J Mater Sci

Composites
C O M P O S I T E S & N&
A Nnanocomposites
OC O M P O S I T E S

Effect of triple-tail surfactant on the morphological

properties of polyethersulfone-based membrane and its
antifouling ability
Rosmanisah Mohamat1,2, Suriani Abu Bakar1,2,* , Muqoyyanah1,3, Azmi Mohamed1,4,
Siti Nur Elida Aqmar Mohamad Kamal5, Mohd Hafiz Dzarfan Othman5, Rosiah Rohani6,
Mohamad Hafiz Mamat7, Mohd Khairul Ahmad8, Hamdan Hadi Kusuma9, and
Budi Astuti10

1
Nanotechnology Research Centre, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim,
Perak, Malaysia
2
Department of Physics, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak,
Malaysia
3
Research Center for Advanced Materials, National Research and Innovation Agency (BRIN), 15314 South Tangerang, Banten,
Indonesia
4
Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak,
Malaysia
5
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
6
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia
(UKM), 43600 Bangi, Selangor, Malaysia
7
NANO-ElecTronic Centre (NET), Faculty of Electrical Engineering, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Selangor,
Malaysia
8
Microelectronic and Nanotechnology-Shamsuddin Research Centre (MiNT-SRC), Faculty of Electrical and Electronic Engineering,
Universiti Tun Hussein Onn Malaysia, Parit Raja, 86400 Batu Pahat, Johor, Malaysia
9
Physics Department, Faculty of Sciences and Technology, Universitas Islam Negeri Walisongo Semarang, Semarang, Central Java,
Indonesia
10
Physics Department, Faculty of Mathematics and Natural Science, Universitas Negeri Semarang, Semarang, Indonesia

Received: 13 June 2022 ABSTRACT

Accepted: 14 August 2022 This study presents a simpler approach to directly synthesize graphene oxide
(GO) via electrochemical exfoliation method utilizing customized triple-tail
Ó The Author(s), under 1-butyl-3-methyl-imidazolium, 1, 4-bis(neopentyoxy)-3-(neopentyloxycar-
exclusive licence to Springer bonyl)-1, 4-dioxobutane-2-sulfonate (BMIM-TC14) and sodium 1,4-bis(-
Science+Business Media, LLC, neopentyloxy)-3-(neopentylcarbonyl)-1,4-dioxobutane-2-sulfonate (TC14)
part of Springer Nature 2022 surfactants. The synthesized GO and titanium dioxide (TiO2) were then used as
additives in the fabrication of polyethersulfone (PES)-based nanofiltration (NF)
membrane via non-solvent-induced phase separation method. The dye rejection

Handling Editor: Dale Huber.

Address correspondence to E-mail: [email protected]

https://doi.org/10.1007/s10853-022-07646-2
 J Mater Sci

performance and antifouling ability of the fabricated PES/GOBMIM-TC14/TiO2

and PES/GOTC14/TiO2 NF membranes were then investigated by comparing it
with pristine PES membrane. It is worth noting that the utilization of triple-tail
surfactant obviously enhanced membrane’s morphology in which PES/
GOTC14/TiO2 NF membrane showed the highest hydrophilicity as shown by its
lowest contact angle (68.98°). According to dead-end cell measurement, higher
pure water flux (200.265 L/m2h) and dye rejection (86.58%) were also obtained
by PES/GOTC14/TiO2 NF membrane compared to other fabricated membranes.
Higher GO amount in the sample resulted from the utilization of triple-tail
surfactants that was believed to improve the dye rejection performance and
antifouling abilities. Both GO-based NF membranes also showed a high flux
recovery ratio ([ 100%) compared to the pristine PES membrane (5.88%),
thereby implied their excellent antifouling ability.

GRAPHICAL ABSTRACT

Introduction contamination and becomes the most preferred

method to treat wastewater due to their merits of
removing a wide range of contaminants, high effi-
Over the past years, textile industries development cient, no phase change, low energy consumption and
has led to a major problem of water pollution since a low chemical sludge effluent [2–6].
huge amount of waste from these industries has been Polyethersulfone (PES) is a well-known polymeric
released directly into the water. The presence of material which is widely employed in the nanofiltra-
organic dyes in the wastewater effluents can cause tion (NF) membrane fabrication for numerous appli-
severe problems since they are toxic, carcinogenic cations. Its unique characteristics include excellent
and dangerous to human health [1]. In this kind of chemical, mechanical and thermal resistance, soluble
situation, there is an urgent need to expand some in aprotic organic solvent and relative resistance to
technologies that are led to eliminate the environ- heat aging making it ideal for asymmetric membrane
ment pollutant, low cost and eco-friendly. Membrane preparation [7–9]. However, PES membrane is sus-
separation has grown exponentially to remove dye ceptible to membrane fouling during filtration
J Mater Sci

processes due to its inherited hydrophobic nature GO also known for its large surface area and excellent
which in turn resulting severe flux decline, shortening chemical stability. Many efforts have been done to
membrane lifespan and maintenance cost increment develop a large-scale, high quality and purity of
[10]. Blending with hydrophilic additive has acquired graphene production including electrochemical
much interest in order to change the PES membrane exfoliation method. Electrochemical exfoliation offers
surface properties to be more hydrophilic due to their several benefits including one-step method, low cost,
easy operation, high efficiency and lower cost. In par- simple in operation and environmentally friendly
ticular, metal oxide particles (zinc oxide (ZnO) and since it can avoid harsh chemical consumption [18].
titanium dioxide (TiO2)) and carbon-based material Through this method, GO can be exfoliated in
(carbon nanotubes (CNTs) and graphene oxide (GO)) ambient condition with the presence of an aqueous or
[8, 11–14] have been successfully mixed to the polymer non-aqueous electrolyte solution, graphite as an
matrix to improve membrane hydrophilicity and electrode and an electrical current.
antifouling properties. GO-based membrane has been highlighted by many
TiO2 is known for its special properties such as researchers, and its reports have been published for a
commercial availability, low toxicity and chemical long time [8, 16, 19–22]. In spite of its advantages, the
stability. Furthermore, its large surface area and GO agglomeration in polymer matrix is still
unique self-cleaning behavior make them as a inevitable which may result in poor membrane per-
potential candidate material to be studied for formance. Concerning this limitation, the utilization of
wastewater treatment [11, 15]. Its capability to surfactant for better GO dispersion in the polymer
increase water permeability and antifouling proper- matrix is essentially needed. Previous work has
ties has been recognized by many researchers since it reported that the triple-tail sodium 1,4-bis(neopenty-
is highly hydrophilic. Several reports have demon- loxy)-3-(neopentylcarbonyl)-1,4-dioxobutane-2-sul-
strated that incorporation of TiO2 could improve the fonate (TC14) surfactant presented the highest CNTs
membrane surface and fouling resistance. Guo and dispersion as compared to the single- and double-tail
Kim [15] showed that hydrophilicity of the fabricated surfactants [23]. In addition, a low GO agglomeration
membrane measured by contact angle was improved was obtained when the synthesized triple-tail TC14-
from 68 to 57° for pristine PES and PES/TiO2, based GO was intermixed with natural rubber latex
respectively. PES/TiO2 membrane also showed [24]. The previous report has also showed that the
higher Bovine serum albumin rejection (99%) com- utilization of triple-tail TC14 surfactant during GO
pared to that pristine PES membrane (96.5%). In synthesis has presented a smooth membrane surface
addition, Ahmad et al. [11] agreed that TiO2 can act and high dye rejection of 92.61% as compared to the
as an excellent additive to enhance surface single- and double-tail surfactants [21, 22].
hydrophilicity and increased the membrane perfor- In this work, the effect of different customized
mance. They reported that the incorporation of 1 wt% triple-tail surfactants’ utilization; 1-butyl-3-methyl-
of TiO2 resulted a membrane with lower contact imidazolium, 1, 4-bis(neopentyoxy)-3-(neopenty-
angle (67°) and higher water flux of 27. 262 L/m2h loxycarbonyl)-1, 4-dioxobutane-2-sulfonate (BMIM-
compared with pristine PES membrane (72° and TC14) and TC14 for better homogeneity and disper-
21.196 L/m2h, respectively). sion of GO sheet in polymer matrix has been inves-
On the other hand, graphene oxide (GO) is also one tigated. It is believed that the utilization of these
of the promising materials to modify membrane surfactants resulted in excellent performance of PES/
surface properties. GO is a single layer of graphite GO-based membrane for wastewater treatment
oxide with one-atom layer thick. It has gained application. As far as it is known, the novelty of this
tremendous consideration in the membrane fabrica- study lies on the utilization of customized triple-tail
tion, and the research on its application value is still BMIM-TC14 and TC14 surfactants for GO synthesis
rising due to their distinctive properties. GO consists via electrochemical exfoliation and further utilized
of abundance number of oxygen-functional groups for methylene blue (MB) dye rejection application.
(hydroxyl, carboxyl and epoxy groups) which make This is the first attempt in comparing the effect of two
them highly hydrophilic [16]. As the consequence, different types of customized triple-tail surfactant on
GO can be easily dispersed into water or organic membrane morphology and performance. It has
solvent [8, 17]. Alongside with these characteristics, commonly been assumed that these surfactants’
 J Mater Sci

utilization for PES/GO membrane fabrication will overnight. After the initial phase separation, the
enhance membrane hydrophilicity, permeability, dye fabricated membrane was kept in DI water until
rejection and antifouling properties. further measurements.

