Journal of Environmental Chemical Engineering 10 (2022) 107454

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Journal of Environmental Chemical Engineering

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

High-performance thin-film composite forward osmosis membranes with

hydrophilic PDA@TiO2 nanocomposite substrate for the treatment of oily
wastewater under PRO mode
Parashuram Kallem a, b, *, Ravi P. Pandey a, b, Hanaa M. Hegab a, b, Ruchi Gaur c,
Shadi W. Hasan a, b, Fawzi Banat a, b, *
a
Center for Membranes and Advanced Water Technology (CMAT), Khalifa University of Science and Technology, PO Box 127788, Abu Dhabi, United Arab Emirates
b
Department of Chemical Engineering, Khalifa University of Science and Technology, PO Box 127788, Abu Dhabi, United Arab Emirates
c
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 Karnataka, India

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

Editor: Dr. Zhang Xiwang The applications of thin-film composite (TFC) forward osmosis (FO) membranes are limited by low flux and
strong internal concentration polarization (ICP). In this study, a simple, facile, and eco-friendly approach to
Keywords: improve the wettability of the FO membrane substrate using hydroxyl- and amino-functionalized TiO2 nano­
Functionalized TiO2 composites by polydopamine (PDA) coating on TiO2 particles is demonstrated. In our research, a composite
Eco-friendly approach
membrane substrate was fabricated by incorporating PDA@TiO2 into polyethersulfone (PES) through the non-
Forward osmosis
solvent induced phase separation (NIPS) process. Then, a selective active polyamide layer was formed by
High flux
Anti-fouling interfacial polymerization on top of the PES-PDA@TiO2 membrane substrate to obtain the resulting TFC-FO
Oily wastewater membrane. The composite membrane substrate exhibited higher hydrophilicity (about 25% lower contact
angle) and higher porosity than the pristine membrane substrate. The water flux (Jw) of 34.3 L/m2h and 60.1 L/
m2h was achieved for the resulting TFC-PDA@TiO2 FO membrane under FO and pressure retarded osmosis (PRO)
modes which was ~174% and ~183% higher than that of the pristine TFC-FO membrane under FO and PRO
modes respectively. Furthermore, the TFC-PDA@TiO2 membrane exhibited enhanced selectivity, as expressed by
the decrease in the specific salt flux (Js/JW) values (from 0.48 g/L and 0.53 g/L of pristine TFC to 0.27 g/L and
0.28 g/L for TFC-PDA@TiO2 under the FO and PRO modes respectively). More importantly, the TFC-PDA@TiO2
membrane exhibited better fouling behavior with the organic foulant solution. These results demonstrate that the
fabricated TFC-FO membranes have significant potential for sustainable water reclamation from oily wastewater
via FO under the PRO mode.

1. Introduction
Rapid industrial developments in the oil and gas sector have gener­
ated large volumes of oily wastewater worldwide. Oily wastewater
pollution adversely affects groundwater and drinking water resources
threatening aquatic life and human health, and thus is a problem to be
addressed and remedied through a recycling process [1]. Generally, oily
wastewater exists in free droplets, dispersed and emulsified organ­
ic/inorganic materials, and immersed particulates [2]. The discharge of
such oily wastewater into uncontaminated water sources without prior
treatment has become a considerable global concern. Demand for fresh
and clean water has led to the development of sustainable processes for
wastewater treatment. However, remedying oily wastewater pollution
using conventional approaches, such as absorbent materials, flotation,
gravity separation, centrifugation, and coagulation, is inefficient and
generates secondary pollution [3]. Therefore, it is essential to develop
proficient, effective, and low-cost techniques for oil/water separation
[4].
Forward osmosis (FO) is an osmotically-driven membrane separation
process that has received intensive attention for treating emulsified oily
wastewater due to its low energy input, ease of function, low operating
costs, high rejection rate, and high water recovery [5–7]. Several studies

* Corresponding authors at: Center for Membranes and Advanced Water Technology (CMAT), Khalifa University of Science and Technology, PO Box 127788, Abu
Dhabi, United Arab Emirates.
E-mail addresses: parashuram.kallem@ku.ac.ae (P. Kallem), fawzi.banat@ku.ac.ae (F. Banat).

