3344 © 2021 The Authors Water Supply | 21.

7 | 2021

High flux membrane based on in-situ formation of zirconia

layer coated the polyethersulfone substrate for ions
separation
Chabi Noël Worou, Jing Kang, Eric A. Alamou, Arcadius Degan,
Pengwei Yan, Yingxu Gong, Razack L. Guene and Zhonglin Chen

ABSTRACT

A flawless, extremely loose, membrane, efficient for multivalent ions separation, has been Chabi Noël Worou (corresponding author)
Jing Kang
successfully synthesized by the in-situ formation approach. The as-synthesized nanofiltration (NF) Pengwei Yan
Yingxu Gong
membrane, NF_PES-Zr, proceeded from a thin film layer of nanoparticles (NPs) zirconium that coated Razack L. Guene
Zhonglin Chen
the platform of the polyethersulfone (PES) ultrafiltration (UF) membrane through a bio-glue made State Key Laboratory of Urban Water Resource and
from dopamine hydrochloric and sodium bicarbonate buffer. The estimation of the average pore size Environment, School of Environment,
Harbin Institute of Technology,
of the novel organic-inorganic NF membrane NF_PES-Zr using the filtration velocity approach of Harbin 150090,
China
Guerout-Elford-Ferry was close to 0.9 nm. NF_PES-Zr membrane holds a record in permeate water E-mail: worouccc@yahoo.fr;

1 worouccc@stu.hit.edu.cn
flux release of about 62.5 L:m
2 :h and was revealed to be effective for multivalent ions separation.
A 5 days-test performed on NF_PES-Zr demonstrated its long-term stability and showed a rejection Eric A. Alamou
Laboratory of Geoscience, Environment and
rate of 93.4% and 37.8% respectively for Ca2þ and Naþ . Applications,
National School of Public Works, National
Key words | ions rejection, nanofiltration, nanoparticle, organic-inorganic membrane, University of Sciences, Technologies,
Engineering and Mathematics,
polyethersulfone, zirconium
BP: 2282 Abomey,
Benin

Arcadius Degan
HIGHLIGHTS Laboratory of Mechanics and Energetics applied,
Polytechnic School of Abomey-Calavi,

•
01 BP 2009 Cotonou,
Organic-inorganic membrane preparation. Benin

• Nanoparticle zirconium deposition by in-situ formation method. and

Laboratory of Applied Hydrology,

• Modification of an ultrafiltration membrane to a nanofiltration membrane. Polytechnic School of Abomey-Calavi,

•
01 BP:526 INE/UAC, Cotonou,
Energy dispersive spectrometry (EDS) associated with field emission scanning electron Benin

microscopy (FESEM) for membrane surface structures characterization.

• High flux membrane for ions separation.

This is an Open Access article distributed under the terms of the Creative
Commons Attribution Licence (CC BY-NC-ND 4.0), which permits copying
and redistribution for non-commercial purposes with no derivatives,
provided the original work is properly cited (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