Membrane’s characterizations
Materials and methods
The surface and cross-sectional images of the fabricated
Materials NF membranes were observed via field emission scan-
ning electron microscopy (FESEM) (Hitachi SU8020).
Graphite rods (99.99% purity, 10 mm diameter and Prior to analysis, to obtain a good membrane fracture for
150 mm length) obtained from GoodFellow GmbH, cross-sectional observation, the fabricated membranes
Germany were used as electrodes for GO synthesis. were immersed in liquid nitrogen followed by coating
Other materials for GO synthesis include the cus- with a gold layer to improve its conductivity. ImageJ
tomized triple-tail surfactants (BMIM-TC14 and software was also further used to confirm the pore size of
TC14) and dimethylacetamide (DMAC) (Sigma- the fabricated membranes. Meanwhile, energy-disper-
Aldrich) as solvent. The PES (grade in palette form) sive X-ray (EDX) instrument (Horiba EMAX) was per-
and commercial TiO2 nanoparticles (C 99.5%, Sigma- formed to confirm the elemental composition of the
Aldrich) were used as the main polymer additive, fabricated NF membranes. The fabricated NF mem-
respectively, to fabricate NF membrane. Meanwhile, branes’ structural properties were then examined via
the MB dye for dye rejection test was obtained from micro-Raman spectroscopy (Renishaw InVia microRa-
Sigma-Aldrich. man system) and X-ray diffraction (XRD) analysis
(MiniFlex, Rigaku).
Graphene oxide synthesis
Nicolet 6700 Fourier transformed infrared spec-
troscopy (FTIR) analysis was performed to assess the
GO was synthesized via electrochemical exfoliation
fabricated NF membranes functionalities. Next, the
approach as reported by previous studies [21, 22, 25].
surface morphology and roughness of the fabricated
First, the customized triple-tail surfactants (BMIM-
NF membranes were analyzed using atomic force
TC14 and TC14) were dissolved in DMAC solution to
micrograph (AFM) (Park System XE-100, Korea).
compose 0.1 M electrolyte solution. Two pieces of
Water contact angle measurement was then con-
graphite rods were then partially immersed in the
ducted using drop shape analysis (Optical Contact
electrolyte solution followed by connecting to the 7 V
Angle 15EC, Dataphysics) to signify the membrane
DC power supply for 24 h.
hydrophilicity. In brief, the dry membrane was
PES/GO-based NF membrane preparation placed on a glass slide and a droplet of water was
dropped on the membrane surface followed by cap-
PES/GO-based NF membrane was fabricated via turing the image.
non-solvent induced phase separation (NIPS) Membrane porosity can be determined as the ratio
method. The casting solution consists of 20 wt% of of the membrane pores volume and its membrane
PES and 1 wt% of TiO2 which were dissolved in total volume [5]. Therefore, to determine the mem-
DMAC_GOBMIM-tc14 and DMAC_GOTC14 solution (79 brane porosity, it was assumed that all the pores were
wt%), respectively. On the other hand, pristine PES completely filled with water. The gravimetric method
membrane was only dissolved into DMAC for com- was applied to determine the fabricated NF mem-
parison. Subsequently, the casting solution was stir- branes porosity and further calculated using the fol-
red for 48 h at 70 °C until the homogenous solution lowing equation:
was obtained. Thereafter, the well-mixed casting ðw1  w2 Þ=qw
e¼
 100% ð1Þ
solution was placed at room temperature for over- ½ðw1  w2 Þ=qw Þ þ w2 =qp
night to ensure complete release of air bubbles before
casting process. Once the casting solution had been where e is membrane porosity (%), w1 and w2 are the
prepared, the membrane was casted on a glass plate wet and dry membrane weights (g), respectively, qw
using a casting knife with 200 lm casting gap and is the water density (0.998 g/cm3) and qp is the PES
then immersed in a deionised (DI) water for density (1.37 g/cm3).
J Mater Sci

The Sterlitech HP4750 dead-end cell system (ef- FESEM, and the results are depicted in Fig. 1. Based
fective membrane area 7.55 cm3) with a capacity of on the surface morphology presented in Fig. 1a, e,
200 mL was utilized to evaluate membrane perme- and i, further measurement was carried out using an
ation flux, dye rejection and antifouling properties of ImageJ software to confirm the fabricated mem-
the fabricated NF membranes. Prior to permeation brane’s pore size. Based on the measurement, all of
analysis, each membrane was pre-compacted with DI the fabricated membranes presented a nanopore size,
water at 0.6 MPa for 30 min to obtain a steady flux. where the pristine PES, PES/GOBMIM-TC14/TiO2 and
Afterward, water flux measurement was conducted PES/GOTC14/TiO2 membranes pore size were 2.276,
for 10 min by applying 5 different pressure levels 2.673 and 4.343 nm, respectively. Therefore, it is
(0.1–0.5 MPa). The water flux was then calculated confirmed that all of the fabricated membranes were
using the following equation: NF membrane. Moreover, all of the fabricated mem-
V branes consist of asymmetric structure with finger-
J ¼ ð2Þ like structure. Still, the hybrid membrane had a dif-
ADt
ferent void structure as compared to pristine mem-
where J is the permeated flux (L/m2h), V is the per-
brane. As could be seen from Fig. 1a, pristine PES
meated water volume (m3), A is the membrane area
membrane surface consists of smooth surface with
(m2) and Dt is the permeation time (h).
small amount of nodule shapes on its surface (refer
In order to evaluate the fabricated NF membranes
black rectangle shape), which indicated the presence
performance for dye rejection, 10 ppm concentration
of PES polymer [26]. For instance, the PES membrane
of MB dye solution was employed as feed solution.
presented short finger-like pores with the size ranged
Then, it was followed by absorbance measurement of
from 357 nm to 2.78 lm with thicker bottom layer
the treated dye solution by using UV–Vis spec-
lookalike sponge structure than the hybrid mem-
troscopy. The dye rejection efficiency was then cal-
brane (Fig. 1b). This morphology is frequently
culated using the following equation:
  detected in PES membrane with additive-free [27, 28].
Cp Meanwhile, the active layer thickness of PES
Rð%Þ ¼ 1   100% ð3Þ
Co membrane was found to be 516 nm as presented in
where R is the dye rejection efficiency (%), Cp is the per- Fig. 1c. EDX analysis in Fig. 1d then showed higher C
meate dye concentration (ppm), and Co is the initial dye atomic percentage of 74.77% over O and S element;
concentration (ppm). After each dye rejection experi- 19.27 and 5.73%, respectively. The presence of S ele-
ment, the fabricated NF membranes were thoroughly ment was due to the sulfone and ether group of PES
cleaned with DI water by pressuring the post-treated polymer. Next, as can be seen from Fig. 1 e and i,
membrane for 30 min. Then, the water flux measure- PES/GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2
ment of regenerated membrane was again evaluated at hybrid membranes exhibited smooth surface without
0.2 MPa for 10 min. The flux recovery ratio (FRR) was any crack, thereby representing good surface dura-
calculated by the following formula: bility of the fabricated NF membranes with GO and
  TiO2 additives [29, 30]. Previous study reported that
Jw2 GOBMIM-TC14 presented a slightly better dispersion
FRR ¼  100% ð4Þ
Jw1 compared to GOTC14 due to the sodium counterions
where FRR is the flux recovery ratio, J w1 and J w2 are the (Na?) replacement with imidazolium cations which
initial water flux of the membrane before filtration pro- simply affect the surfactant stability system [31].
cess and water flux of the membrane after backwash Nevertheless, this study demonstrated that triple-tail
process (membrane cleaning), respectively (L/m2h). TC14 resulted better exfoliation level of graphite and
its stability in polymer matrix compared to triple-tail
BMIM-TC14 when the electrolyte was replaced by
Results and discussion DMAC. Consequently, higher GO content presence
in PES/GOTC14/TiO2 membrane is observed as
FESEM and EDX analysis illustrated by its darker top surface than PES/GOB-
MIM-TC14/TiO2 membrane. In conclusion, the stabi-
The surface and cross-sectional morphology of the lizer and solvent choices have influenced the GO
fabricated NF membranes were examined via exfoliation degree and dispersion ability as well as
 J Mater Sci

Figure 1 FESEM images of:

a–d pristine PES, e–h PES/
GOBMIM-TC14/TiO2 and i–
l PES/GOTC14/TiO2 NF
membranes.

the dye rejection capability of the fabricated could be corresponded to the PES polymer (black
membrane. rectangle shape) and the entrapped TiO2 particle
In addition, it is interesting to consider the pres- (blue rectangle shape), respectively [11, 26]. More-
ence of nodules shape and white spot on both hybrid over, higher amount of nodule shape and white spot
membrane’s surfaces as well as on the cross-sectional in PES/GOTC14/TiO2 compared to the PES/GOBMIM-
images. Nevertheless, the nodules shape on the TC14/TiO2 sample might be caused by the agglomer-
hybrid membrane’s surface is uniform with no sub- ation of TiO2 and PES polymer.
stantial defects. The presence of these nodules shape Considering Fig. 1f and j, there was no significant
and white spot on both hybrid membrane’s surfaces difference on the morphological properties of PES/
J Mater Sci

Figure 1 continued.

GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 sample. It NF membranes and its spongy-like bottom support
can be seen from the cross-sectional images of the almost unnoticeable. Besides, the pores of the inter-
fabricated hybrid NF membrane, an asymmetric connected support layer become close to each other
structure including dense-skin layer and porous fin- and this kind of structure was believed to be a great
ger-like structure as sublayer was observed in both help to assist membrane permeation.
samples. These skin layer played a pivotal role for the Next, by comparing Fig. 1f and j, significant dif-
permeation and solute rejection, while porous sub- ferences in the sublayer’s structure can be observed.
layer enacts as mechanical support along with low PES/GOTC14/TiO2 apparently showed longer finger-
resistance to water permeation [32, 33]. In the PES/ like structure with bulkier void structure at the bot-
GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 samples, tom as compared to pristine PES and PES/GOBMIM-
the thickness of selective layer was found to be 1.29 TC14/TiO2 membrane. In addition, the sizes of finger-
(Fig. 1g) and 1.49 lm (Fig. 1k), respectively, thereby like structure of PES/GOBMIM-TC14/TiO2 sample were
confirming that these two samples possessed higher in range of 1.19–3.17 lm, while PES/GOTC14/TiO2
selective layer thickness than pristine membrane sample was within range of 992 nm–437 lm, which
(only 516 nm). Thicker selective layer of PES/ was bigger than pristine PES. These results could be
GOTC14/TiO2 compared to PES/GOBMIM-TC14/TiO2 explained by the phenomenon of the accelerating
sample was believed attributed to the presence of solvent and non-solvent exchange rate induced by
higher GO content resulted from better exfoliation the GO in the phase inversion process [5, 35]. As one
assisted by TC14 surfactant [34]. would expect, GO contained a large number of
It is also known that the obtained membrane’s hydrophilic functional groups; therefore, blending
structure is strongly related to the mechanisms of the GO into the polymer matrix promotes the water
NIPS process. The introduction of hydrophilic addi- diffusion from the coagulant bath to the membrane
tive in the membrane obviously alters the pore solution. In addition, during the phase inversion
structures. In a general view, both of these mem- process, the macrovoid structure initially formed by
branes showed typical well-developed finger-like the nucleation and grows in liquid–liquid phase
structure and spongy-like bottom support. As shown separation [33]. Therefore, with the increase in the
by the cross-sectional FESEM images, the finger-like GO content, membrane solution become more
structures become elongated and even extending hydrophilic which resulted in the faster diffusion of
toward the bottom region of both fabricated hybrid water into the polymer lean phases of the polymer
 J Mater Sci

solution. This situation led to the big finger-like square roughness (Rq) and average third highest peak
macrovoid formation in PES/GOTC14/TiO2 mem- to third lowest valley height (Rz) are summarized in
brane [33]. Table 1. Generally, larger value of Ra, Rq and Rz
In fact, the rapid exchange rate between the solvent indicated higher surface roughness [40]. As displayed
and non-solvent during the membrane formation also by AFM images, the membrane roughness increases
affected the fabricated NF membrane thickness. from 32.693 to 108.146 nm upon the addition of GO
Thicker PES/GOTC14/TiO2 sample (113 lm) in com-
parison with pristine PES (86.2 lm) (Fig. 1b) and
PES/GOBMIM-TC14/TiO2 (90.8 lm) (Fig. 1f) is obvi-
ously observed (Fig. 1j). It is generally accepted that
higher GO content promotes a rapid phase demixing
during coagulation which then caused faster polymer
chains precipitation and sequentially increased the
membrane thickness [22, 36, 37]. Additionally, some
transverse holes were observed in PES/GOTC14/TiO2
sublayer as highlighted by rectangle shape in Fig. 1j.
The orientation of these holes was affected by the
arbitrary of GO sheet in the polymer dopes. Since the
GO was highly hydrophilic and PES/GOTC14/TiO2
membrane possess higher GO amount than PES/
GOBMIM-TC14/TiO2 membrane, it promoted the water
to surround GO sheet and form polymer lean phase.
As the water molecules flew along the GO surface,
the orientation of microvoids formation in the sub-
layer was parallel to the GO surface [33]. Therefore, it
is believed that hydrophilic nature and high amount
of GO content resulted the transverse hole formation.
Consequently, the water flux of the membrane may
be affected since the original finger hole and the
water flux communication may be interrupted with
these transverse holes presence [33]. However, as
being reported by Guo and Kim [15], this transverse
orientation could also result in higher membrane
permeability. Some structural and morphological
similarities are in a good agreement with the previ-
ous reports [4, 15, 38, 39].
EDX analysis validates the existence of C, O, Ti,
and S element in the fabricated hybrid NF mem-
branes as depicted in Fig. 1h and l. PES/GOBMIM-
TC14/TiO2 consists of C and O atomic percentage of
72.55 and 21.73%, respectively (Fig. 1h). Meanwhile,
PES/GOTC14/TiO2 possessed lower and higher C
(70.75%) and O (22.76%) content, respectively, as
compared to PES/GOBMIM-TC14/TiO2 (Fig. 1l). Low
Au atomic percentage (* 0.30%) indicated the thin
gold coating for FESEM analysis.
Further membrane’s surface morphology investi-
gation was performed using AFM, and the results are
depicted in Fig. 2. Meanwhile, the obtained parame- Figure 2 AFM images of: a pristine PES, b PES/GOBMIM-TC14/
ters including roughness average (Ra), root mean TiO2 and c PES/GOTC14/TiO2 NF membranes.
J Mater Sci

and TiO2 as additives (see Rq values in Table 1). It is

well known that the addition of hydrophilic GO and
higher GO content could promote the top surface
solidification rate which then can resulted in 1D
shrinkage on the top surface of fabricated membrane
once the casting solution was in contact with coagu-
lating bath. This situation could lead to the spheres or
nodules of polymer formation and causes the
increased of the surface roughness [41]. There had
been reported that the increase in surface roughness
increases the effective membrane filtration area [42].
The increment in surface area and longer finger-like
structure of PES/GOBMIM-TC14/TiO2 and PES/
GOTC14/TiO2 membrane (as presented in FESEM
images) are expected to improve the fluxes as com-
pared to pristine PES.