https://doi.org/10.1016/j.jece.2022.107454
Received 28 December 2021; Received in revised form 10 February 2022; Accepted 21 February 2022
Available online 22 February 2022
2213-3437/© 2022 Elsevier Ltd. All rights reserved.
P. Kallem et al.
on FO have been conducted on polyamide (PA)-based thin film com­
posite (TFC) membranes due to their higher water permeability, selec­
tivity, and good mechanical strength [8,9]. Recently, alternative
membrane fabrication approaches have been utilized to further improve
the separation performance of TFC membranes [10–12]. A number of
commonly used membrane substrates made of polymers, such as poly­
vinylidene fluoride (PVDF), polyacrylonitrile (PAN), polybenzimidazole
(PBI) polysulfone (PSf), and polyethersulfone (PES), have been deployed
[13–17]. PES possesses excellent chemical strength, thermal stability,
and superior mechanical properties. However, PES is not sufficiently
hydrophilic thereby limiting its FO treatments [18]. Further, the
incorporation of nanoparticles into typical polymeric membrane mate­
rials, known as nanocomposite membranes, has been presented as a way
to develop high-performance membranes [19]. Incorporating hydro­
philic nanomaterials into the substrate layer of FO membranes helps
improve hydrophilicity, separation performance, and fouling-resistant
properties. Various types of inorganic nanomaterials, such as carbon
nanotubes (CNTs), TiO2, SiO2, graphene oxide (GO), and zeolite, have
been introduced to functionalize TFC membranes [20–23]. Among these
various nanomaterials TiO2 nanoparticles have been seen to have
particular advantages due to their low cost, high chemical stability,
non-toxicity, and photocatalytic activity [24,25]. Studies demonstrate
the feasibility of improving the FO performance through the incorpo­
ration of TiO2 particles into the substrate of the FO membrane [26,27].
Despite this, the benefits of improving membrane hydrophilicity and
fouling resistance have been limited [8,28]. There is a considerable
desire to functionalize TiO2 with hydrophilic groups to improve hy­
drophilicity and dispersibility so that TiO2 can prove its significant
positive effects [29].
Dopamine (DA) is a mussel-inspired biomolecule consisting of
abundant functional groups such as imine, amine, and catechols. It can
undergo self-polymerization on material surfaces in mild alkaline
media, producing a thin film of polydopamine (PDA). PDA has been
widely used to improve the surface charge, permeability, and anti-
fouling properties in various membranes [4,30]. Combining the prop­
erties of TiO2 and PDA, such as hydrophilicity and negative surface
charge, would in a result in a hybrid material that would enhance the
permeability and fouling resistance of the FO membrane substrates. This
study then, describes the use of environmentally friendly PDA-coated
TiO2 composites (PDA@TiO2) as nanocomposites for the fabrication of
highly permeable and fouling-resistant FO membrane substrates for the
treatment of oily wastewater.
2. Materials and methods
2.1. Materials
Polyethersulfone (PES pellets, Mw: 58 kDa) was purchased from
Good Fellow Co., UK. Polyvinylpyrrolidone (PVP, Mw: 40 kDa), N-
methyl-2-pyrrolidone (NMP; 99%), dopamine hydrochloride (DH; 99%),
Trizma®hydrochloride (THCl;>99.0%), and titanium oxide (TiO2;
99.8%) were supplied from Sigma-Aldrich. Soy vegetable oil (commer­
cial grade) was purchased from a local supermarket. Sodium alginate,
calcium sulfate (CaSO4; 98%), 1,3-phenylenediamine (MPD; >99.0%)
and acyl chloride monomer i.e. 1,3,5-benzene-tricarbonyl trichloride
(TMC; >98.0%) were obtained from Sigma-Aldrich. Deionized water
(DI) (resistivity = 15 Mcm at 25 ◦ C), acquired from a Milli-Q Plus 185
purification system (Millipore Corp., USA), was consistently used
throughout the experimental process,
2.2. Synthesis of PDA-coated TiO2
TiO2 nanocomposites coated with PDA (named PDA@TiO2) were
prepared as described in our previous publication [4]. The 5:1 ratio of
fresh TiO2 and dopamine was mixed in the 20 mL Tris-HCl solution
adjusted to pH 8.5. The dispersed solution was stirred for 12 h at
2
Journal of Environmental Chemical Engineering 10 (2022) 107454
constant room temperature. The color of the dispersed solution changed
to dark brown indicating the formation of PDA@TiO2 composites.
PDA@TiO2 composites were washed thrice with DI water and kept in a
drying oven at 80 ◦ C for 12 h. A schematic representation of the syn­
thesis protocol is given in Fig. 1a.
2.3. Fabrication of PES-PDA@TiO2 nanocomposite substrates
The nonsolvent-induced phase separation (NIPS) method was used to
fabricate a pristine and composite PES FO membrane. The casting so­
lution was prepared by sonication of PDA@TiO2 nanocomposite parti­
cles in NMP for 1 h to minimize the agglomeration of particles on the
membrane surface. The PVP and PES were added simultaneously to the
casting solution for 24 h under a vigorous stirring protocol. The homo­
geneous casting solution was left for 2 h to remove air bubbles from the
solution. The prepared solution was then uniformly cast on a non-woven
supported glass plate using a casting knife. The plate was then immersed
in an aqueous coagulation bath at room temperature for phase separa­
tion (Fig. 1b). After the membrane solidified on a glass plate, it was
moved to an additional coagulation bath to wash and remove the
possible residual NMP. Finally, the membrane substrates were immersed
and stored in DI water until required. Three substrates for the FO
membrane, namely, PES, PES-TiO2, and PES-PDA@TiO2, were prepared
according to the compositions shown in Table S1.
2.4. Preparation of the TFC-FO membrane
For the preparation of thin TFC membranes, the polyamide (PA)
selective skin layer was deposited on the surface of the substrates via
interfacial polymerization (IP) [7]. As illustrated in Fig. 1c, the first 2%
(w/v) MPD in a 100 mL DI solution was introduced on the surface of the
membrane substrates and allowed for 10 min to ensure complete
dispersion of the MPD solution within the pore. The residual MPD so­
lution was drained from the membrane substrate surface using a rubber
roller. The acyl halide solution (0.1% (w/v) TMC in 100-mL hexane) was
cast on the substrate surface with a contact time of 2 min to react with
the MPD. To remove the excessive acyl halide solution, the substrate
surface was rinsed and washed with pure n-hexane. Subsequently, the
substrate surface was dried in an oven at 60 ◦ C for 8 min. The resulting
TFC-FO membrane was kept in DI water for further characterization.
The resulting TFC membranes obtained from the substrates PES, PES-­
TiO2 and PES-PDA@TiO2 were named TFC, TFC-TiO2 and TFC-PDA@­
TiO2 respectively.
2.5. Membrane characterization
Bruker ALPHA-Platinum ATR FTIR was used to detect the functional
groups present in the pristine TiO2 structure and functionalized
PDA@TiO2 nanocomposite in the range of 400–4000 cm− 1. The crys­
tallinity and size of the samples were measured at 2θ range of 10◦ − 80◦
via X-ray diffraction (XRD) PANalytical Empyrean at 0.01◦ step size.
Morphology studies were established by FEG QUANTA 250 scanning
electron microscopy (SEM). Thermal analysis was carried out in a
temperature range of 30–600 ◦ C at a rate of 10 ◦ C/minute by using TGA
4000, Perkin Elmer. FEI Tecnai 20 was used to study the transmission
electron microscopy (TEM) analysis at 200 kV. The water contact angle
(θ) of each membrane substrate was measured using the Krüss GmbH’
Drop Shape Analyzer (DSA) at room temperature 25 ◦ C. The zeta po­
tential (ζ) values of the membrane substrates were obtained using with
Anton Paar SurPASS Electrokinetic Analyzer. The porosity (ε) of the
membrane substrate was calculated by the gravimetric method. First,
the weight of the dried porous substrate was estimated and then the
membrane was soaked in DI water. After removing the substrate from
the DI water, the surface was wiped with tissue paper. Finally, the
weight of the wet membrane surface was measured and which had
increased due to the penetration of water between the pores. The bulk
P. Kallem et al. Journal of Environmental Chemical Engineering 10 (2022) 107454

