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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:m2 :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 Water Supply | 21.7 | 2021

GRAPHICAL ABSTRACT

INTRODUCTION

Nanofiltration (NF) membranes possess properties between interactions between the membrane surface and the charged
reverse osmosis (RO) and ultrafiltration (UF) with a pore species inside the feed solution (Worou et al. a, b).
size close to 1 nm, which corresponds to a molecular Neutral solutes transport is performed via the steric mechan-
weight cut-off (MWCO) between 300 and 500 Da and can ism, which is a size-based exclusion, and was already well
nowadays reach 300 kDa. Nanofiltration membranes settled through various studies on ultrafiltration (UF) mem-
(NFMs) in contact with aqueous solution are lightly charged branes (Deen ). NF membranes’ charge originates from
because of the adsorption of charged solute on its surface and their surface functional groups that ionize and also from
mainly due to surface functional groups dissociation that the structure of their pores (Hagmeyer & Gimbel ;
occurred (Mohammad et al. ). In the case of polymeric Ernst et al. ). These functional groups could be basic in
NFMs, which possess ionizable groups such as sulfonic nature, acidic, or indeed both, depending on the nanoparti-
acid groups, carboxylic groups, etc., that result in the charged cles (NPs) materials utilized during the preparation
surface in contact with feed solutions. NFMs exhibited high process. It was demonstrated that the pH of the solution
performance in the rejection of inorganic salts even of strongly influenced the dissociation of such surface groups,
small molecular organics in the same way as RO membranes since the membrane, at a specific pH value, may display an
(Worou et al. a, b; Zhu et al. ). Distinguishing fea- isoelectric point (Childress & Elimelech ). In addition,
tures of NFMs are best performance rejection towards Afonso et al., have established that Nanofiltration mem-
multivalent ions, higher flux permeation in comparison branes show a weak ion-exchange ability, and even
with RO membranes, and low monovalent ions removal on some occasions, ions from feed solution can adsorb to
(Elcik et al. ; Lv et al. ; Nicomel et al. ). These tre- the NFM surface generating a modification of membrane
mendous properties have promoted NFMs to be used in charge (Afonso et al. ). The fixed membrane charge
niche applications in several areas particularly in drinking and ion valence in solution in contact with membrane deter-
water production, wastewater treatment, food engineering, mine the electrostatic attraction or repulsion force that
biotechnology, and pharmaceutical (Donnan ; Moham- appears on the localized ionic surroundings as a direct con-
mad et al. ; Siddique et al. ). sequence of the aforementioned dielectric phenomena. The
The NF process is reported to be extremely complex and dielectric exclusion phenomena are not well understood
dependent on both interfacial and micro-hydrodynamic yet since there are two competing hypotheses that try
events that occur at its surface, even within its nanopores. obscurely to explain the exact nature of interaction that
Donnan, steric, transport, and dielectric effects combined takes place. The first hypothesis is called the ‘image forces’
determine the NF membranes removal performance phenomenon (Yaroshchuk ; Nicomel et al. ) while
(Worou et al. a, b). The famous Donnan effect the second is called the ‘solvation energy barrier’ mechanism
makes clear not only the equilibria but also the potential (Bowen & Welfoot ). These two exclusion phenomena

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3346 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