Micro-Raman analysis

Figure 3 shows micro-Raman spectra of the fabri-

cated NF membranes. Basically, Raman spectroscopy
was applied to provide the significant insights
regarding the quantitative chemical composition in
the fabricated membrane. There are several peaks
observed for pristine membrane that associated with
PES in the range of 1000–1600 cm-1 (Fig. 3a). The
intense peak around 1148 cm-1 associated with C–S
(C–O) stretching mode of PES, while the other two
peaks around 1072 and 1110 cm-1 ascribed to the
symmetric and asymmetric O=S=O groups stretching
vibrations, respectively [43]. There also a peak at
1610 cm-1 which correlated with in-plane benzene
ring deformation [44].
Figure 3 Micro-Raman Spectroscopy of the fabricated NF
Nevertheless, the PES peaks were unobserved for membranes: a Pristine PES, b PES/GOBMIM-TC14/TiO2 and PES/
both hybrid membranes due to the weaker intensity GOTC14/TiO2.
peak of PES (Fig. 3b). Several peaks located at *
149, * 396, * 512 and * 638 cm-1 proved the The presence of GO as additive also evidenced by
existence of TiO2 as additive in the hybrid membrane two distinctive peaks (D- and G-band) observed in
matrixes. These peaks were matching to the TiO2 PES/GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 NF
anatase phase of Eg, B1g, A1g and Eg mode [21, 45]. membranes. As depicted in Fig. 3b, it also can be seen
that the D-band intensity of these hybrid membranes
showed higher intensity than G-band, proved the
Table 1 Surface roughness of the fabricated NF membranes
based on AFM analysis
successful exfoliation of graphite via electrochemical
exfoliation method. D-band is related to the defects
Membrane Ra (nm) Rq (nm) Rz (nm) level in the graphite domain due to the presence of
PES 21.644 32.693 373.257
oxygen-containing functional group in the sample,
PES/GOBMIM-TC14/TiO2 47.393 61.927 558.580 while G-band is associated with the graphitic carbon
PES/GOTC14/TiO2 81.001 108.146 758.501 in the structure.
The D- and G-band of PES/GOBMIM-TC14/TiO2
membrane was located at 1335.27 and 1569.61 cm-1,
 J Mater Sci

respectively. These peaks were shifted toward higher

wavelength of 1337.03 and 1579.46 cm-1, respec-
tively, in PES/GOTC14/TiO2 membrane. This result
suggests that PES/GOTC14/TiO2 membrane consists
of fewer layer of exfoliated GO as compared to PES/
GOBMIM-TC14/TiO2 membrane [18]. In addition, the
shifted peak between these two hybrid samples was
believed due to a higher oxidation process promoted
by TC14 surfactant during electrochemical exfoliation
process [21].
Furthermore, the ratio between D- and G-band
intensity (ID/IG) is related to the structural defect and
often become a quality indicator to the produced
material. It is believed that the ratio with high value
showed higher defect density [18]. Based on calcu-
lation, PES/GOTC14/TiO2 possessed higher ID/IG
ratio (1.04) compared to PES/GOBMIM-TC14/TiO2 Figure 4 XRD analysis of the fabricated NF membranes:
membrane (0.95), indicated that more defects exist in (a) Pristine PES, (b) PES/GOBMIM-TC14/TiO2 and (c) PES/
GOTC14/TiO2.
the PES/GOTC14/TiO2 sample [46, 47]. This result
then confirmed that the utilization of triple-tail TC14
peaks in both samples confirmed that the TiO2
surfactant during GO synthesis provided a better
nanoparticles did not leach out from the dope solu-
exfoliation of graphite and induce higher amount
tion during the process of phase inversion.
oxygen-containing functional group of GO than tri-
Nevertheless, the XRD analysis confirmed that the
ple-tail BMIM-TC14 surfactant [21]. It is also believed
TiO2 nanoparticles remained in the membrane matrix
that higher oxidation and exfoliation process may
during the phase inversion process and have been
have enhanced the dye rejection and antifouling
distributed to the membrane [52, 53]. In addition, the
ability.
crystalline peaks of TiO2 for both hybrid samples
exhibit a slight shift from typical TiO2 peaks [54, 55],
XRD analysis
which was believed due to the interaction between
Apart from its function to determine the changes in PES and GO. However, it was notice that the
the material crystallinity, XRD analysis can also be diffraction peak of GO at 2h = * 10° disappears in
used to spot the materials presence. Figure 4 depicts both of PES/GOBMIM-TC14/TiO2 and PES/GOTC14/
the XRD patterns of the fabricated NF membranes TiO2 NF membranes. This might be due to the GO
that clearly demonstrates a prominent diffraction sheets regular stack that has been destroyed by TiO2
peak without any crystallinity at * 18°, thereby intercalation [51, 55].
confirming the amorphous nature of PES polymer in
all samples [48, 49]. After the incorporation of GO FTIR analysis
and TiO2 in the sample, new peak formations were
The chemical structure of the fabricated NF mem-
observed. In PES/GOBMIM-TC14/TiO2 sample
branes was examined by FTIR analysis. The FTIR
(Fig. 4b), the diffraction peaks of TiO2 were distin-
spectra of pristine PES, PES/GOBMIM-TC14/TiO2 and
guished at 25.06, 27.08, 37.3, 47.72, 53.76, 54.74 and
PES/GOTC14/TiO2 NF membranes are illustrated in
62.34°, which is consistent with the identified anatase
Fig. 5. The aromatic ether (–C–O–C–) chemical bond
phase peaks [50, 51]. Meanwhile, the pattern of ana-
of pristine PES, PES/GOBMIM-TC14/TiO2 and PES/
tase TiO2 for PES/GOTC14/TiO2 sample (Fig. 4c)
GOTC14/TiO2 NF membranes can be found at
showed the crystalline characteristic peak at 24.61,
1011.87, 1012.27 and 1012.42 cm-1, respectively [56].
25.72, 27.01, 37.08, 47.38, 53.34, 54.44 and 62.04°.
Meanwhile, the peaks around 1153.20 and
Frequently, the incorporated additives may leach out
1323.14 cm-1 appeared in the pristine PES membrane
of the polymer matrix due to their affinity with a non-
were caused by sulfone groups (SO2) stretching
solvent (water) [52]. However, the existence of TiO2
J Mater Sci

Hydrophilicity, contact angle and porosity

analysis

The hydrophilicity of the fabricated membranes was

determined by static contact angle measurement.
Ordinarily, lower contact angle value indicated that
the membrane surface exhibits higher hydrophilicity
and better wettability to the water. As stated in
Table 2, pristine PES membrane exhibited the highest
contact angle value (77.35°) as compared to others
fabricated membranes. This confirmed the high
hydrophobic properties and poor wettability of PES
membrane to water. In contrast, lower contact angle
of PES/GOBMIM-TC14/TiO2 (70.99°) and PES/
GOTC14/TiO2 (68.98°) membranes were observed and
suggested an improved hydrophilicity of hybrid
Figure 5 FTIR spectra of the fabricated NF membranes: membranes.
(a) Pristine PES, (b) PES/GOBMIM-TC14/TiO2 and (c) PES/ As expected, the addition of GO and TiO2
GOTC14/TiO2. increased the membrane’s hydrophilicity. The
hydrophilic GO may migrate to the fabricated mem-
brane surface during the demixing process then
vibration [57]. However, these peaks were slightly leading to the hydrophilicity increment. In addition,
shifted for both hybrid membranes; 1152.84 and the highest hydrophilicity possessed by PES/
1322.76 cm-1 for PES/GOBMIM-TC14/TiO2 and 1152.89 GOTC14/TiO2 sample might be owed to the utilization
and 1322.81 cm-1 for PES/GOTC14/TiO2 membrane. of triple-tail TC14 surfactant during GO synthesis
Lower wave number observed in both hybrid mem- which provided a better exfoliation of graphite and
branes was believed due to the formation of hydro- induced higher amount of oxygen-functional group
gen bond between oxygen-functional group of GO in GOTC14 solution as being demonstrated by higher
and oxygen atom of the sulfone group. Meanwhile, ID/IG ratio of Raman analysis. In fact, PES/GOTC14/
C=O stretching vibration of PES/GOBMIM-TC14/TiO2 TiO2 may also contained more hydrogen bonds than
and PES/GOTC14/TiO2 membrane were located at other sample. Therefore, it was believed that
1737.88 and 1739.34 cm-1, respectively [41]. More- hydrophilicity improvement of the hybrid membrane
over, the backbone vibrations of benzene groups will affect membrane flux due to better attraction
were also observed for pristine PES (1487.78 and force between membrane surface and water droplet.
1579.65 cm-1), PES/GOBMIM-TC14/TiO2 (1487.78 and Concurrently, antifouling ability was also expected to
1579.35 cm-1) and PES/GOTC14/TiO2 (1487.70 and improve from the hydration layer presence on the
1579.37 cm-1) membranes [56]. membrane surface, i.e., higher flux recovery.
As demonstrated in Fig. 5b and c, two new for- Furthermore, as clearly depicted in Table 2, the
mations of sharp peak at 1656.15 and 1653.06 cm-1 porosity measurement revealed an increment in the
were observed in both hybrid membranes that porosity as the incorporation of hydrophilic additives
attributed to the Ti–O bond, thus confirmed the
existence of TiO2 as additive. In addition, a broad
Table 2 Contact angle and porosity measurement of the
band at 3402.45 and 3427.86 cm-1 associated with the fabricated NF membranes
stretching vibration of –OH group was also observed
for PES/GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 Membrane Contact angle (°) Porosity (%)
NF membranes, respectively. However, due to the PES 77.35 88.40
PES bonds interference, most of the peak related to PES/GOBMIM-TC14/TiO2 70.99 90.14
the GO structure cannot be identified clearly in the PES/GOTC14/TiO2 68.98 91.25
FTIR spectra [58].
 J Mater Sci