Fig. 1. Schematic illustration of (a) synthesis of PDA@TiO2 (b) fabrication of PES-PDA@TiO2 substrates and (c) preparation of TFC-FO membrane.

porosity was calculated using Eq. 1 [31]: applied pressure (bar) respectively.
The solute rejection (R) and salt permeability coefficient B (L/m2h)
ε (%) = (w₁ − w₂)
(1) of the membranes were acquired in the presence of 100 mM NaCl feed
Aρ∂ × 100
solution by Eqs. (3) and (4):
( )
where w1 and w2 represent the weights of the wet and dry membrane Cp
substrates respectively in g. A, ρ, and ∂ denote the area of the substrate R(%) = 1 − x100 (3)
Cf
surface (cm2), water density (g/cm3), and thickness of the membrane
( )
(cm) respectively. 1
B = A(ΔP − Δπ ) − 1 (4)
R

2.6. Membrane performance evaluation
Intrinsic separation properties, i.e., water permeability coefficient
(A, L/m2h bar), salt permeability coefficient (B, L/m2h), and salt
rejection (R) were measured using a lab-scale cross-flow reverse osmosis
(RO) unit, as described in our previous work [32]. The pure water
permeability coefficient (A) was evaluated at 3 bars and calculated using
Eq. 2:
ΔV
A =
Am Δt ΔP
where ΔV, Am, Δt, and ΔP are the volume of obtained permeate (L),
effective area of the membrane (m2), a specific duration of time (h), and
where Cp, Cf, and Δπ denote the concentrations of permeate (g/L), feed
solution (g/L), and the change in osmotic pressure across the membrane
(bar) respectively.
The osmotic performance of the TFC membranes was performed
using a lab-scale FO system with an effective membrane area of 36 cm2
at room temperature using 1 M NaCl as the draw solution (DS) and DI
water as the feed solution (FS) [32]. FO measurements were evaluated in
FO (AL faces the FS) and PRO (AL faces the DS) modes at 1 M NaCl as DS
and DI water as FS. The impact of different concentrations of draw so­
(2) lution (0.5–2.0 M of aqueous NaCl) on the membrane surface was also
investigated. The water flux, Jw (L/m2h), was calculated by Eq. (5):

3
P. Kallem et al. Journal of Environmental Chemical Engineering 10 (2022) 107454

Fig. 2. (a) FT IR spectra and (b) Raman spectra of TiO2 and PDA@TiO2. (c-d) SEM microimages of TiO2 and PDA@TiO2. TEM micrographs of (e) TiO2 and
(f) PDA@TiO2.