were investigated in detail (Oatley et al. ), and it was EXPERIMENTAL SESSION
shown that they are a fruit of both nano-length scales and
extreme spatial confinement that occur during NFMs separ- Materials and agents
ations mechanism. It was also reported that solutes moving
freely in feed solution were disrupted by dragging forces Polyethersulfone (PES) ultrafiltration (UF) membrane
exerted by the solvent passing by the confined pores’ struc- (MWCO ¼ 100 kDa; L ¼ 1 m; l ¼ 1 m) was a commercial
ture. The transport of this solute across the nanopores product of Shanghai Corun Membrane Technology Co. Ltd
structure is highly affected by the local environment and is (China); PES represented the substrate. Various salts includ-
credibly considered as hindered. Since it’s understood that ing CaCl2 and NaCl were supplied by Aladdin (China) for
the dimensions of the NFMs layers are close to atomic membrane separation tests. Deionized (DI) water, dopamine
length scale, the limitations in available measurement tech- hydrochloride (98%, (HO)2C6H3CH2 CH2NH2.HCl), and
nologies, the knowledge of NFMs surface properties and sodium bicarbonate buffer (pH 8.0, NaHCO3) solution were
structural characterization has been delayed and resulted in purchased from Aladdin (China) for substrate preparation
a significant debate (Schafer ), and the dielectric exclu- and to conduct interfacial polymerization. Zirconium sulfate
sion phenomenon is especially contested (Wong et al. ). tetrahydrate (Zr (SO4)2.4(H2O)), hydrochloric acid solution
Currently, there are satisfactory results available to con- (12 mol/L), butanol, and sodium hydroxide (NaOH) were
clude the existence of a porous active film in most NFMs. To all obtained from Sino Pharm Chemical Reagent Co.
achieve the characterization of these pores, four main
methodologies are used, (i) the gas adsorption/desorption
method or Brunauer-Emmett-Teller (BET) technique The fabrication process for the novel membrane
(Wang et al. ; Fang et al. ), (ii) indirect measurement NF_PES-Zr
of pore size that consists of the use of neutral solute removal
investigation and models (Oatley et al. ; García-Martín Small pieces of about 2,922 mm2 of polyethersulfone ultrafil-
et al. ), (iii) reverse surface impregnation (RSI) com- tration membrane were introduced in sodium hydroxide
bined with transmission electron microscopy (TEM) solution (2.0 mol/L) for 2 h at 50  C. A fresh solution was
(Mohammad et al. ), and (iv) atomic force microscopy prepared for deposition by dissolving 4 g of dopamine
(AFM) for direct measurement of pore size, surface rough- hydrochloride in 1 L of sodium bicarbonate buffer solution
ness, topography, etc. (Misdan et al. ). (pH ¼ 8.0, 40 mmol/L). The deposition time was set at 2 h.
Zirconium dioxide (ZrO2 ) was adopted as the inorganic Both dopamine and sodium bicarbonate buffer acted like
selective layer because it has been widely used for high-perform- ‘bio-glue’ to prepare the top surface of PES. The resulting
ance filtration membranes as an inorganic component with membrane pieces were pre-wetted in butanol for 25 min
superior physical, chemical, and thermal stability and and then immersed into the fresh solution (‘bio-glue’) and
good hydrophilicity (Lv et al. ; Worou et al. a, stirred at 25  C for 2 h. The resulting membranes at this
b). The thin ZrO2 -layer was then obtained from the last step were called G-PES. Dopamine/sodium bicarbonate
controlled hydrolysis process of zirconium sulfate tetra- buffer coated PES was G-PES. The as-synthesized mussel-
hydrate (Zr (SO4 )2 ) under equilibrium reactions (Equations inspired platform (G-PES or dopamine HCl/sodium bicar-
(1)–(3)) developed later. In this article, AFM associated bonate buffer coated PES) was washed in deionized (DI)
with scanning electron microscopy (SEM) and energy disper- water several times and dried in the ambient environment.
sive spectrometry (EDS) were used to characterize the as- 1 g of zirconium sulfate tetrahydrate (Zr (SO4)2.4(H2O))
synthesized membrane structure after the growth of zirconia was dissolved in 250 mL of hydrochloric solution
(ZrO2 ) on polyethersulfone (PES) ultrafiltration platform by (40 mmol/L). Then, pieces of G-PES were introduced into
the in-situ formation approach. Water contact angles (WCA) the solution for 2 days at room temperature of 25  C. The
and zeta potential were also measured with the aim of deter- resulting membrane was called NF_PES-Zr. This organic-
mining the novel membrane properties. inorganic membrane was washed in DI water several

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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 brane (g), ρf is water density (g=cm3 ) and Vm is membrane
NF_PES-Zr small size volume in cm3 .
For the estimation of pore size, the filtration velocity
The membrane performance of NF_PES-Zr was evaluated by approach was used, and for that the Guerout-Elford-Ferry
using a laboratory scale cross-flow flat membrane module equation have been used (Wan Ikhsan et al. ; Worou et al.
under 6 bars at 25  C. The effective area was 2,922 mm2 for a, b):
each sample. Two different salts CaCl2 and NaCl have been dis-  1
(2:9  1:75ε)8ηIQ 2
solved in DI water with a concentration of 1,000 mg/L and rm ¼ (7)
εAΔP
used as feed solutions with a fixed cross-flow rate of 30 L/h.
The water flux (Lw , L:m2 h1 ) and rejection (R, %) were where η is water viscosity (8.9×104 Pa:s), Q is permeate flux
calculated by the following equations, Equations (4) and (5): (m3 :s1 ), ΔP is operating pressure 6 bars, I is membrane thick-
ness (m), and A is the surface area of the membrane sample (m2 ).
Q The measuring was performed at least five times and the
Fw ¼ (4)
A:t average was chosen. The NF_PES-Zr membrane was also
continuously tested on the cross-flow flat membrane
where Q, A, and t represent the volume of permeated water, the module for 5 days with a report of salt removal rate and
effective membrane area, and the permeation time, 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 Water Supply | 21.7 | 2021