in the membrane matrix. For instance, the membrane addition of hydrophilic GO and TiO2, the pure water
porosity increased from * 88% (pristine PES) to * flux and permeability value significantly increased.
90 and * 91% for PES/GOBMIM-TC14/TiO2 and In fact, it was believed that the incorporation of
PES/GOTC14/TiO2 membrane, respectively. This triple-tail surfactant (BMIM-TC14 and TC14) pro-
could be related to the functional group of GO and vides an extra chain for GO and polymer intercon-
TiO2 which rapidly promoted the diffusion of solvent nection with water molecules [21]. Generally, the
molecules from the polymer matrix to the coagula- hydrophobic nature of surfactant’s tail is attached to
tion bath [27]. Therefore, higher porosity of PES/ the carbon bonds, while its hydrophilic head resides
GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 mem- in the electrolyte solution. Therefore, the triple-tail
brane was obtained than those of pristine PES. The surfactant is capable in providing triple interaction
porosity values were in line with the FESEM obser- between GO layers and surfactant which further
vation, where PES/GOTC14/TiO2 showed more por- boost surfactant’s intercalation into the GO inner
ous structure and presented lower contact angle layer spacing and resulted more stable GO sheets
value than those other membranes. [24]. When these stable GO sheets were intermixed
into polymer matrix, it is highly expected that better
Water flux based on different operating interaction between the polymer and GO was
pressure formed. This interaction will provide the triple
pathway for water permeation through PVDF mem-
The pure water flux and permeability are correlated brane thus resulted in higher water flux and perme-
with the fabricated membrane’s hydrophilicity ability as the consequences.
[27, 59]. In most cases, the water passage through Overall, the maximum pure water flux of the fab-
membrane can be influenced by hydrophilicity, ricated membrane was obtained to be 200.265 L/m2h
additional water channel provided by hydrophilic for PES/GOTC14/TiO2 membrane. Meanwhile, the
additives and the mean pore size of the fabricated lowest pure water flux was presented by PES mem-
membrane [59]. Figure 6 shows the pure water flux of brane (20.839 L/m2h) (see Table 3). In addition, PES/
the fabricated membranes at different applied pres- GOBMIM-TC14/TiO2 membrane presented fourfold
sures (0.1 to 0.5 MPa). As expected, the fluxes increase in pure water flux (85.121 L/m2h) than PES
increased apparently by the trans-membrane pres- membrane, but still lower than PES/GOTC14/TiO2
sure increment. Table 3 shows the pure water flux membrane. This is consistent with the reported
and water permeability of the fabricated pristine PES, observation of their permeability, hydrophilicity and
PES/GOBMIM-TC14/TiO2 and PES/GOTC14/TiO2 porosity. This confirmed that both hydrophilicity and
membranes. It is well portrayed that upon the porosity portrayed crucial contribution toward the
membrane flux behavior. Furthermore, higher water
flux and permeability of PES/GOBMIM-TC14/TiO2 and
PES/GOTC14/TiO2 membranes compared to the
pristine membrane could be attributed to the GO and
TiO2 presence [13]. Hydrophilic functional group
contents providing additional spaces of water storage
which further increases GO ability to attract water
molecules. In addition, this also might be due to the
size of water molecules itself, which are relatively
small enough to pass freely through the GO nano-
channels within the membrane surface [43]. On the
hydrophilic surface, water droplet captivated onto
membrane surface have greater surface energy that
overpowers water surface tension. In consequence,
this water droplet then passes smoothly into the
hydrophilic pores, thus resulted a higher water flux
Figure 6 Water flux measurements of the fabricated NF [13].
membranes based on different level of driving pressure.
J Mater Sci

Table 3 Dead-end filtration analysis on basis of pure water flux, water permeability, dye flux and rejection rate of the fabricated NF
membranes

Membrane Pure water flux (L/m2h) Water permeability (L/m2hMPa) Dye flux (L/m2.h) Rejection rate (%)

PES 20.839 9.142 3.311 87.67

PES/GOBMIM-TC14/TiO2 85.121 28.780 29.801 86.14
PES/GOTC14/TiO2 200.265 85.725 399.185 86.58

Dye rejection performance of the fabricated fouling [9]. Antifouling property can be evaluated
NF membrane through membrane fouling evaluation. The results of
antifouling experiments at the pressure of 0.2 MPa
Generally, the rejection performance of pristine PES are illustrated in Fig. 7. The PES/GOTC14/TiO2 and
and the modified hybrid membranes are all found to PES/GOBMIM-TC14/TiO2 membranes flux decline was
be higher than 80% (Table 3). It appeared that the dye rapidly drop during the first 2 min before remain
rejection efficiency (R) value of PES/GOTC14/TiO2 steady for the rest minute. Meanwhile, the flux
sample was slightly higher (86.58%) than that of PES/ decline curve of pristine PES was observed to be
GOBMIM-TC14/TiO2 samples (86.14%). However, the maintained from the first minute until the end. The
pristine PES presented higher R value (87.67%) than slower flux decline claimed to be better antifouling
hybrid membranes. Lower rejection rate of PES/ property [61]. However, FRR value must take into
GOTC14/TiO2 and PES/GOBMIM-TC14/TiO2 samples consideration since it is the best index to describe
could be a result of the dye interaction with the antifouling property of the fabricated membrane.
composites, where positive charges of MB dye and its Higher FRR value indicated that the fabricated
hydrophilic properties caused MB passing through membrane owns better antifouling property after
the hydrophilic membrane surface [60]. Nevertheless, easily swept away the foulant on its surface. As
the rejection trend was reversely corresponded to the expected, PES/GO/TiO2 membrane demonstrated
dye flux as the membrane with high rejection rate high FRR compared to pristine PES membrane. The
possessed low dye flux and vice versa. According to result revealed that pristine PES membrane only
the dye flux measurement, PES/GOTC14/TiO2 sample recovered the initial water flux value of about 5.88%.
exhibited the highest dye flux (399.185 L/m2.h), This might be due to an interaction between the
which was almost than four 100-fold and 13-fold
higher than pristine PES (3.311 L/m2.h) and PES/
GOBMIM-TC14/TiO2 (29.801 L/m2.h), respectively. This
situation can be explained by its high hydrophilicity
and porosity as compared to other membranes. In
addition, the existence of higher hydrophilic groups
on the PES/GOTC14/TiO2 surface plays a pivotal role
in increasing dye flux. Hence, these finding leads to
the conclusion that incorporation of triple-tail TC14
during GO synthesis offers better exfoliation thus
affected the membrane performance.

Antifouling properties of the fabricated NF

membrane

Membrane fouling occurred frequently and affected

the membrane performance. During the filtration
process, the foulant tends to be adsorbed on the Figure 7 Flux decline curve of the fabricated NF membranes
membrane surface which then lead to the severe measured at 0.2 MPa pressure.
 J Mater Sci

foulant and hydrophobic surface of pristine PES related to covalent bonding and coordination inter-
membrane suggestive of irreversible fouling process action formed between specific functional groups
[13]. In contrast, higher FRR value was noticed for the such as metal-carbonyl and amino-carbonyl. Mean-
PES/GOBMIM-TC14/TiO2 (125.81%) and PES/GOTC14/ while, nonspecific interaction attributed to the inter-
TiO2 membrane (305.29%) owing to their higher action of hydrogen bonding, hydrophobic, and
hydrophilicity that portrayed a vital role in mem- electrostatic of the foulant and membrane surface.
brane fouling. It can be explained by higher mem- Figure 8 encapsulated the proposed fouling mecha-
brane hydrophilicity which leading to the nism of the pristine PES and PES-based hybrid
hydrophilic water layer formation on membrane membrane. Generally, pore blocking due to the
surface. This water layer will act as protective layer hydrophobic interaction is one of the factors that
and repels the foulant from attaching to the mem- governed the membrane fouling for pristine mem-
brane surface [11, 27]. The antifouling properties brane. When the hydrophilic organic or foulant with
improvement as discovered in this study was large molecular weight diffuse through the mem-
believed not only increase the lifespan of membrane brane, the tendency of these molecules to block the
but also can reduce cleaning cost and energy used for membrane passage is higher. At the moment of
operation over time. pristine PES making a contact with MB dye solution,
In addition, higher FRR value ([ 100%) indicated the water molecule and membrane surface will resist
that PES/GO/TiO2 membrane was not only capable to make a contact, and this situation is known as
of restoring fouling, but at the same time, could retain hydrophobic interaction [64]. This situation further
additional flux after cleaning. This additional flux resulted in direct contact of foulant particle and the
might be counteracted to the pore size enlargement membrane surface of pristine PES. The hydrophobic
after the filtration and cleaning process. This pattern adsorption between membrane surface–foulants
has also been highlighted by several previous studies commonly leading to irreversible fouling. This may
which discussed that the membrane pores size was explain the poor antifouling properties of pristine
increased as the filtration progressed [62, 63]. Mar- PES since simple backwashing is not efficient in
belia et al. [63] reported that over each stage of fil- removing irreversible fouling [65].
tration and maintenance cleaning, flux of the sample
increased by more than 300% over time. They
believed that the additive was slowly released over
each stage of filtration and cleaning processes.
Eventually, this situation might lead to a porosity
increment (larger pore size). Therefore, we believed
that higher FRR value of PES/GO/TiO2 membrane
might attribute to the additives that continue to leach
out during the filtration or cleaning process, further
leads to bigger pore size compared to the initial
condition before the filtration process. This might
explain the reason of higher FRR value of PES/
GOTC14/TiO2 membrane since it already presented
bigger pore size than that of pristine PES and PES/
GOBMIM-TC14/TiO2 as being discussed in FESEM
analysis (Fig. 1j). Therefore, pore size enlargement
not only resulted in bigger pore size but also
increases the membrane porosity.