4
P. Kallem et al.
ΔV
Jw = (5)
Δt × Am
where ΔV, Δt, and Am are volume changes (L), specific duration of
time (h), and the effective membrane area (m2). The reverse salt flux, Js
(g/m2h), was determined using Eq. (6):
Js =
VtCt − VoCo
(6)
Δt × Am
where Ct and Co are the initial and final concentrations (g/L), while
Vt and Vo are the initial and final volumes (L) of the feed solution.
The fouling behavior of the TFC-FO membrane was determined by
SA polysaccharide as a model foulant agent in AL-DS mode. The con­
centration of the SA solution was 200 mg/L with 1 mM calcium cation.
SA emulsion and NaCl were used in the fouling studies as feed and draw
solutions [33]. After stabilizing the permeate water flux, the fouling
investigation was conducted continuously for 6 h and the normalized
water flux was measured based on the decline in the water flux.
Furthermore, the flux recovery capability of the membrane was evalu­
ated using 1 M NaCl salt as DS and DI water as FS after a simple physical
washing. Oil/water separation experiments were performed to assess
the applicability of pristine TFC and TFC-PDA@TiO2 FO membranes
under the PRO mode. In this part of the experiment 500 mg/L of
oil-water (O/W) or 0.1 g of sodium dodecyl sulfate (SDS)
surfactant-added oil-water (S/O/W) mixed solutions were used as FS
and 1.0 M NaCl as DS [34]. Oil/water separation experiments were
performed for 7 h and the normalized water flux was measured based on
the flux decline.
3. Results and discussion
3.1. Characterization of TiO2 and PDA@TiO2
The chemical structure of the TiO2 and PDA@TiO2 nanocomposite
was examined using FT-IR spectra, as shown in Fig. 2a. Compared to
Fig. 3. SEM micrographs of fabricated pristine PES and nanocomposite PES membrane substrates.
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Journal of Environmental Chemical Engineering 10 (2022) 107454
unmodified TiO2, the FTIR spectrum of the PDA@TiO2 nanocomposite
showed additional high-intensity peaks at 1290 cm− 1, 1670 cm− 1, and
1482 cm− 1 which corresponds to the aromatic ring of dopamine [35].
The characteristic peak at 3300 and 3210 cm− 1 is attributed to -NH and
-OH vibrations suggesting a successful PDA coating on the TiO2 surface.
Furthermore, strong peaks at 1183 cm− 1and 1070 cm− 1 were distinctly
noticeable representing C–O–C stretching and C–O–H stretching vibra­
tions. This confirms the formation of the PDA@TiO2 nanocomposite
through chemical reactions between the PDA and TiO2 surfaces. In
addition, the Raman spectra of TiO2 and the PDA@TiO2 nanocomposite
(depicted in Fig. 2b) displayed four common characteristic peaks be­
tween 133 and 600 cm− 1 in both pristine TiO2 and PDA@TiO2 nano­
composite confirming the distinctive TiO2 phase. A broad peak at
1580 cm− 1 in the PDA@TiO2 nanocomposite indicated the coating of
the PDA on the TiO2 [24].
The surface morphological structures of the pristine TiO2 and
PDA@TiO2 nanocomposite are shown in Fig. 2c-d at a magnification of
5 µm. The SEM micrographs of TiO2 and PDA@TiO2 nanocomposites
indicate uniform and compact spherical particles. The structures of the
pristine TiO2 and PDA@TiO2 nanocomposite were further evaluated by
HR-TEM micrographs (Fig. 2e-f). It can be seen from Fig. 2e that the TiO2
particles were unevenly distributed and agglomerated strongly in the
matrix while the PDA@TiO2 nanocomposites (Fig. 2f) showed good
dispersion. This could be due to the PDA coating on the TiO2 surface
acting as a surfactant and providing reactive sites for the secondary
organic reaction [35,36].
3.2. Characterization of FO membrane substrates and TFC membranes
The surface morphologies of the membrane substrates are shown in
Fig. 3. In the bottom-surface images, the membrane substrate showed a
good distribution of pores, while top-surface images revealed a smooth
surface without visible pores. Compared to the pristine PES membrane
substrate some particle aggregates were embedded on the surface of the
P. Kallem et al.
PES-TiO2 and PES-PDA@TiO2 membrane substrates. Furthermore, the
EDS spectrum (Fig. S1) supports the presence of C, O, S, and Ti elements
in the PES-TiO2 membrane substrate, whereas the N element was also
observed in the PES-PDA@TiO2 membrane substrate.
The porosity was influenced by the incorporation of nanoparticles
into the membrane substrate (Fig. S2). The bulk porosity of the pristine
PES, PES-TiO2, and PES-PDA@TiO2 membrane substrate was found to be