MEMBRANE CHARACTERIZATION Stability test in various solvents

Surface properties characterization An immersion test has been performed on NF_PES-Zr to


determine its long-stability in solvents for a five-day test at
Water contact angle (WCA) room temperature. Water flux and rejection were measured
at each 12 h. Membranes withdrawn after this period were
Water contact angle measurements have been done with a carefully rinsed with deionized (DI) water and dried in
Drop Meter A-200 contact angle system purchased from atmospheric conditions. The results are reported in
MAIST Vision Inspection & Measurement Co. Ltd, China. Figure 7(b).
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- Surface structures characterization
tact angles were measured Figure 5(a)).
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
Zeta potential ZEISS Sigma 500 purchased from Pittsburgh, PA, USA, has
been used in this study to analyze the surface morphology
An electrokinetic analyzer, purchased from SurPASS Anton of the synthesized organic-inorganic membrane NF_PES-Zr.
Paar, GmbH, Austria, was used to evaluate the charging Atomic force microscopy (AFM), Multi-Mode Vecco,
property of each membrane’s surface. Three (03) samples from Denton, TX, USA, has been very useful for the novel
had their zeta potential measured, PES, G-PES, and organic-inorganic NF_PES-Zr membrane morphology and
NF_PES-Zr membranes, as made explicit in Figure 5(b). roughness measurement.

Figure 2 | AFM associated with FESEM and EDS to characterize the surface structure of the NF_PES-Zr membrane.

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3349 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

An energy dispersive spectrometer (EDS) was combined RESULTS AND DISCUSSION


in this study with field emission scanning electron
microscopy for more insights on the membrane surface Surface structures of novel synthesized NF_PES-Zr
elements’ charge, their arrangement, and especially about membrane
the phase state of the zirconium film. The three elements
especially observed on the membrane’s surface were zirco- Figure 3(a) shows the surface morphology observed through
nium (Zr), carbon (C), and oxygen (O). 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-
Figure 3 | (a) Field emission scanning electron microscopy (FESEM) of NF_PES-Zr (b) bined with scanning electron microscopy (SEM) to gain
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) accurate insights into the arrangement and eventual func-
oxygen energy spectrum. tion of nanoparticles (NPs) ZrO2. NF_PES-Zr samples

Figure 4 | Energy spectrum analysis results of novel organic-inorganic NF_PES-Zr membrane.

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3350 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

have been tested and the results are reported as graphs in the novel synthesized organic-inorganic nanofiltration mem-
Figures 4 and 3(c)–3(f). EDS’ measures focused on three brane has characteristic peaks at around 2,200, 1,100, and
(03) elements, carbon (C) in Figure 3(d), oxygen (O) in 900 cm1 in the FT-IR/ATR spectrum, which are assigned
Figure 3(f), and zirconium (Zr) in Figure 3(e) due to their to the O-H, C-C (double covalent bond), and Zr-O stretching
unique X-ray emissions. Thus, each atomic position has vibrations in the pyrocatechol groups. Furthermore, this
been located by its unambiguous chemical signal. The emis- analysis revealed that zirconia (ZrO2 ) exists in two distinct
sion light of each atom of C, O, and Zr was distinct from geometric forms: (i) monoclinic zirconia (m) and (ii) tetra-
their neighbors due to their high contrast. With this infor- gonal zirconia (t). The sharpest peaks reaching 1700 are
mation, it is henceforth possible to characterize and attributable to the solid double covalent bond of carbon
modify the materials at the atomic scale. The chemical atoms. The softest peaks are characteristic of the single
elements carbon (C), oxygen (O), and zirconium (Zr) were covalent bond between the oxygen atom and the hydrogen
well arranged on the NF_PES-Zr membrane surface, atom, which must undergo deprotonation.
Figure 3(d)–3(f), respectively. This view was once again sus-
tained by the SEM image in Figure 3(a). Surface properties of NF_PES-Zr membrane
The chemical structure of the NF_PES-Zr membrane sur-
face was then investigated by FT-IR/ATR. Figure 5 shows that 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
Figure 5 | FT-IR/ATR of NF_PES-Zr membrane. PES, G-PES, and NF_PES-Zr membranes, with a

