e. 459 kJ/mol.
Therefore, the amidation of HPEI with GO is more favored, relative to
the esterification of maleic acid. The enhanced kinetics due to lower
energy of the CeN bond improved interaction of GO with CeN linkage
and contributed to lower pore sizes in M2 and M3.
A. Giwa and S.W. Hasan Separation and Purification Technology 241 (2020) 116735

Fig. 6. The morphology of the surfaces of (a) M1, (b) M2, and (c) M3 membrane observed at 2 µm resolution.

Fig. 7. Porosity and mean pore sizes of the membranes.

Consequently, the highest mean pore size was exhibited by M1

membrane. Also, M3 membrane showed higher mean pore size than M2
membrane because the COeNH group formed in chitosan-fGO is less.
M1, M2, and M3 membranes exhibited mean pore sizes of 42, 15, and Fig. 8. FTIR spectra showing the functional groups on the membrane surfaces.
24 nm, respectively (Fig. 7). The bond energies influenced the demixing
rate of the dope solutions into polymer-rich and polymer-lean phases
during phase inversion. The varied pore sizes on the membrane surfaces
were as a result of the differences in the rate of inter-diffusional ex-
changes between the solvent (NMP) and coagulant (water) during NIPS.
Nucleophilic substitution induced by the modifiers influenced the rate
of out-diffusion of NMP and in-diffusion of the coagulant (water), such
that higher bond energies promoted thermodynamic instability. This, in
turn, increased the demixing rate and sizes of the pores formed.
Meanwhile, the relationship between the porosity and pore sizes of the
membranes was opposite, as shown in Fig. 7. M2 showed the highest
porosity of 27% while the porosity of M1 and M3 were 24 and 25%,
respectively. Although these porosity values were close, the slight dif-
ferences might be connected to the presence of more reactive sites in
fGO in M2 and M3 membranes.
The functional groups on the membrane surfaces, as identified
through FT-IR analysis, are shown in Fig. 8. The functional groups at-
tributable to GO can be identified as follows: (i) the broad peaks ap-
pearing at 3300 cm−1 are assigned to OeH stretching vibrations on GO;
(ii) the peaks at 1049–1090 cm−1 are assigned to stretching vibrations
of alkoxy and epoxy groups; (iii) the peaks at 1385 cm−1 correspond to
the vibrational frequency of CeC bond in the aromatic ring of GO
[20–22]. The peaks at 700–900 cm−1 can be assigned to aromatic CeH Fig. 9. Permeate flux across the membranes at the operating pressure and
bend which signifies that the reduction of eCOOH on the edges of GO permeability in flux per bar. Permeability is shown by the continuous lines.
to eCH2 might have occurred. The peaks at 1242 cm−1 are attributed to
S]O stretching vibrations in PES [22]. A new stretching peak that can groups with the eCO groups on the edges of GO [18,21].
be ascribed to CeH appears at 680 cm−1 for M1, which signifies the All membranes were hydrophilic, as revealed by the water contact
appearance of maleic acid [20]. The eC]O functionality of the di- angles shown in Fig. 9. As expected, the inclusion of GO imparted hy-
carboxylic acids crosslinked the eOH group on GO to form the GO drophilicity to the fabricated membranes. In addition, due to the in-
maleate. The absorption peaks in the IR spectra of M2 and M3 at corporation of nucleophilic agents, all mixed matrix membranes con-
1643–1668 cm−1 are assigned to the stretching and bending vibrations tained hydrophilic groups which reduced the mass transfer resistance of
of the secondary amide (CeN) formed from the interaction of amino water across the membrane surfaces. The hydrophilic surfaces