~72, ~75, and ~78%, respectively. The increased porosity in the
composite membrane substrates is due to the immediate exchange of the
solvent and non-solvent formed by nanoparticles during the NIPS
process.
Wettability is a key factor affecting the fouling resistance of the
membranes. The contact angle (dynamic and static) of the FO membrane
supports is shown in Fig. 4a. Throughout the 80 s, the contact angle for
the pristine PES membrane substrate decreased with the addition of
TiO2 and PDA@TiO2 particles indicating that the hydrophilicity of the
membrane substrate is improved. Among all membrane substrates PES
with PDA@TiO2 had the best hydrophilicity due to the well-dispersed
hydroxyl- and amino-functionalized TiO2 particles in the membrane
substrate and which is anticipated to improve the permeability anti-
fouling performance of the FO membrane. Furthermore, all membrane
substrates exhibited excellent thermal stability, as shown in Fig. 4b, with
a slight enhancement of the thermal stability due to the incorporation of
nanoparticles. For instance, the decomposition temperature Td (defined
at 15% weight loss) improved from 519 ◦ C in the pristine PES membrane
substrate to ~548 and ~534 ◦ C in PES-TiO2 and PES-PDA@TiO2
membrane substrates respectively. The zeta potential values obtained
for the pristine PES, PES-TiO2, and PES-PDA@TiO2 substrates (Fig. 4c)
were − 13, − 24, and − 41 mV at a pH of 7.
Adding PDA@TiO2 resulted in the surface of the membrane substrate
becoming even more negative because of the negative − OH in PDA
moiety. An AFM analysis was carried out to study the effect of PDA@­
TiO2 filler on the PES surface. Changes in the surface roughness pa­
rameters, including average roughness (Ra) and root mean square
roughness (Rq), are presented in Fig. 4d. It can be seen that the surface
roughness of the PES-PDA@TiO2 substrate Ra = 21.4 nm) is greater
than that of pristine PES substrate Ra = 17.0 nm). It is thus established
Fig. 4. The water contact angle (a), TGA (b), Zeta potential (c), and AFM (d) results of the prepared membrane substrates.
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Journal of Environmental Chemical Engineering 10 (2022) 107454
that the membrane substrate with higher surface roughness has a higher
permeability owing to the improved surface area. The surface SEM
morphology of the prepared TFC membranes was also examined and
presented here in Fig. 5. Defect-free films with typical ridge-and-valley
surface structures were observed for all TFC FO membranes.
3.3. Membrane separation properties
The important properties of the FO membrane separation properties,
including water permeability (A) and salt permeability (B), are tabu­
lated in Table 1. The TFC-PDA@TiO2 membrane showed higher water
permeability with good salt rejection compared to the pristine TFC and
TFC-TiO2 membranes. The B/A ratio is a direct indicator of membrane
selectivity. A minimal B/A ratio is usually preferred to lower reverse
diffusion of the solute [17]. In this study, the B/A value of the
TFC-PDA@TiO2 membrane was less than that of the pristine TFC
membrane.
3.4. FO performance of TFC membranes
The FO performance of fabricated TFC membranes is assessed in
terms of water flux (Jw), reverse solute flux (Js), and specific solute flux
(Js/Jw). Fig. 6a shows the Jw in both the FO (AL-FS) and PRO (AL-DS)
modes at 1 M NaCl as DS and DI water as FS. The results showed that the
composite TFC-TiO2 and TFC-PDA@TiO2 FO membranes exhibited
higher Jw compared to the control TFC membrane. In the FO mode, the
TFC-PDA@TiO2 FO membrane displayed the maximum Jw of ~34 L/
m2h corresponding to a ~174% enhancement compared to the TFC-FO
membrane. A similar trend was noticed in the PRO mode, but with a
high water flux and a reverse solute flux generated. To illustrate, the
TFC-PDA@TiO2 membrane tested in the PRO mode showed around
~60 L/m2h water flux and 9 g/m2h reverse solute flux corresponding to
a ~75 and ~79% improvement over Jw and Js achieved in the FO mode
respectively. The membrane substrates were also investigated for their
pure water flux using an ultrafiltration unit with the results presented in
Fig. S3. Additionally, the pure water flux of membrane substrates with
increasing PDA@TiO2 content is shown in Fig. S4. The improved Jw
P. Kallem et al. Journal of Environmental Chemical Engineering 10 (2022) 107454