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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3351 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

DropMeter A-200 contact angle system purchased from and NF_PES-Zr membranes’ surface charge was measured in
MAIST Vision Inspection & Measurement Co. Ltd, China. the pH range 3–10. G-PES membrane (dopamine hydro-
The PES membrane displayed the best hydrophilicity due chloric/sodium bicarbonate buffer coated PES) exhibited a
to its ether groups combining with the porous structure. negatively charged surface in contact with a basic solution
Mohammad et al. demonstrated that PES exhibits good (pH > 6), because of the deprotonation of its pyrocatechol
hydrophilicity due to its molecular structure, which facili- groups (C6 H4 (OH)2 ! C6 H4 (O)2 ) on its top layer surface.
tates hydrogen bonding with water molecules. Therefore, a NF_PES-Zr membrane surface is less negatively charged
higher volume of permeate could be attained using PES than G-PES membrane surface since the NPs zirconium in
membrane (Mohammad et al. ). The same trend has solution generates positive ions Zr4þ . The three membranes
been earlier observed by two of the world’s leading manufac- possessed a negative charge above pH 9.5. The negative
turers of filter solutions such as polyethersulfone (PES), ions could be easily and efficiently removed for pH > 9.5
GVS Group and Pall, which described PES as ‘an inherently according to the Donnan effect.
hydrophilic membrane that wets out quickly and completely
resulting in fast filtration with superior flow rates and high Performance evaluation of NF_PES-Zr
throughputs’.
The water contact angles of both G-PES and NF_PES-Zr The average pore size evaluated with Equations (7) is now
were quite similar from 80 s. The WCA increased with the expressed in graphs for more understanding. Figure 7(a)
deposition of zirconium nanoparticles (NPs). The as-syn- shows the evolution of pore size with the deposition of the
thesized NF_PES-Zr membrane is the least hydrophilic of different layers of ‘bio-glue’ for G-PES membrane and NPs
the three membranes tested. The novel organic-inorganic zirconium layer with the novel organic-inorganic thin-film
membrane NF_PES-Zr exhibits excellent hydrophilicity composite NF_PES-Zr membrane. The pore size decreases
(30–70 ) and could be fast spread out by the water, which with the formation of layers on the PES platform. The
is required for a good performance for NF membranes. pore size of NF_PES-Zr is around 0.9 nm, which is in tune
A pseudo-measurement of the Donnan potential was with the NFMs’ class. The porosity of PES, G-PES, and
then used to investigate the membrane surface zeta potential NF_PES-Zr are respectively 68.5, 64, and 53% (Figure 7(b)).
(ζ) and the results are shown in Figure 6(b) (Cheng et al. ; This variation in porosity is understandable, the nano-
Déon et al. ; Bauman et al. ). The state of PES, G-PES, particles, because of their very small size (the order of a

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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3352 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

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 rejection and water flux were reported each 12 h. The rejec-
without changing its volume. It was also reported early in tion decreased very slightly during the 120 h of the long test
this study that the PES membrane exhibited the most excel- and stabilized around 93.4%. The water flux also was
lent hydrophilicity due to its porous structure Figure 6(a). almost constant throughout the five-day test.
Moreover, it is well known that NPs, especially if they are Figure 9 depicts a comparative rejection of divalent
hydrophilic, tend to migrate and stay on the membrane cation Ca2þ of PES, G-PES, and NF_PES-Zr. The rejection
top layer surface, leading to a reduction of the pore size performance of the three membranes was respectively
(Daneshvar et al. ). about 26, 32, and 94%. This result is hardly surprising
Nanofiltration membranes (NFMs) are nowadays since only the NF membranes have proven their compe-
applied to separate and remove ions with different valences tence in effectively rejecting multivalent ions. On the other
from drinking water production and wastewater treatment. hand, PES and G-PES membranes are extremely porous
The water flux of PES, G-PES, and NF_PES-Zr membranes with flow rates reaching 87 L:m2 :h1 . The flow rate of
are respectively 87, 85.7, and 62.5 L:m2 :h1 (Figure 8(a)). the NF_PES-Zr membrane is reduced due to the deposition
The water flux from the PES membrane to the G-PES mem- on its surface of a layer of fine elements, known under the
brane decreases very slightly while the PES platform was name of nanoparticles (NPs), contributing to reducing the
coated by ‘bio-glue’ dopamine hydrochloric/sodium bicar- size of the pores in the active layer of the membrane.
bonate buffer solutions. Both membranes are very loose. Thus, the water flux of NF_PES-Zr decreases dramatically
From G-PES membrane to NF_PES-Zr membrane the to stabilize around 62.5 L:m2 :h1 .
water flux decreases dramatically because of the change Table 1 is about the water flux and rejection performance
that occurs in the membrane nature from UF membrane of some earlier synthesized membranes and of this study.
to NF membrane at the time of in-situ formation of the
zirconium layer.
The novel NF_PES-Zr membrane exhibits excellent Ca2þ CONCLUSION
rejection of about 94%. But this membrane is not competent
to remove monovalent ions such as Naþ (Figure 8(b)). A five- A new membrane was fabricated, and in comparison with
day test has been performed on the NF_PES-Zr membrane to other membranes manufactured before it using the same
verify its performance stability (Figure 8(b)). NF_PES-Zr platform (Vatanpour et al. ; Vatanpour et al. ) and
membrane, during 120 h, was tested continuously and both the same coating layer (Lv et al. ), was found to be