7
A. Giwa and S.W. Hasan Separation and Purification Technology 241 (2020) 116735

promoted stronger interaction with water molecules via hydrogen

bonding. Although all membranes contained hydrogen bonds in the
linkages between the SO2 group of PES and fGO, M1 and M3 displayed
more hydrophilicity because these membranes contained more hy-
drogen bonds. These additional hydrogen bonds include the eOH
formed in the esterified GO in M1 and hydrolyzed epoxy in M2. The
water contact angles of M1, M2, and M3 membranes were 72, 81, and
77°, respectively (Fig. 9). The hydrophilic properties of the membranes
also correlated with the permeate flux and membrane permeability. The
permeate flux across the membranes was influenced by: (i) ease of
water transport across the membranes as a result of hydrophilicity; (ii)
additional water channels created by the interfacial gaps between the
fGO sheets resulting in low friction; and (iii) the mean pore size of the
mixed matrix membranes. As M1 was the most hydrophilic membrane
with the largest mean pore size, the highest stable permeate flux and
permeability of 54 LMH and 82 LMH/bar, respectively were shown by
M1 membrane (Fig. 9). Conversely, M2 membrane displayed the lowest
stable permeate flux and permeability of 8.9 LMH and 13.6 LMH/bar,
respectively, due to its compactness. The stable permeate flux and
permeability shown by M3 membrane were 22 LMH and 33.7 LMH/bar,
respectively. M1 and M3 membranes also showed faster flux stability
than M2 membrane due to enhanced hydrophilicity. Permeate flux
across these membranes stabilized after 120 min while flux across M2
membrane remained unstable until after 280 min.
The faster rate of water flux stability across M1 and M3 membranes
were also evident in the viscosity of the dopes, as shown in Fig. 10(a).
The viscosity of M1 and M3 dope solutions became stable at a faster
rate than that of M2 membrane under a constant shear rate of 240 s−1.
M1 and M3 dope viscosity became stable after 13 s, compared to 25 s
for M2 membrane. The mean values of the dope viscosity were 5678,
3110, and 4880 mPas for M1, M2, and M3, respectively. The stress
required to maintain the shear rate correlated with the dope viscosity,
as shown in Fig. 10(b). The flexible NeH chains in M2 contributed to
the relatively low viscosity and shear stress required to exert a strain on
M2 dope solution. Meanwhile, dope viscosity had less impact on
membrane pore sizes. Although dope solutions with higher viscosity
showed greater kinetic hindrance of demixing, the effect of thermo-
dynamic instability caused by the fGO interactions on the membrane Fig. 10. The kinetic stability of dope solutions, as observed from (a) viscosity of
pore sizes was dominant over the competing kinetic hindrance. Con- dope solutions; (b) applied shear stress; and (c) membrane tensile strength and
sequently, dope viscosity had less impact on the membrane tensile maximum allowable load.
strength and maximum allowable load (Fig. 10(c)). The highest tensile
strength and maximum allowable load of 22 MPa and 40 N, respec- COD, and 26.8 mg/L BOD. However, the concentrations of pollutants in
tively, were exhibited by M2 membrane. the eMBR effluent were still higher than the concentrations suitable for
The tensile strengths of M1 and M3 were 8 and 11 MPa, respectively some general and wholesome applications. Meanwhile, the removal of
while the maximum loads required to break 12 mm × 3 mm samples of the residual pollutants obtained through the PES-fGO membrane fil-
the membranes at a deformation rate of 1 mm/min were 35 and 30 N, tration showed significant improvement as can be observed in Table 2
respectively. The lower mechanical strengths of M1 and M3 were also and 3, respectively.
evident in the spongy morphology of these membranes, as already
discussed. Meanwhile, for all membranes, breaking stress remained
high (more than 8 MPa) to withstand the operating pressure due to
inclusion of GO. Reduction in GO defects was achieved by functiona-
lization with all three nucleophilic modifiers but the amino groups in Table 2
HPEI effectively covered the surface defects and significantly narrowed Pollutant concentrations in raw wastewater, eMBR effluent, and final effluent
the membrane's pore size. after PES-fGO mixed matrix membrane filtration.
Contaminant Raw eMBR Final effluent through PES-fGO
3.3. Removal efficiency of contaminants wastewater effluent membranes