Fig. 5. Surface images of prepared TFC-FO membranes.

Table 1
Separation properties of the membranes.
Membrane Water permeability, A (L/m2h bar) Salt rejection, R (%) Salt permeability, B (L/m2h) B/A (bar)

TFC 1.62 95.2 1.11 0.68

TFC-TiO2 2.21 93.1 1.22 0.55
TFC-PDA@TiO2 3.19 91.1 1.23 0.38

70 18 (b) (c) FO
FO (a) FO
0.6
PRO PRO PRO
60
15
0.5
50
12
0.4
Js (g/m2h)

40

Js/Jw (g/L)
Jw (L/m2h)

9
0.3
30
6
0.2
20

3 0.1
10

0 0 0.0
TFC TFC-TiO2 TFC-PDA@TiO2 TFC TFC-TiO2 TFC-PDA@TiO2
TFC TFC-TiO2 TFC-PDA@TiO2

Fig. 6. FO performance of the fabricated TFC, TFC-TiO2, and TFC-PDA@TiO2 membranes under FO and PRO mode (DS: 1 M NaCl and FS: DI water).

performance can be attributed to the following two reasons: firstly, the
presence of hydrophilic groups such as hydroxyl and amino functional
groups on the surface of PDA@TiO2, which improved hydrophilicity and
porosity, thus increasing water flux [30]; secondly, the incorporation of
PDA@TiO2 particles increases the roughness of the membrane substrate
layer (Fig. 4d) contributing to higher surface area and improved water
flux. The increase in water flux was consistent with the enhanced A
value. When comparing RO performance (Table 1) and FO performance,
Js in FO (Fig. 6b) is well correlated with NaCl rejection in RO where a
high removal rate corresponds to low Js and vice versa. The specific
solute flux (Js/Jw ratio), an important factor for the selectivity of FO
membranes for both FO and PRO modes, is shown in Fig. 6c. In general,
a highly selective FO membrane should possess a low Js/Jw ratio value.
As observed, the improvement in selectivity indicated by the decrease in
the Js/Jw values (from 0.48 g/L of pristine TFC to 0.26 g/L for the
TFC-PDA @TiO2 FO) of the FO membrane by the incorporation of
PDA@TiO2 is due to the smaller B/A ratio of the TFC-PDA @TiO2 FO
membrane. Taking into account the A, B, B/A values and the Js/Jw ratio
of all TFC membranes from this study, the TFC-PDA@TiO2 FO mem­
brane seems the most promising for FO applications.
Meanwhile, the performance of the FO membrane as a function of the
DS concentration (0.5–2.0 M) was measured under both modes and is
presented in Fig. 7. As shown in Fig. 7a and c, the Jw values rise with the
increasing DS (NaCl) concentration due to the increased osmotic driving
force released by the higher concentration of DS. Furthermore, an
enhancement in the Js and Js/Jw values with DS (NaCl) concentration
was also observed. Usually, the higher the DS concentration, the higher
the salt leakage, and consequently, the greater the external concentra­
tion polarization (ECP) and ICP effect.
3.5. Anti-fouling capacity
Organic anti-fouling tests were performed to evaluate the fouling
capacity of FO membranes. Fig. 8 shows the normalized membrane
water flux (Jw/Jw0) of the TFC, TFC-TiO2, and TFC-PDA@TiO2 mem­
branes in AL-DS mode with respect to the SA model organic foulant. As
observed, the normalized water flux progressively decreased for all TFC
membranes compared to the model foulant as the transport resistance
increased due to the accumulation of SA foulant on the membrane
substrates ultimately hindering the permeation of water through the
membranes [8]. The TFC-PDA@TiO2 membrane effectively repelled
negatively charged SA foulants and demonstrated a lower flux decline at
the end of the fouling study compared to the other two TFC membranes
which can be attributed to the high anti-fouling capacity of the devel­
oped TFC-PDA@TiO2 membrane. The TFC, TFC-TiO2, and TFC-PDA@­
TiO2 membranes reached normalized fluxes of 0.61, 0.67, and 0.72
respectively at the end of the 6 h fouling test. The flux recovery capacity
of the membrane was evaluated after a simple backwash. The pristine
TFC FO membrane showed a recovery of ~86%, and in the case of
TFC-FO membranes with nanocomposite substrates the recovery was
found to be a maximum of ~92 and ~96% for TFC- TiO2 and
TFC-PDA@TiO2 respectively. As mentioned above, the incorporation of
hydrophilic PDA@TiO2 particles provides more hydrophilic properties
and larger pore size in the membrane substrate which leads to better