Membrane fouling mechanism

Basically, membrane fouling can be caused by

specific or nonspecific interactions between mem- Figure 8 The proposed mechanism of membrane fouling for:
brane surface and foulants. The specific interaction is a pristine PES and b PES/GO/TiO2 hybrid membrane.
J Mater Sci

Table 4 Performance comparison of PES-based NF membrane with different additives

Additive Water flux (L/ Dye flux ((L/ Rejection rate (%) Reference
m2h) m2h)

Tannic acid-coated boehmite (TA-BM) 111 – Direct red 16: * 96 [4]

GO-ZnO 13.5 – Trace organic compound: [8]
75
Polyvinyl alcohol-Sodium alginate-GO 115.7 – Lanasol blue 3R: 86.2 [27]
Dendrimer-polycitrate-alumoxane/polyvinyl pyyrolidone 22.6 17.3 Direct red 16: 99 [66]
(PVP)
1, 3, 5-benzene-tricarbonyltri chloride (TMC), 6.1 – Salt rejection (Na2SO4): [67]
Pentaerythritol (PE) 98.1
Deep eutectic solvent/PVP 241.3 * 100 Bovine serum albumin: [68]
99
GOBMIM-TC14-TiO2 85.121 29.801 MB: 86.14 This
study
GOTC14-TiO2 200.265 399.185 MB: 86.58 This
study

With respect to the incorporation of hydrophilic further explored to obtain more accurate information
additives; GO and TiO2, the hydrophilicity of mem- before taking into consideration. For the moment, the
brane could be enhanced by constructing the pro- main fouling mechanism for PES-based membrane
tective layers on membrane surface and increasing might be hydrophobic interaction and hydrogen
the network of hydrogen bonds of water. This pro- bonding rather than electrostatic interaction.
tective layer can reduce the interaction force between
the foulant and membrane surface, then leading to Comparative study of nanofiltration
the prevention of irreversible foulant adsorption. The membrane
water molecules can easily pass through this protec-
tive layer since the hydrophilic additives tends to The fabricated PES/GO/TiO2 membrane’s effective-
form hydrogen bond with water, further provided ness was then compared with identical class of NF
the path for them to pass through it. Nonetheless, the membranes reported by other researchers to identify
unwanted species or foulant were more prone to their performance, and the results are summarized in
attach on the membrane surface and form a cake- Table 4. It can be clearly seen that various additives
layer. These cake-layer of foulant on the hybrid have been employed to enhance PES membrane
membrane surface owns a loose structure with properties. However, none of these studies investi-
weakened adhesion force. By using the simple gated PES membrane performance for MB dye
cleaning or backwashing, these foulant can be easily rejection. In this study, two types of triple-tail sur-
removed from the membrane surface. Therefore, factant (BMIM-TC14 and TC14) were also introduced
PES/GO/TiO2 hybrid membrane displayed the bet- to the PES/GO/TiO2 membrane fabrication and its
ter antifouling properties. effect on morphological and rejection performance
On the other hand, the membrane surface and was studied. It should be note that the rejection rate
foulant interaction might also include the electrostatic of the fabricated membrane in this study might be
interaction. It could be either repulsive or attractive lower than other researchers; however, the perfor-
depending on the charges carried by the membrane mance of the fabricated membranes was accept-
and foulant. The foulant with the same charge of able and its permeability was significantly improved
membrane surface will repel, while the opposite compared to its pristine membrane and comparable
charge will promote the foulant adsorption on the to other previous works.
surface. This interaction might occur in PES-based
membrane. However, the zeta potential should be
 J Mater Sci

Conclusions Sci 575:38–49. https://doi.org/10.1016/j.memsci.2018.12.

070
The PES-based membranes incorporated with [2] Kim BS, Lee J (2016) Macroporous PVDF/TiO2 membranes
hydrophilic additives were successfully fabricated with three-dimensionally interconnected pore structures
via NIPS method employing customized triple-tail produced by directional melt crystallization. Chem Eng J
BMIM-TC14 and TC14 surfactants for GO synthesis 301:158–165. https://doi.org/10.1016/j.cej.2016.05.003
by electrochemical exfoliation method. The influence [3] Nasrollahi N, Ghalamchi L, Vatanpour V, Khataee A (2021)
of triple-tail surfactant on the membrane capability Photocatalytic-membrane technology: a critical review for
and fouling endurance was elucidated with emphasis membrane fouling mitigation. J Ind Eng Chem 93:101–116.
on pure water flux, MB dye rejection and FRR value. https://doi.org/10.1016/j.jiec.2020.09.031
Based on the obtained results, it was found that tri- [4] Oulad F, Zinadini S, Akbar A, Ashraf A (2020) Fabrication
ple-tail TC14 surfactant resulted the highest mem- and characterization of a novel tannic acid coated boehmite/
brane’s porosity (91.296%) and hydrophilicity as PES high performance antifouling NF membrane and
indicated by the lowest contact angle value (68.98°) as application for licorice dye removal. Chem Eng J
compared to all fabricated membranes. In addition, 397:125105. https://doi.org/10.1016/j.cej.2020.125105
higher dye flux (399.185 L/m2.h) and dye rejection [5] Xia S, Ni M (2014) Preparation of poly(vinylidene fluoride)
(86.58%) was presented by PES/GOTC14/TiO2 NF membranes with graphene oxide addition for natural organic
membrane. Besides, its higher FRR value (305.29%) matter removal. J Memb Sci 473:54–62. https://doi.org/10.
confirming that PES/GOTC14/TiO2 NF membrane 1016/j.memsci.2014.09.018
owns acceptable antifouling ability. Overall, the [6] Wang K, Qin Y, Quan S et al (2019) Development of highly
acquired results proposed that the incorporation of permeable polyelectrolytes (PEs)/UiO-66 nanofiltration
particular GO and TiO2 as hydrophilic additives had membranes for dye removal. Chem Eng Res Des
major influence to boost membrane performance and 147:222–231. https://doi.org/10.1016/j.cherd.2019.05.014
antifouling ability. [7] Dehban A, Kargari A, Ashtiani FZ (2020) Preparation and
optimization of antifouling PPSU/PES/SiO2 nanocomposite
ultrafiltration membranes by VIPS-NIPS technique. J Ind
Acknowledgements Eng Chem 88:292–311. https://doi.org/10.1016/j.jiec.2020.
04.028
The authors acknowledge the financial support from [8] Mahlangu OT, Nackaerts R, Thwala JM et al (2017)
the Fundamental Research Grand Scheme (grant no. Hydrophilic fouling-resistant GO-ZnO/PES membranes for
2020-0254-103-02) and Newton Fund: Use of ISIS wastewater reclamation. J Memb Sci 524:43–55. https://doi.
Neutron and Muon Source (grant no. 2019-0257-103- org/10.1016/j.memsci.2016.11.018
11). [9] Ma J, Guo X, Ying Y et al (2017) Composite ultrafiltration
membrane tailored by MOF@GO with highly improved
water purification performance. Chem Eng J 313:890–898. h
Data availability ttps://doi.org/10.1016/j.cej.2016.10.127
[10] Matindi CN, Hu M, Kadanyo S et al (2021) Tailoring the
Not applicable.
morphology of polyethersulfone/sulfonated polysulfone
Declarations ultrafiltration membranes for highly efficient separation of
oil-in-water emulsions using TiO2 nanoparticles. J Memb Sci
Conflicts of interest The authors have no conflict of 620:118868. https://doi.org/10.1016/j.memsci.2020.118868
interest to declare. [11] Ahmad AL, Pang WY, Mohd Shafie ZMH, Zaulkiflee ND
(2019) PES/PVP/TiO2 mixed matrix hollow fiber membrane
with antifouling properties for humic acid removal. J Water
References Process Eng 31:1–9. https://doi.org/10.1016/j.jwpe.2019.
100827
[1] Van TTT, Kumar SR, Lue SJ (2019) Separation mechanisms [12] Algamdi MS, Alsohaimi IH, Lawler J et al (2019) Fabrica-
of binary dye mixtures using a PVDF ultrafiltration mem- tion of graphene oxide incorporated polyethersulfone hybrid
brane: donnan effect and intermolecular interaction. J Memb ultrafiltration membranes for humic acid removal. Sep Purif
J Mater Sci