doi: 10.2166/ws.2021.092

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 3345 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
GRAPHICAL ABSTRACT
INTRODUCTION
Nanofiltration (NF) membranes possess properties between
reverse osmosis (RO) and ultrafiltration (UF) with a pore
size close to 1 nm, which corresponds to a molecular
weight cut-off (MWCO) between 300 and 500 Da and can
nowadays reach 300 kDa. Nanofiltration
(NFMs) in contact with aqueous solution are lightly charged
because of the adsorption of charged solute on its surface and
mainly due to surface functional groups dissociation that
occurred (Mohammad et al. ). In the case of polymeric
NFMs, which possess ionizable groups such as sulfonic
acid groups, carboxylic groups, etc., that result in the charged
surface in contact with feed solutions. NFMs exhibited high
performance in the rejection of inorganic salts even of
small molecular organics in the same way as RO membranes
(Worou et al. a, b; Zhu et al. ). Distinguishing fea-
tures of NFMs are best performance rejection towards
multivalent ions, higher flux permeation in comparison
with RO membranes, and low monovalent ions removal
(Elcik et al. ; Lv et al. ; Nicomel et al. ). These tre-
mendous properties have promoted NFMs to be used in
niche applications in several areas particularly in drinking
water production, wastewater treatment, food engineering,
biotechnology, and pharmaceutical (Donnan ; Moham-
mad et al. ; Siddique et al. ).
The NF process is reported to be extremely complex and
dependent on both interfacial and micro-hydrodynamic
events that occur at its surface, even within its nanopores.
Donnan, steric, transport, and dielectric effects combined
determine the NF membranes removal performance
(Worou et al. a, b). The famous Donnan effect
makes clear not only the equilibria but also the potential
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interactions between the membrane surface and the charged
species inside the feed solution (Worou et al. a, b).
Neutral solutes transport is performed via the steric mechan-
ism, which is a size-based exclusion, and was already well
membranes settled through various studies on ultrafiltration (UF) mem-
branes (Deen ). NF membranes’ charge originates from
their surface functional groups that ionize and also from
the structure of their pores (Hagmeyer & Gimbel ;
Ernst et al. ). These functional groups could be basic in
nature, acidic, or indeed both, depending on the nanoparti-
cles (NPs) materials utilized during the preparation
process. It was demonstrated that the pH of the solution
strongly influenced the dissociation of such surface groups,
since the membrane, at a specific pH value, may display an
isoelectric point (Childress & Elimelech ). In addition,
Afonso et al., have established that Nanofiltration mem-
branes show a weak ion-exchange ability, and even
on some occasions, ions from feed solution can adsorb to
the NFM surface generating a modification of membrane
charge (Afonso et al. ). The fixed membrane charge
and ion valence in solution in contact with membrane deter-
mine the electrostatic attraction or repulsion force that
appears on the localized ionic surroundings as a direct con-
sequence of the aforementioned dielectric phenomena. The
dielectric exclusion phenomena are not well understood
yet since there are two competing hypotheses that try
obscurely to explain the exact nature of interaction that
takes place. The first hypothesis is called the ‘image forces’
phenomenon (Yaroshchuk ; Nicomel et al. ) while
the second is called the ‘solvation energy barrier’ mechanism
(Bowen & Welfoot ). These two exclusion phenomena
 3346 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
were investigated in detail (Oatley et al. ), and it was
shown that they are a fruit of both nano-length scales and
extreme spatial confinement that occur during NFMs separ-
ations mechanism. It was also reported that solutes moving
freely in feed solution were disrupted by dragging forces
exerted by the solvent passing by the confined pores’ struc-
ture. The transport of this solute across the nanopores
structure is highly affected by the local environment and is
credibly considered as hindered. Since it’s understood that
the dimensions of the NFMs layers are close to atomic
length scale, the limitations in available measurement tech-
nologies, the knowledge of NFMs surface properties and
structural characterization has been delayed and resulted in
a significant debate (Schafer ), and the dielectric exclu-
sion phenomenon is especially contested (Wong et al. ).
Currently, there are satisfactory results available to con-
clude the existence of a porous active film in most NFMs. To
achieve the characterization of these pores, four main
methodologies are used, (i) the gas adsorption/desorption
method or Brunauer-Emmett-Teller (BET)
(Wang et al. ; Fang et al. ), (ii) indirect measurement
of pore size that consists of the use of neutral solute removal
investigation and models (Oatley et al. ; García-Martín
et al. ), (iii) reverse surface impregnation (RSI) com-
bined with transmission electron microscopy (TEM)
(Mohammad et al. ), and (iv) atomic force microscopy
(AFM) for direct measurement of pore size, surface rough-
ness, topography, etc. (Misdan et al. ).
Zirconium dioxide (ZrO2 ) was adopted as the inorganic
selective layer because it has been widely used for high-perform-
ance filtration membranes as an inorganic component with
superior physical, chemical, and thermal stability and
good hydrophilicity (Lv et al. ; Worou et al. a,
b). The thin ZrO2 -layer was then obtained from the
controlled hydrolysis process of zirconium sulfate tetra-
hydrate (Zr (SO4 )2 ) under equilibrium reactions (Equations
(1)–(3)) developed later. In this article, AFM associated
with scanning electron microscopy (SEM) and energy disper-
sive spectrometry (EDS) were used to characterize the as-
synthesized membrane structure after the growth of zirconia
(ZrO2 ) on polyethersulfone (PES) ultrafiltration platform by
the in-situ formation approach. Water contact angles (WCA)
and zeta potential were also measured with the aim of deter-
mining the novel membrane properties.
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EXPERIMENTAL SESSION
Materials and agents
Polyethersulfone (PES) ultrafiltration (UF) membrane
(MWCO ¼ 100 kDa; L ¼ 1 m; l ¼ 1 m) was a commercial
product of Shanghai Corun Membrane Technology Co. Ltd
(China); PES represented the substrate. Various salts includ-
ing CaCl2 and NaCl were supplied by Aladdin (China) for
membrane separation tests. Deionized (DI) water, dopamine
hydrochloride (98%, (HO)2C6H3CH2 CH2NH2.HCl), and
sodium bicarbonate buffer (pH 8.0, NaHCO3) solution were
purchased from Aladdin (China) for substrate preparation
and to conduct interfacial polymerization. Zirconium sulfate
tetrahydrate (Zr (SO4)2.4(H2O)), hydrochloric acid solution
(12 mol/L), butanol, and sodium hydroxide (NaOH) were
all obtained from Sino Pharm Chemical Reagent Co.
technique The fabrication process for the novel membrane
NF_PES-Zr
Small pieces of about 2,922 mm2 of polyethersulfone ultrafil-
tration membrane were introduced in sodium hydroxide
solution (2.0 mol/L) for 2 h at 50  C. A fresh solution was
prepared for deposition by dissolving 4 g of dopamine
hydrochloride in 1 L of sodium bicarbonate buffer solution
(pH ¼ 8.0, 40 mmol/L). The deposition time was set at 2 h.
Both dopamine and sodium bicarbonate buffer acted like
‘bio-glue’ to prepare the top surface of PES. The resulting
membrane pieces were pre-wetted in butanol for 25 min
and then immersed into the fresh solution (‘bio-glue’) and
stirred at 25  C for 2 h. The resulting membranes at this
last step were called G-PES. Dopamine/sodium bicarbonate
buffer coated PES was G-PES. The as-synthesized mussel-
inspired platform (G-PES or dopamine HCl/sodium bicar-
bonate buffer coated PES) was washed in deionized (DI)
water several times and dried in the ambient environment.
1 g of zirconium sulfate tetrahydrate (Zr (SO4)2.4(H2O))
was dissolved in 250 mL of hydrochloric solution
(40 mmol/L). Then, pieces of G-PES were introduced into
the solution for 2 days at room temperature of 25  C. The
resulting membrane was called NF_PES-Zr. This organic-
inorganic membrane was washed in DI water several
 3347 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