7
P. Kallem et al. Journal of Environmental Chemical Engineering 10 (2022) 107454

Fig. 7. FO performance of the TFC and TFC-PDA@TiO2 membranes at various concentrations of DS under FO (a-b) and PRO mode (c-d).

water permeability. Furthermore, the formation of a hydration layer on

the TFC membrane substrate due to PDA@TiO2 particles decreased the
adhesion of SA foulants to the surface of the membrane substrate which
would ultimately improve the anti-fouling performance of the mem­
brane. Furthermore, the anti-fouling capability may also be ascribed to
the electrostatic repulsion between -COOH in SA and -OH groups in
PDA@TiO2 composites (see the more significantly negatively charged
membrane substrate in Fig. 4c).

3.6. Application of TFC-PDA@TiO2 membrane for oily wastewater

treatment

To evaluate the potential use of FO for the reclamation of water from

emulsified oil/water solutions, 500 mg/L oil/water (O/W) and 0.1 g of
SDS added to S/O/W mixture solutions were used as FS and 1.0 M NaCl
as DS. Fig. 9a shows the normalized evolutionary behavior of the water
flux of the TFC-PDA@TiO2 membranes under PRO mode during 7 h tests
and compares them to the pristine TFC membrane. A gradual decline in
normalized flux over time was noticed for both solution mixtures. The
TFC membrane exhibited a continuous and severe flux reduction
compared to the TFC-PDA@TiO2 membrane and obtained a normalized
Fig. 8. Anti-fouling behavior of the TFC and TFC-PDA-TiO2 membranes (FS:
flux of 0.32 and 0.4 for the treatment of O/W and S/O/W mixtures
sodium alginate (SA) and CaCl2 with a concentration of 200 mg/L and 1 mM,
respectively. The TFC-PDA@TiO2 membrane had a higher normalized
respectively, DS: 1 M NaCl).
flux of 0.63 and 0.73 for the treatment of O/W and S/O/W mixtures
respectively. As discussed in previous sections, the improved hydro­
philicity, tight hydration layer, and enhanced negative charge of the
TFC-PDA@TiO2 membrane substrate layer plays an important role in
normalized flux (Fig. 9b) [34,37]. Furthermore, the S/O/W emulsion
contains an anionic SDS surfactant and may have a strong electrostatic

8
P. Kallem et al. Journal of Environmental Chemical Engineering 10 (2022) 107454

Fig. 9. (a) Normalized flux of TFC-FO and TFC-PDA@TiO2 FO with O/W and S/O/W mixture solutions over 7 h cycle operation. (b) Schematic representation of the
TFC-PDA@TiO2 FO membrane to anti-fouling mechanisms in the TFC-PDA@TiO2 FO membrane to avoid oil adhesion on the membrane surface. SEM images of the
pristine TFC (c) and TFC-PDA@TiO2 (d) membrane with S/O/W emulsion.

repulsion with a more negatively charged TFC-PDA@TiO2 membrane
substrate [38]. Therefore, the reduction in the flux of the FO membrane
with the S/O/W mixture is less than with the O/W solution. Fouling of
the pristine TFC and TFC-PDA@TiO2 membranes used with the S/O/W
emulsion was further evaluated by SEM (Fig. 9c-d). As can be seen in the
SEM images, in contrast to the TFC-PDA@ TiO2 membrane (Fig. 9d), the
pristine TFC FO membrane (Fig. 9c) was covered by a fouling layer
containing some crystals after filtration of the S/O/W wastewater
demonstrating that both fouling and scaling had formed on the mem­
brane surface [39,40]. These results demonstrate that the prepared
TFC-PDA@TiO2 membrane can be efficiently applicable for sustainable
water reclamation of oily wastewater by FO in the PRO mode.
Table 2 displays a performance comparison between the results of
the present study and other reported works to better indicate fabricated
membrane performance.
4. Conclusions
This work investigated the fabrication of FO TFC-PDA@TiO2 mem­
branes and their anti-fouling behavior in the treatment of oily