Technol 223:17–23. https://doi.org/10.1016/j.seppur.2019.0 [23] Mohamed A, Anas AK, Abu Bakar S et al (2014) Prepara-
4.057 tion of multiwall carbon nanotubes (MWCNTs) stabilised by
[13] Makhetha TA, Moutloali RM (2021) Incorporation of a highly branched hydrocarbon surfactants and dispersed in
novel Ag – Cu@ZIF-8@GO nanocomposite into natural rubber latex nanocomposites. Colloid Polym Sci
polyethersulfone membrane for fouling and bacterial resis- 292:3013–3023. https://doi.org/10.1007/s00396-014-3354-1
tance. J Memb Sci 618:118733. https://doi.org/10.1016/j.me [24] Suriani AB, Nurhafizah MD, Mohamed A et al (2016)
msci.2020.118733 Highly conductive electrodes of graphene oxide/natural
[14] Shahruddin MZ, Zakaria N, Diana Junaidi NF et al (2017) rubber latex-based electrodes by using a hyper-branched
Study of the effectiveness of Titanium Dioxide (TiO2) surfactant. JMADE. https://doi.org/10.1016/j.matdes.2016.0
nanoparticle in Polyethersulfone (PES) Composite mem- 3.067
brane for removal of oil in oily wastewater. J Appl Membr [25] Suriani AB, Muqoyyanah MA et al (2018) Reduced gra-
Sci Technol 19:33–42. https://doi.org/10.11113/amst.v19i1. phene oxide-multiwalled carbon nanotubes hybrid film with
21 low Pt loading as counter electrode for improved photo-
[15] Guo J, Kim J (2017) Modifications of polyethersulfone voltaic performance of dye-sensitised solar cells. J Mater Sci
membrane by doping sulfated-TiO2 nanoparticles for Mater Electron 29:10723–10743. https://doi.org/10.1007/s1
improving anti-fouling property in wastewater treatment. 0854-018-9139-4
RSC Adv 7:33822–33828. https://doi.org/10.1039/c7ra [26] Rahimpour A, Madaeni SS, Amirinejad M et al (2009) The
06406c effect of heat treatment of PES and PVDF ultrafiltration
[16] Zhao G, Hu R, Zhao X et al (2019) High flux nanofiltration membranes on morphology and performance for milk fil-
membranes prepared with a graphene oxide homo-structure. tration. J Memb Sci 330:189–204. https://doi.org/10.1016/j.
J Memb Sci 585:29–37. https://doi.org/10.1016/j.memsci.2 memsci.2008.12.059
019.05.028 [27] Amiri S, Asghari A, Vatanpour V, Rajabi M (2020) Fabri-
[17] Ray SC (2015) Application and uses of Graphene oxide and cation and characterization of a novel polyvinyl alcohol-
reduced Graphene oxide. Appl Graphene Graphene-Oxide graphene oxide-sodium alginate nanocomposite hydrogel
Based Nanomater. https://doi.org/10.1016/b978-0-323-3752 blended PES nano filtration membrane for improved water
1-4.00002-9 purification. Sep Purif Technol 250:117216. https://doi.org/
[18] Konstantopoulos G, Fotou E, Ntziouni A et al (2021) A 10.1016/j.seppur.2020.117216
systematic study of electrolyte effect on exfoliation effi- [28] Ocakoglu K, Dizge N, Colak SG et al (2021) Polyethersul-
ciency and green synthesis of graphene oxide. Ceram Int fone membranes modified with CZTS nanoparticles for
47:32276–32289. https://doi.org/10.1016/j.ceramint.2021.08 protein and dye separation: Improvement of antifouling and
.122 self-cleaning performance. Colloids Surfaces A Physic-
[19] Bagheripour E, Moghadassi AR, Hosseini SM et al (2018) ochem Eng Asp 616:126230. https://doi.org/10.1016/j.colsu
Novel composite graphene oxide/chitosan nanoplates incor- rfa.2021.126230
porated into PES based nanofiltration membrane: chromium [29] Karimipour H, Shahbazi A, Vatanpour V (2021) Fouling
removal and antifouling enhancement. J Ind Eng Chem decline and retention increase of polyethersulfone membrane
62:311–320. https://doi.org/10.1016/j.jiec.2018.01.009 by incorporating melamine-based dendrimer amine func-
[20] Chen C, Yang QH, Yang Y et al (2009) Self-assembled free- tionalized graphene oxide nanosheets (GO/MDA). J Environ
standing graphite oxide membrane. Adv Mater Chem Eng 9:104849. https://doi.org/10.1016/j.jece.2020.
21:3007–3011. https://doi.org/10.1002/adma.200803726 104849
[21] Mohamat R, Suriani AB, Mohamed A et al (2021) Effect of [30] Safarpour M, Vatanpour V, Khataee A (2016) Preparation
Surfactants’ tail number on the PVDF/GO/TiO2-Based and characterization of graphene oxide/TiO2 blended PES
Nanofiltration membrane for dye rejection and antifouling nanofiltration membrane with improved antifouling and
performance improvement. Int J Environ Res 15:149–161. h separation performance. Desalination 393:65–78. https://doi.
ttps://doi.org/10.1007/s41742-020-00299-6 org/10.1016/j.desal.2015.07.003
[22] Suriani AB, Muqoyyanah Mohamed A et al (2019) Incor- [31] Mohamed A, Ardyani T, Bakar SA et al (2018) Preparation
poration of electrochemically exfoliated graphene oxide and of conductive cellulose paper through electrochemical
TiO2 into polyvinylidene fluoride-based nanofiltration exfoliation of graphite: the role of anionic surfactant ionic
membrane for dye rejection. Water Air Soil Pollut 230:176. h liquids as exfoliating and stabilizing agents. Carbohydr
ttps://doi.org/10.1007/s11270-019-4222-x Polym 201:48–59. https://doi.org/10.1016/j.carbpol.2018.08.
040
 J Mater Sci