times and dried in an oven for 5 h to evaluate its perform- respectively.

ance. The reactions and steps for the fabrication process

Cp
for the novel membrane NF_PES-Zr are shown in R¼ 1
× 100 % (5)
Cf
Equations (1)–(3) and Figure 1.
where Cp and Cf are respectively the solute concentrations in
Hydrolysis process of zirconium sulfate tetrahydrate to permeate and feed sides, which were measured by a conduc-
zirconia (ZrO2 ) tivity meter (Metrohm AG) and inductively coupled plasma
optical emission spectroscopy (ICP-OES, Optima 7300 DV,
2[Zr (SO4 )2 ] þ 3H2 O ! [Zr2 (OH)3 (SO4 )4 ]3
þ 3Hþ (1)
PerkinElmer).
[Zr2 (OH)3 (SO4 )4 ]3
þ 3OH
The next equation was used to evaluate the overall por-
osity (ε) (Xu et al. ; Worou et al. a, b):
! Zr2 (OH)6 SO4 þ 3SO2

4 (2) !
Ww
Wd
ε(%) ¼ × 100 (6)
Zr2 (OH)6 SO4 þ 2OH
! 2Zr O2 þ SO2

4 4H2 O (3) ρf Vm

where Ww , Wd , are the weight and dry weight of the mem-

Performance of the novel synthesized membrane
NF_PES-Zr
The membrane performance of NF_PES-Zr was evaluated by
using a laboratory scale cross-flow flat membrane module
under 6 bars at 25  C. The effective area was 2,922 mm2 for
each sample. Two different salts CaCl2 and NaCl have been dis-
solved in DI water with a concentration of 1,000 mg/L and
used as feed solutions with a fixed cross-flow rate of 30 L/h.
The water flux (Lw , L:m
2 h
1 ) and rejection (R, %) were
calculated by the following equations, Equations (4) and (5):
Q The measuring was performed at least five times and the
Fw ¼
A:t
where Q, A, and t represent the volume of permeated water, the
effective membrane area, and the permeation time,
brane (g), ρf is water density (g=cm3 ) and Vm is membrane
small size volume in cm3 .
For the estimation of pore size, the filtration velocity
approach was used, and for that the Guerout-Elford-Ferry
equation have been used (Wan Ikhsan et al. ; Worou et al.
a, b):

1
(2:9
1:75ε)8ηIQ 2
rm ¼ (7)
εAΔP
where η is water viscosity (8.9×10
4 Pa:s), Q is permeate flux
(m3 :s
1 ), ΔP is operating pressure 6 bars, I is membrane thick-
ness (m), and A is the surface area of the membrane sample (m2 ).
(4)
average was chosen. The NF_PES-Zr membrane was also
continuously tested on the cross-flow flat membrane
module for 5 days with a report of salt removal rate and
water flux every 12 h.

Figure 1 | Deposition of zirconium nanoparticles on a layer of polydopamine/sodium bicarbonate buffer.