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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:m2 :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- ultrafiltration (UF) membrane through a bio-glue made
valent ions separation membrane has been successfully from dopamine hydrochloric and sodium bicarbonate
synthesized by the in-situ formation approach. The as- buffer. The estimation of the average pore size of the novel
synthesized nanofiltration (NF) membrane, NF_PES-Zr, organic-inorganic NF membrane NF_PES-Zr using the
proceeded from a thin film layer of nanoparticles (NPs) filtration velocity approach of Guerout-Elford-Ferry was
zirconium coating the platform of polyethersulfone (PES) close to 0.9 nm. NF_PES-Zr membrane holds a record in

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3354 C. N. Worou et al. | Novel high flux synthesized membrane for efficient ions removal Water Supply | 21.7 | 2021

permeate water flux release of about 62.5 L:m2 :h1 and Cheng, S., Oatley, D. L., Williams, P. M. & Wright, C. J. 
was revealed to be effective for multivalent ions Positively charged nanofiltration membranes: review of
current fabrication methods and introduction of a
separation. A five-day test performed on NF_PES-Zr demon- novel approach. Advances in Colloid and Interface Science
strated its long-term stability and showed a rejection rate of 164 (1–2), 12–20.
93.4% and 37.8% respectively for Ca2þ and Naþ : We hope Childress, A. E. & Elimelech, M.  Effect of solution chemistry
on the surface charge of polymeric reverse osmosis and
that this simple technique to implement will inspire the
nanofiltration membranes. Journal of Membrane Science
fabrication of a new generation of membranes. 119 (2), 253–268.
Daneshvar, N., Aleboyeh, A. & Khataee, A.  The evaluation of
electrical energy per order (EEo) for photooxidative
decolorization of four textile dye solutions by the kinetic
ACKNOWLEDGEMENTS
model. Chemosphere 59 (6), 761–767.
Deen, W.  Hindered transport of large molecules in liquid-
The authors would like to thank our group members for filled pores. AIChE Journal 33 (9), 1409–1425.
their kind help and suggestions. Déon, S., Fievet, P. & Doubad, C. O.  Tangential streaming
potential/current measurements for the characterization of
composite membranes. Journal of Membrane Science 423,
413–421.
CONFLICT OF INTEREST Donnan, F. G.  Theory of membrane equilibria and membrane
potentials in the presence of non-dialysing electrolytes. A
contribution to physical-chemical physiology. Journal of
The authors declare no competing financial interest Membrane Science 100 (1), 45–55.
Elcik, H., Celik, S. O., Cakmakci, M. & Özkaya, B. 
Performance of nanofiltration and reverse osmosis
DATA AVAILABILITY STATEMENT membranes for arsenic removal from drinking water.
Desalination and Water Treatment 57 (43), 20422–20429.
Ernst, M., Bismarck, A., Springer, J. & Jekel, M.  Zeta-
All relevant data are included in the paper or its Supplemen- potential and rejection rates of a polyethersulfone
tary Information. nanofiltration membrane in single salt solutions. Journal of
Membrane Science 165 (2), 251–259.
Fang, Y., Bian, L., Bi, Q., Li, Q. & Wang, X.  Evaluation of the
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First received 16 November 2020; accepted in revised form 20 March 2021. Available online 30 March 2021

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