[32] Wang J, Lang WZ, Xu HP et al (2015) Improved poly(vinyl [42] Mahmoudi E, Yong L, Lun W et al (2020) Improving
butyral) hollow fiber membranes by embedding multi-walled membrane bioreactor performance through the synergistic
carbon nanotube for the ultrafiltrations of bovine serum effect of silver-decorated graphene oxide in composite
albumin and humic acid. Chem Eng J 260:90–98. https://doi. membranes. J Water Process Eng 34:101169. https://doi.org/
org/10.1016/j.cej.2014.08.082 10.1016/j.jwpe.2020.101169
[33] Yang M, Zhao C, Zhang S et al (2017) Preparation of gra- [43] Ly QV, Matindi C, Kuvarega AT et al (2020) Exploring the
phene oxide modified poly(m-phenylene isophthalamide) novel PES/malachite mixed matrix membrane to remove
nanofiltration membrane with improved water flux and organic matter for water purification. Chem Eng Res Des
antifouling property. Appl Surf Sci 394:149–159. https://doi. 160:63–73. https://doi.org/10.1016/j.cherd.2020.05.022
org/10.1016/j.apsusc.2016.10.069 [44] Ahmad MW, Dey B, Al Saidi AKA, Choudhury A (2020)
[34] Wang J, Wang Y, Zhu J et al (2017) Construction of Functionalized-graphene reinforced polyethersulfone
TiO2@graphene oxide incorporated antifouling nanofiltra- nanocomposites with improved physical and mechanical
tion membrane with elevated filtration performance. J Memb properties. Polym Compos 41:4104–4116. https://doi.org/10.
Sci 533:279–288. https://doi.org/10.1016/j.memsci.2017.03. 1002/pc.25697
040 [45] Kumi-Barimah E, Penhale-Jones R, Salimian A et al (2020)
[35] Wu L, Zhang X, Wang T et al (2019) Enhanced performance Phase evolution, morphological, optical and electrical
of polyvinylidene fluoride ultrafiltration membranes by properties of femtosecond pulsed laser deposited TiO2 thin
incorporating TiO2/graphene oxide. Chem Eng Res Des films. Sci Rep 10:1–12. https://doi.org/10.1038/s41598-020-
141:492–501. https://doi.org/10.1016/j.cherd.2018.11.025 67367-x
[36] Esmaeili M, Lahti J, Virtanen T et al (2020) The interplay [46] Francolini I, Perugini E, Silvestro I et al (2019) Graphene
role of vanillin, water, and coagulation bath temperature on oxide oxygen content affects physical and biological prop-
formation of antifouling polyethersulfone (PES) membranes: erties of scaffolds based on chitosan/graphene oxide conju-
application in wood extract treatment. Sep Purif Technol gates. Materials (Basel) 12:1142–1158. https://doi.org/10.
235:116225. https://doi.org/10.1016/j.seppur.2019.116225 3390/ma12071142
[37] Nikooe N, Saljoughi E (2017) Preparation and characteri- [47] Khan U, O’Neill A, Lotya M et al (2010) High-concentration
zation of novel PVDF nanofiltration membranes with solvent exfoliation of graphene. Small 6:864–871. https://d
hydrophilic property for filtration of dye aqueous solution. oi.org/10.1002/smll.200902066
Appl Surf Sci 413:41–49. https://doi.org/10.1016/j.apsusc. [48] Kazemi M, Peyravi M, Jahanshahi M (2020) Multilayer UF
2017.04.029 membrane assisted by photocatalytic NZVI@TiO2
[38] Vatanpour V, Madaeni SS, Khataee AR et al (2012) TiO2 nanoparticle for removal and reduction of hexavalent chro-
embedded mixed matrix PES nanocomposite membranes: mium. J Water Process Eng 37:101183. https://doi.org/10.
influence of different sizes and types of nanoparticles on 1016/j.jwpe.2020.101183
antifouling and performance. Desalination 292:19–29. http [49] Abdulkarem E, Ibrahim Y, Naddeo V et al (2020) Devel-
s://doi.org/10.1016/j.desal.2012.02.006 opment of Polyethersulfone/a-Zirconium phosphate (PES/a-
[39] Jiang B, Zhang N, Zhang L et al (2018) Enhanced separation ZrP) flat-sheet nanocomposite ultrafiltration membranes.
performance of PES ultrafiltration membranes by imidazole- Chem Eng Res Des 161:206–217. https://doi.org/10.1016/
based deep eutectic solvents as novel functional additives. j.cherd.2020.07.006
J Memb Sci 564:247–258. https://doi.org/10.1016/j.memsci. [50] Khalid F, Tabish M, Bora KAI (2020) Novel poly(vinyl
2018.07.034 alcohol) nanofiltration membrane modified with dopamine
[40] Balkanloo PG, Mahmoudian M, Hosseinzadeh MT (2020) A coated anatase TiO2 core shell nanoparticles. J Water Process
comparative study between MMT-Fe3O4/PES, MMT-HBE/ Eng 37:101486. https://doi.org/10.1016/j.jwpe.2020.101486
PES, and MMT-acid activated/PES mixed matrix mem- [51] Li C, Sun W, Lu Z et al (2019) Systematic evaluation of
branes. Chem Eng J 396:125188. https://doi.org/10.1016/j.ce TiO2-GO-modified ceramic membranes for water treatment:
j.2020.125188 retention properties and fouling mechanisms. Chem Eng J
[41] Chu Z, Chen K, Xiao C et al (2020) Performance 378:122138. https://doi.org/10.1016/j.cej.2019.122138
improvement of polyethersulfone ultrafiltration membrane [52] Kusworo TD, Ariyanti N, Utomo DP (2020) Effect of nano-
containing variform inorganic nano-additives. Polymer TiO2 loading in polysulfone membranes on the removal of
(Guildf) 188:122160. https://doi.org/10.1016/j.polymer.202 pollutant following natural-rubber wastewater treatment.
0.122160 J Water Process Eng 35:101190. https://doi.org/10.1016/j.
jwpe.2020.101190
J Mater Sci

[53] Wu G, Gan S, Cui L, Xu Y (2008) Preparation and char- polyethersulfone ultrafiltration membrane by blending with
acterization of PES/TiO2 composite membranes. Appl Surf bio-based dragonbloodin resin. Polymers (Basel). https://doi.
Sci 254:7080–7086. https://doi.org/10.1016/j.apsusc.2008.0 org/10.3390/polym13244436
5.221 [63] Marbelia L, Bilad MR, Vankelecom IFJ (2019) Gradual PVP
[54] Jaleh B, Zare E, Azizian S et al (2020) Preparation and leaching from PVDF/PVP blend membranes and its effects
characterization of polyvinylpyrrolidone/polysulfone ultra- on membrane fouling in membrane bioreactors. Sep Purif
filtration membrane modified by graphene oxide and tita- Technol 213:276–282. https://doi.org/10.1016/j.seppur.2018.
nium dioxide for enhancing hydrophilicity and antifouling 12.045
properties. J Inorg Organomet Polym Mater 30:2213–2223. [64] Xu H, Xiao K, Wang X et al (2020) Outlining the roles of
https://doi.org/10.1007/s10904-019-01367-x membrane-Foulant and Foulant-Foulant interactions in
[55] Zhang H, Wang X, Li N et al (2018) Synthesis and char- organic fouling during microfiltration and ultrafiltration: a
acterization of TiO2/graphene oxide nanocomposites for mini-review. Front Chem 8:1–14. https://doi.org/10.3389/fc
photoreduction of heavy metal ions in reverse osmosis hem.2020.00417
concentrate. RSC Adv 8:34241–34251. https://doi.org/10.1 [65] Gao Y, Qin J, Wang Z, Østerhus SW (2019) Backpulsing
039/c8ra06681g technology applied in MF and UF processes for membrane
[56] Farnam M, Mukhtar H, Shariff AM (2016) An investigation fouling mitigation: a review. J Memb Sci 587:117136. h
of blended polymeric membranes and their gas separation ttps://doi.org/10.1016/j.memsci.2019.05.060
performance. RSC Adv 6:102671–102679. https://doi.org/ [66] Zinadini S, Gholami F (2016) Preparation and characteri-
10.1039/c6ra21574b zation of high flux PES nanofiltration membrane using
[57] Li YN, Li H, Ye H et al (2019) Preparation and characteri- hydrophilic nanoparticles by phase inversion method for
zation of poly(ether sulfone)/fluorinated silica organic– application in advanced wastewater treatment. J Appl Res
inorganic composite membrane for sulfur dioxide desulfur- Water Wastewater 5:232–235
ization. High Perform Polym 31:72–85. https://doi.org/10. [67] Cheng J, Shi W, Zhang L, Zhang R (2017) A novel polyester
1177/0954008317752072 composite nanofiltration membrane formed by interfacial
[58] Alkindy MB, Naddeo V, Banat F, Hasan SW (2020) Syn- polymerization of pentaerythritol (PE) and trimesoyl chlo-
thesis of polyethersulfone (PES)/GO-SiO2 mixed matrix ride (TMC). Appl Surf Sci 416:152–159. https://doi.org/10.
membranes for oily wastewater treatment. Water Sci Technol 1016/j.apsusc.2017.04.173
81:1354–1364. https://doi.org/10.2166/wst.2019.347 [68] Vatanpour V, Dehqan A, Harifi-Mood AR (2020) Ethaline
[59] Giwa A, Hasan SW (2020) Novel polyethersulfone-func- deep eutectic solvent as a hydrophilic additive in modifica-
tionalized graphene oxide (PES-fGO) mixed matrix mem- tion of polyethersulfone membrane for antifouling and sep-
branes for wastewater treatment. Sep Purif Technol aration improvement. J Memb Sci 614:118528. https://doi.
241:116735. https://doi.org/10.1016/j.seppur.2020.116735 org/10.1016/j.memsci.2020.118528
[60] Makhetha TA, Moutloali RM (2018) Antifouling properties
of Cu (tpa)@GO/PES composite membranes and selective Publisher’s Note Springer Nature remains neutral with
dye rejection. J Memb Sci 554:195–210. https://doi.org/10. regard to jurisdictional claims in published maps and
1016/j.memsci.2018.03.003 institutional affiliations.
[61] Zhu Z, Wang L, Xu Y et al (2017) Preparation and charac-
teristics of graphene oxide-blending PVDF nanohybrid Springer Nature or its licensor holds exclusive rights to this
membranes and their applications for hazardous dye article under a publishing agreement with the author(s) or
adsorption and rejection. J Colloid Interface Sci other rightsholder(s); author self-archiving of the accepted
504:429–439. https://doi.org/10.1016/j.jcis.2017.05.068 manuscript version of this article is solely governed by the
[62] Ambarita AC, Mulyati S, Arahman N et al (2021) terms of such publishing agreement and applicable law.
Improvement of properties and performances of