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 3348 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
MEMBRANE CHARACTERIZATION
Surface properties characterization
Water contact angle (WCA)
Water contact angle measurements have been done with a
Drop Meter A-200 contact angle system purchased from
MAIST Vision Inspection & Measurement Co. Ltd, China.
Measurements have been performed on PES, G-PES, and
NF_PES-Zr membranes. These membranes were immersed
in ethanol for 25 min and dried in an oven before the con-
tact angles were measured Figure 5(a)).
Zeta potential
An electrokinetic analyzer, purchased from SurPASS Anton
Paar, GmbH, Austria, was used to evaluate the charging
property of each membrane’s surface. Three (03) samples
had their zeta potential measured, PES, G-PES, and
NF_PES-Zr membranes, as made explicit in Figure 5(b).
Figure 2 | AFM associated with FESEM and EDS to characterize the surface structure of the NF_PES-Zr membrane.
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Stability test in various solvents
An immersion test has been performed on NF_PES-Zr to
determine its long-stability in solvents for a five-day test at
room temperature. Water flux and rejection were measured
at each 12 h. Membranes withdrawn after this period were
carefully rinsed with deionized (DI) water and dried in
atmospheric conditions. The results are reported in
Figure 7(b).
Surface structures characterization
Figure 2 shows the diagram of the main tools used in this study to
characterize the surface structure of the NF_PES-Zr membrane.
Field emission scanning electron microscopy (FESEM), with a
ZEISS Sigma 500 purchased from Pittsburgh, PA, USA, has
been used in this study to analyze the surface morphology
of the synthesized organic-inorganic membrane NF_PES-Zr.
Atomic force microscopy (AFM), Multi-Mode Vecco,
from Denton, TX, USA, has been very useful for the novel
organic-inorganic NF_PES-Zr membrane morphology and
roughness measurement.
 3349 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
An energy dispersive spectrometer (EDS) was combined
in this study with field emission scanning electron
microscopy for more insights on the membrane surface
elements’ charge, their arrangement, and especially about
the phase state of the zirconium film. The three elements
especially observed on the membrane’s surface were zirco-
nium (Zr), carbon (C), and oxygen (O).
Figure 3 | (a) Field emission scanning electron microscopy (FESEM) of NF_PES-Zr (b)
atomic force microscopy (AFM) of NF_PES-Zr, (c) energy dispersive spec-
trometry of NF_PES-Zr membrane, (d) carbon (C), (e) zirconium (Zr), and (f)
oxygen energy spectrum.
Figure 4 | Energy spectrum analysis results of novel organic-inorganic NF_PES-Zr membrane.
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RESULTS AND DISCUSSION
Surface structures of novel synthesized NF_PES-Zr
membrane
Figure 3(a) shows the surface morphology observed through
FESEM of the novel organic-inorganic membrane NF_PES-
Zr and its roughness is immediately depicted in Figure 3(b).
Figure 3(b) confirms what has been observed in Figure 4(a),
especially since the maximum roughness is evaluated at
8.02 nm. This membrane is very smooth, and this is under-
standable, given that NF_PES-Zr stayed for two days in a
solution of zirconium sulfate tetrahydrate (Zr (SO4)2.4
(H2O)). The dopamine hydrochloric and sodium bicarbon-
ate buffer solutions mixture plays its role of bio-glue well
since it promotes the deposition of the upper layer of zirco-
nium nanoparticles. The hydrolysis process of zirconium
sulfate tetrahydrate to the zirconium dioxide (ZrO2) is
explained by Equations (1)–(3).
An energy-dispersive spectrometer (EDS) has been com-
bined with scanning electron microscopy (SEM) to gain
accurate insights into the arrangement and eventual func-
tion of nanoparticles (NPs) ZrO2. NF_PES-Zr samples
 3350 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
have been tested and the results are reported as graphs in
Figures 4 and 3(c)–3(f). EDS’ measures focused on three
(03) elements, carbon (C) in Figure 3(d), oxygen (O) in
Figure 3(f), and zirconium (Zr) in Figure 3(e) due to their
unique X-ray emissions. Thus, each atomic position has