Table 2
Comparison of FO membrane performance.
FO membrane Water flux, Jw (L/m2h), FO/PRO Reverse solute flux, Js (g/m2h) Feed solution Draw solution Ref

CTA-NW (commercial) 4.4/8.19 0.6/2.8 10 mM NaCl 0.5 M NaCl [41]

CTA-HW (commercial) 9.03/15.4 5.3/9.4 10 mM NaCl 0.5 M NaCl [41]
CTA-W (commercial) 5.0/6.55 2.9/4.8 10 mM NaCl 0.5 M NaCl [41]
TFC-PES-GO/Ag 20/- 1.45/- DI water 0.7 NaCl [42]
TFC-PSf 8.9/16.1 1.7/4.0 10 mM NaCl 0.5 M NaCl [26]
TFC-PSf/TiO2 17.1/31.2 1.6/4.0 10 mM NaCl 0.5 M NaCl [26]
29.7/56.2 8.1/14.0 10 mM NaCl 2.0 M NaCl
TFC-PSf/f-CNFs 13.8/18.8 3.3/5.0 DI water 1.0 M NaCl [11]
TFC-PES 12.5/21.2 6.1/11.3 DI water 1.0 M NaCl Present work
TFC-PES/TiO2 26.5/47.5 8.8/14.5 DI water 1.0 M NaCl Present work
TFC-PES/ PDA@TiO2 34.3/60.1 9.2/16.5 DI water 1.0 M NaCl Present work

9
P. Kallem et al.
wastewater. A simple, facile, and eco-friendly approach was introduced
to enhance the wettability of the TFC-FO membrane substrate by
incorporating PDA-coated TiO2 particles into the PES membrane sub­
strate. The following are the main findings of this study:
1. The composite FO membrane substrate exhibited more hydrophi­
licity due to the hydroxyl and amino functional groups in the
modified TiO2 nanocomposite resulting in an approximately 25%
lower water contact angle and a higher porosity than the pristine
membrane substrate.
2. The water flux (Jw) of 34.3 L/m2h and 60.1 L/m2h was obtained for
the resulting TFC-PDA@TiO2 FO membrane under FO and PRO
modes, which was ~174% and ~183% higher than that of the
pristine TFC-FO membrane under FO and PRO modes respectively,
due to the synergistic effect of hydrophilic TiO2 and PDA resulting in
the higher hydrophilicity of the hybrid TFC membrane.
3. An improvement in selectivity, as indicated by the decrease in Js/Jw
values (from 0.48 g/L of pristine TFC to 0.26 g/L for the TFC-
PDA@TiO2 FO) of the FO membrane by incorporation of PDA@TiO2,
due to the smaller B/A ratio of the TFC-PDA@TiO2 FO membrane.
4. More importantly, the TFC-PDA@TiO2 membrane exhibited better
fouling resistance (recovery was ~96%) with the organic foulant
solution of the SA model.
5. Considering the A, B, B/A values and Js/Jw ratio of all TFC mem­
branes used in this study, the TFC-PDA@TiO2 FO membrane would
seem the most suitable for FO.
6. At the end of the 7 h test, the TFC and TFC-PDA@TiO2 membranes
achieved normalized fluxes of 0.32 and 0.63 with the O/W, 0.4 and
0.73 with the S/O/W mixtures respectively indicating that the
resulting TFC FO membrane can be efficiently used for sustainable
water recovery from oily wastewater via FO in the PRO mode.
This study, therefore, provides an alternative perspective for the
design of high-performance membranes with low fouling FO to treat oily
wastewater.
CRediT authorship contribution statement
Parashuram Kallem: Conceptualization, Validation, Formal anal­
ysis, Investigation, Data curation, Writing – original draft, Writing –
review & editing, Visualization Ravi P. Pandey: Validation, Data cura­
tion, Writing – review & editing. Hanaa M. Hegab: Validation, Data
curation, Writing – review & editing. Ruchi Gaur: Validation, Data
curation, Writing – review & editing. Shadi W. Hasan: Resources,
Writing – review & editing. Fawzi Banat: Conceptualization, Valida­
tion, Resources, Writing – review & editing, Visualization, Project
administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This research was supported by a grant (Award No. RC2- 2018-009)
from the Center for Membranes and Advanced Water Technology
(CMAT) funded by Khalifa University of Science and Technology in Abu
Dhabi (UAE).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2022.107454.
10
Journal of Environmental Chemical Engineering 10 (2022) 107454
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