The raw wastewater, obtained from the MBR wastewater treatment M1 M2 M3

plant, consisted of 281 µg/L Fe2+, 2.25 mg/L Zn2+, 1.4 mg/L Cr6+, 2+
Fe (µg/L) 281 28 9.9 8.2 8.6
63 µg/L Cd2+, 3.9 million CFU/100 mL of TBC, 880 mg/L COD, and Zn2+ (µg/L) 2250 476 140.4 104.7 111.9
640 mg/L BOD. Pollutants were removed electrokinetically from the Cd 2+
(µg/L) 63 13 5.3 4.6 4.7
raw wastewater by eMBR through the mechanisms of electromigration Cr6+ (µg/L) 1400 14 2 1.2 1.4
and electrophoresis, electrocoagulation, electroreduction and deposi- COD (mg/L) 880 36.9 17.6 17.5 17.4
BOD (mg/L) 640 26.8 12.8 12.7 12.6
tion on the electrodes, and electrooxidation as reported in literature
Bacteria (CFU/ 3,900,000 18,300 641 311 476
[2,3,5]. The eMBR effluent contained 28 µg/L Fe2+, 476 µg/L Zn2+, 100 mL)
14 µg/L Cr6+, 13 µg/L Cd2+, 18,300 CFU/100 mL TBC, 36.9 mg/L

8
A. Giwa and S.W. Hasan Separation and Purification Technology 241 (2020) 116735

Table 3 (pH 8.0). The eMBR effluent pH avoided the deprotonation of possible
Removal efficiencies (%) of eMBR and overall removal efficiencies of the in- unreacted amino groups on the membrane during filtration. M1 mem-
tegrated system of eMBR and PES-fGO mixed matrix membrane filtration. brane removed 86% Cr6+, 71% Zn2+, 65% Fe2+, and 60% Cd2+.
Contaminant eMBR PES-fGO membranes

M1 M2 M3
3.4.2. Removal of residual bacteria and organics
In spite of electrostatic repulsive force offered by M2 and M3
Fe2+ 90.0 96.5 97.1 96.9 membranes due to the amino groups, these membranes also showed
Zn2+ 78.8 93.8 95.3 95.0 higher rejection of residual soluble organics and bacteria (Fig. 11). The
Cd2+ 79.4 91.6 92.7 92.5
Cr6+ 99.0 99.9 99.9 99.9
nanosized pores and hydrophilic channels on the membrane surface,
COD 95.8 98.0 98.0 98.0 rather than electrostatic repulsion, were mainly responsible for the
BOD 95.8 98.0 98.0 98.0 removal of organics and bacteria. However, as expected, negatively
Bacteria 99.5 99.98 99.99 99.99 charged organic matter became attracted to the membrane surface and
caused a shield effect on the positively charged membrane. The mem-
branes removed more bacteria than organic matter (BOD) because the
3.4. Removal mechanisms of contaminants in PES-fGO membranes
sizes of bacteria are larger than those of the soluble organics. Therefore,
the nano-sized membrane pores contributed to the selectivity of the
3.4.1. Removal of heavy metal ions
membranes for bacteria and ensured higher rejection of bacteria. M2
The efficiencies of the membranes to remove residual contaminants
showed the highest removal of residual bacteria (i.e. 98.3%) because
from eMBR treated effluent are shown in Fig. 11. The highest removal
the lowest mean pore size was exhibited by this membrane. M1 and M3
efficiencies of heavy metal ions were provided by M2 membrane be-
removed 96.5 and 97.4% bacteria, respectively. However, in spite of
cause the nucleophilic modification via HPEI increased the surface
the lowest mean pore size provided by M2 membrane, M3 membrane
charge of the membrane more significantly. HPEI imparted positive
exhibited the highest removal efficiency of residual soluble organics
charge to the membrane due to the abundance of amino group which
(i.e. 52.8% BOD), possibly due to the bio-adhesive and bio-compatible
resulted in high rejection of the multivalent ions. The positively
characteristics of the chitosan functionality in M3 membrane [23].
charged membrane surface facilitated repulsive electrostatic force be-
tween the membrane and residual cations, such that the heavy metal
ions experienced a drift away from the membrane surface. The cations 3.5. PES-fGO membrane antifouling and anti-leaching properties
with higher oxidation states exhibited more electrostatic force. So, the
% rejection of multivalent ions with greater co-ion charge/Stokes ra- The surface hydration due to the hydrophilicity of all membranes
dius such as Cr6+ was higher due to stronger repulsive force between ensured the formation of a tightly-bounded water layer that imparted
the membrane surface and these ions [19]. The order of % rejection of anti-fouling properties to the membranes. However, the electrostatic
residual heavy metal ions for all membranes was attraction and bio-adhesion of negatively charged residual con-
Cr6+ > Zn2+ > Fe2+ > Cd2+. M2 membrane removed 91% of taminants to the membranes also influenced the temporal profile of
Cr6+, 78% of Zn2+, 71% of Fe2+, and 64% of Cd2+. water flux across the membranes. Initially, all membranes exhibited
The presence of positively charged amino groups in M2 was con- high water permeability (Fig. 9). The initial permeability across the
firmed from the isoelectric point of fGOb using zeta potential analysis. membranes were 279, 37, and 48 LMH/bar for M1, M2, and M3, re-
The zeta potential of fGOb reached the isoelectric point at pH value of spectively. However, as the negatively charged organics were adsorbed
9.6, which was favorable for the rejection of heavy metal ions. As GO is on the membrane surfaces, the water molecules within the oxidized
negatively charged (GO has a zeta potential of −59 mV in neutral regions of the fGO exhibited lower mobility and the flux changed
aqueous solution), the inclusion of HPEI in M2 moved the isoelectric drastically. The most drastic change was observed for M2 membrane
point towards highly alkaline pH and imparted positive charge via because of its highly positively charged surface. The IR spectrum of the
nucleophilic addition. M3 membrane also showed higher removal ef- fouled M2 membrane obtained after performance test is shown in
ficiencies of heavy metal ions, compared to M1, due to the cationic Fig. 12.
charge density provided by the positively charge amino group in chit- Few new peaks that can be attributed to carbon (organic matter)
osan. M3 membrane removed 90% Cr6+, 77% Zn2+, 70% Fe2+, and appeared in the FT-IR signal of the fouled membrane. These peaks re-
64% Cd2+. The unreacted amino groups were protonated and provided mained after physical cleaning of the membrane with deionized water.
positive charges on the membrane surface at the pH of eMBR effluent However, the new peaks disappeared after chemical cleaning except the
ones at 2850–2900 cm−1, which can be ascribed to CeH stretch. These