been located by its unambiguous chemical signal. The emis-
sion light of each atom of C, O, and Zr was distinct from
their neighbors due to their high contrast. With this infor-
mation, it is henceforth possible to characterize and
modify the materials at the atomic scale. The chemical
elements carbon (C), oxygen (O), and zirconium (Zr) were
well arranged on the NF_PES-Zr membrane surface,
Figure 3(d)–3(f), respectively. This view was once again sus-
tained by the SEM image in Figure 3(a).
The chemical structure of the NF_PES-Zr membrane sur-
face was then investigated by FT-IR/ATR. Figure 5 shows that
Figure 5 | FT-IR/ATR of NF_PES-Zr membrane.
Figure 6 | Water contact angle (a) zeta potential at various pH (b) of PES, G-PES, and NF_PES-Zr membranes.
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the novel synthesized organic-inorganic nanofiltration mem-
brane has characteristic peaks at around 2,200, 1,100, and
900 cm
1 in the FT-IR/ATR spectrum, which are assigned
to the O-H, C-C (double covalent bond), and Zr-O stretching
vibrations in the pyrocatechol groups. Furthermore, this
analysis revealed that zirconia (ZrO2 ) exists in two distinct
geometric forms: (i) monoclinic zirconia (m) and (ii) tetra-
gonal zirconia (t). The sharpest peaks reaching 1700 are
attributable to the solid double covalent bond of carbon
atoms. The softest peaks are characteristic of the single
covalent bond between the oxygen atom and the hydrogen
atom, which must undergo deprotonation.
Surface properties of NF_PES-Zr membrane
Each of the above-mentioned tools provided useful infor-
mation on membrane surface structures. Nevertheless,
because of the length-scales involved and the different
imperfections that may be associated with each technique,
it is recommended to use a combination of tools. Another
key variable recommended for a better NFMs process
understanding is the characterization of the membrane sur-
face properties. For that purpose, the water contact angle
(WCA), depending on the nature of the contact solution
and zeta potential (which is affected by pH and concen-
tration), were evaluated.
Figure 6(a) depicts the evaluation of the wettability of
PES, G-PES, and NF_PES-Zr membranes, with a
 3351 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
DropMeter A-200 contact angle system purchased from
MAIST Vision Inspection & Measurement Co. Ltd, China.
The PES membrane displayed the best hydrophilicity due
to its ether groups combining with the porous structure.
Mohammad et al. demonstrated that PES exhibits good
hydrophilicity due to its molecular structure, which facili-
tates hydrogen bonding with water molecules. Therefore, a
higher volume of permeate could be attained using PES
membrane (Mohammad et al. ). The same trend has
been earlier observed by two of the world’s leading manufac-
turers of filter solutions such as polyethersulfone (PES),
GVS Group and Pall, which described PES as ‘an inherently
hydrophilic membrane that wets out quickly and completely
resulting in fast filtration with superior flow rates and high
throughputs’.
The water contact angles of both G-PES and NF_PES-Zr
were quite similar from 80 s. The WCA increased with the
deposition of zirconium nanoparticles (NPs). The as-syn-
thesized NF_PES-Zr membrane is the least hydrophilic of
the three membranes tested. The novel organic-inorganic
membrane NF_PES-Zr exhibits excellent hydrophilicity
(30–70 ) and could be fast spread out by the water, which
is required for a good performance for NF membranes.
A pseudo-measurement of the Donnan potential was
then used to investigate the membrane surface zeta potential
(ζ) and the results are shown in Figure 6(b) (Cheng et al. ;
Déon et al. ; Bauman et al. ). The state of PES, G-PES,
Figure 7 | (a) Calculated average pore size of PES, G-PES, and NF_PES-Zr membranes, (b) overall porosity of PES, G-PES, and NF_PES-Zr membranes.
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and NF_PES-Zr membranes’ surface charge was measured in
the pH range 3–10. G-PES membrane (dopamine hydro-
chloric/sodium bicarbonate buffer coated PES) exhibited a
negatively charged surface in contact with a basic solution
(pH > 6), because of the deprotonation of its pyrocatechol
groups (C6 H4 (OH)2 ! C6 H4 (O
)2 ) on its top layer surface.
NF_PES-Zr membrane surface is less negatively charged
than G-PES membrane surface since the NPs zirconium in
solution generates positive ions Zr4þ . The three membranes
possessed a negative charge above pH 9.5. The negative
ions could be easily and efficiently removed for pH > 9.5
according to the Donnan effect.
Performance evaluation of NF_PES-Zr
The average pore size evaluated with Equations (7) is now
expressed in graphs for more understanding. Figure 7(a)
shows the evolution of pore size with the deposition of the
different layers of ‘bio-glue’ for G-PES membrane and NPs
zirconium layer with the novel organic-inorganic thin-film
composite NF_PES-Zr membrane. The pore size decreases
with the formation of layers on the PES platform. The
pore size of NF_PES-Zr is around 0.9 nm, which is in tune
with the NFMs’ class. The porosity of PES, G-PES, and
NF_PES-Zr are respectively 68.5, 64, and 53% (Figure 7(b)).
This variation in porosity is understandable, the nano-
particles, because of their very small size (the order of a
 3352 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
Figure 8 | (a) Water flux through PES, G-PES, and NF_PES-Zr membranes; (b) long-term stability test on NF_PES-Zr membrane.
nanometer), succeeded in filling the voids of the platform
without changing its volume. It was also reported early in
this study that the PES membrane exhibited the most excel-
lent hydrophilicity due to its porous structure Figure 6(a).
Moreover, it is well known that NPs, especially if they are
hydrophilic, tend to migrate and stay on the membrane
top layer surface, leading to a reduction of the pore size
(Daneshvar et al. ).
Nanofiltration membranes (NFMs)
applied to separate and remove ions with different valences
from drinking water production and wastewater treatment.
The water flux of PES, G-PES, and NF_PES-Zr membranes
are respectively 87, 85.7, and 62.5 L:m
2 :h
1 (Figure 8(a)).
The water flux from the PES membrane to the G-PES mem-
brane decreases very slightly while the PES platform was
coated by ‘bio-glue’ dopamine hydrochloric/sodium bicar-
bonate buffer solutions. Both membranes are very loose.
From G-PES membrane to NF_PES-Zr membrane the
water flux decreases dramatically because of the change
that occurs in the membrane nature from UF membrane
to NF membrane at the time of in-situ formation of the
zirconium layer.
The novel NF_PES-Zr membrane exhibits excellent Ca2þ
rejection of about 94%. But this membrane is not competent
to remove monovalent ions such as Naþ (Figure 8(b)). A five-
day test has been performed on the NF_PES-Zr membrane to
verify its performance stability (Figure 8(b)). NF_PES-Zr
membrane, during 120 h, was tested continuously and both
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rejection and water flux were reported each 12 h. The rejec-
tion decreased very slightly during the 120 h of the long test
and stabilized around 93.4%. The water flux also was
almost constant throughout the five-day test.
Figure 9 depicts a comparative rejection of divalent
cation Ca2þ of PES, G-PES, and NF_PES-Zr. The rejection
performance of the three membranes was respectively
about 26, 32, and 94%. This result is hardly surprising
are nowadays since only the NF membranes have proven their compe-
tence in effectively rejecting multivalent ions. On the other
hand, PES and G-PES membranes are extremely porous
with flow rates reaching 87 L:m
2 :h
1 . The flow rate of
the NF_PES-Zr membrane is reduced due to the deposition
on its surface of a layer of fine elements, known under the
name of nanoparticles (NPs), contributing to reducing the
size of the pores in the active layer of the membrane.
Thus, the water flux of NF_PES-Zr decreases dramatically
to stabilize around 62.5 L:m
2 :h
1 .
Table 1 is about the water flux and rejection performance
of some earlier synthesized membranes and of this study.
CONCLUSION
A new membrane was fabricated, and in comparison with
other membranes manufactured before it using the same
platform (Vatanpour et al. ; Vatanpour et al. ) and
the same coating layer (Lv et al. ), was found to be
 3353 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