Fig. 11. Efficiencies of the membranes to remove heavy metal ions, COD, BOD, and bacteria from eMBR treated effluent.

9
A. Giwa and S.W. Hasan Separation and Purification Technology 241 (2020) 116735

This study
[24]

[25]

[26]
Ref.

70% flux recovery after membrane agitation in water

81.1% flux recovery during aerobic activated sludge

88.7% flux recovery after two filtration cycles

95% flux recovery after three filtration cycles

Comparison of the performance of M2 membrane with results from prior studies on PES-GO membranes, in terms of the propensity of GO to leach out and the flux recovery ratio.
Flux recovery ratio

filtration
bath
Fig. 12. IR spectra of virgin, fouled, physically cleaned or water-cleaned (WC),
and chemically cleaned or antifouling chemical-cleaned (AC) M2 membrane.

Leaching of GO was not easy; but quantitative values were not

new peaks indicate possible reduction of GO after chemical cleaning.
The chemically cleaned membrane was then re-tested again for filtra-

No leaching of Co but GO leaching was not reported

Leaching of GO from the membrane was observed
tion and a flux recovery ratio of 95% was obtained after three rounds of
filtration, indicating that the membrane’s filtration performance was
influenced by fouling by only 5%. The flux recovery ratio and pro-
pensity of the fGO to leach out from M2 membrane during filtration
were compared with existing studies on PES-GO membranes in the

Leaching of GO was not observed

literature. As shown in Table 4, it can be seen that M2 membrane
Propensity of GO to leach out

compared favorably with results in prior studies.