Figure 9 | Long-term stability test on PES, G-PES, and NF_PES-Zr membranes. Test conditions: 0.6 MPa; cross-flow rate ¼ 30 L/h; pH ¼ 6.0. [Ca2þ ] ¼ 1,500 mg/L.

Table 1 | Synthesized membranes water flux and rejection performance in this study and some earlier reported ones

1
Membrane Water flux (L:m
2 :h ) Rejection (%) References

PES/ZrO2 62.5 93.4 This study

HPAN/ ZrO2 60 >90 Lv et al. ()
Modified membrane (0.5-Ach) 30 95 Bagheripour et al. ()
PES/TiO2-co-MWCNTs 5.6 75.8 Vatanpour et al. ()
PES/TiO2 4.2 81.9 Vatanpour et al. ()
PES/functionalized MWCNTs 24 80 Vatanpour et al. ()
PES/Graphene Oxide 20.4 96 Zinadini et al. ()
Graphene oxide polyamide 42 90 Zhang et al. ()
Carboxyl-functionalized graphene oxide polyamide 49 90 Zhang et al. ()
TFC nanofiltration/functionalized chitosan 22.9 90.8 Miao et al. ()
NF_PAN_Ti 56 89.3 Worou et al. (a)
NF-PANZr 58 99.3 Worou et al. (b)

extremely loose (Table 1). A flawless and efficient multi-
valent ions separation membrane has been successfully
synthesized by the in-situ formation approach. The as-
synthesized nanofiltration (NF) membrane, NF_PES-Zr,
proceeded from a thin film layer of nanoparticles (NPs)
zirconium coating the platform of polyethersulfone (PES)
ultrafiltration (UF) membrane through a bio-glue made
from dopamine hydrochloric and sodium bicarbonate
buffer. The estimation of the average pore size of the novel
organic-inorganic NF membrane NF_PES-Zr using the
filtration velocity approach of Guerout-Elford-Ferry was
close to 0.9 nm. NF_PES-Zr membrane holds a record in

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by guest
 3354 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal
permeate water flux release of about 62.5 L:m
2 :h
1 and
was revealed to be effective for multivalent
separation. A five-day test performed on NF_PES-Zr demon-
strated its long-term stability and showed a rejection rate of
93.4% and 37.8% respectively for Ca2þ and Naþ : We hope
that this simple technique to implement will inspire the
fabrication of a new generation of membranes.
ACKNOWLEDGEMENTS
The authors would like to thank our group members for
their kind help and suggestions.
CONFLICT OF INTEREST
The authors declare no competing financial interest
DATA AVAILABILITY STATEMENT
All relevant data are included in the paper or its Supplemen-
tary Information.
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