4. Conclusions

This study focused on the synthesis of novel PES-GO mixed matrix

membranes through nucleophilic-functionalization. The nucleophilic
reported

actions of maleic acid, HPEI, and chitosan for covalent adsorption to GO

and crosslinking with PES in PES-fGO membranes were studied and
compared. The performance of those membranes were tested on elec-
trokinetically remediated wastewater. It can be concluded that:
UV-induced graft co-polymerization of allylamine

(i) Higher nucleophilic crosslinking degree was observed for M2 and

Blending with cobalt oxide/GO (Co3O4–GO)

M3 membranes due to the positively charged amino groups in

HPEI and chitosan. Consequently, the highest removal efficiencies
of residual heavy metal ions were provided by M2 membrane, as
Blending modification with HPEI

shown in Table 2. M2 membrane reported removal efficiency of

97.1% Fe2+, 95.3% Zn2+, 92.7% Cd2+, 99.9% Cr6+, 98% COD,
Functionalization method

and 99.9% bacteria.

(ii) M2 membrane surface showed the least open structure and
minimum heterogeneity in morphology because the NeH mole-
nanocomposites

cular chains in HPEI tend to aggregate at the GO edges to form

This study

COeNH intermolecular linkages.

monomer

(iii) M1 and M3 displayed more hydrophilicity because these mem-

branes contained more hydrogen bonds, i.e. eOH formed in the
esterified GO in M1 and hydrolyzed epoxy in M2. The water
PES/GO/polyallylamine/trimesoylchloride

contact angles of M1, M2, and M3 membranes were 72, 81, and
77°, respectively.
(iv) M1 membrane had the most open structure due to the attack of the
hydroxyl groups on the basal plane of GO by the terminal ester
(eCOO) groups of maleic acid. Consequently, the highest mean
Membrane components

pore size (45 nm) was exhibited by M1 membrane. M1 also pro-

vided the highest stable permeability of 82 LMH/bar after 300 min
PES/GO/ Co3O4

of filtration.
PES/GO/HPEI

(v) The effect of thermodynamic instability caused by the fGO inter-

This study

actions was dominant over the competing kinetic (viscous) hin-

Table 4

drance. Although M2 exhibited the lowest dope viscosity

(3110 mPas) due to flexible NeH chains, it also showed the

10
A. Giwa and S.W. Hasan
highest tensile strength.
(vi) All PES-fGO membranes showed high removal efficiencies for
bacteria (more than 96%) due to GO and their nanosized pores)
but BOD removal was influenced by surface charges. Meanwhile,
95% of initial flux was recovered after three rounds of filtration,
while using M2 membrane.
(vii) Overall, the developed PES-fGO mixed matrix membranes in this
study showed a great potential to be used as a polishing step to the
water quality obtained from the eMBR. The removal efficiency
after the two-stage treatment has increased by 7%, 17%, and 13%
for Fe2+, Zn2+, and Cd2+; respectively. Also, the integrated
system reported near 100% removal of bacterial with 2% increase
in the removal of COD and BOD. Those results revealed the sig-
nificant contribution of the PES-fGO membranes to the eMBR
through which such membranes can not only be suggested as a
post-treatment, but they can also be integrated within the eMBR in
a hybrid single reactor. The presence of electric field in the eMBR
would have great potential to reduce fouling on the PES-fGO
membranes as reported by our previous research studies [27].
Furthermore, authors would like to highlight their previous re-
search studies on the potential post-treatment methods to eMBR. It
was concluded that eMBR and proposed post-treatment methods
were significantly inter-related through achieving better water
quality effluents that would provide more opportunities for water
re-use related applications [28–31].
CRediT authorship contribution statement
Adewale Giwa: Conceptualization, Methodology, Data curation,
Writing - original draft, Visualization, Investigation, Validation. Shadi
W. Hasan: Conceptualization, Methodology, Writing - review &
editing, Supervision, Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
Authors appreciate Masdar Institute of Science and Technology (as
part of Khalifa University of Science and Technology) in Abu Dhabi
(UAE) for the financial support (Grant No: SS2014-000014). The sup-
port by the Center for Membranes and Advanced Water Technology
(CMAT) at Khalifa University of Science and Technology is also ac-
knowledged.
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