Chemical Engineering & Processing: Process Intensification 158 (2020) 108191

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Chemical Engineering and Processing - Process

Intensification
journal homepage: www.elsevier.com/locate/cep

Antifouling and photocatalytic properties of 2-D Zn/Al layered double

hydroxide tailored low-pressure membranes
Yuvaraj Mutharasi a, Noel Jacob Kaleekkal a, *, Thanigaivelan Arumugham b, Fawzi Banat b,
MSR Sridhar Kapavarapu a
a
Membrane Separation Group, Department of Chemical Engineering, National Institute of Technology Calicut (NITC), Kozhikkode, 673601, Kerala, India
b
Department of Chemical Engineering, Khalifa University, 127788, Abu Dhabi, United Arab Emirates

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

Keywords: In this study, Zinc-Aluminium layered double hydroxide (LDH) was synthesized to fabricate membranes with
Zinc-Aluminium layered double hydroxide superior hydrophilic and photocatalytic characteristics. The prepared LDH was extensively characterized and
Mixed matrix membranes employed for the preparation of polyetherimide mixed matrix ultrafiltration (UF) membranes, which displayed >
Thin-film nanocomposite
96 % BSA rejection and a flux recovery ratio of 88 % even after 3-cycles. M-1 (UF, 1 wt. %) displayed a 94 %
Photocatal
degradation of organic dye (methylene blue) in 120 min when irradiated with UV-light. Further, nanofiltration
Ytic activity
Hydrophilicity (NF) membranes were prepared by incorporating Zn/Al LDH into the polyamide (PA) layer during the in-situ
interfacial polymerization to prepare thin-film nanocomposite membranes. MT-2 (NF, 0.4 wt.% LDH in PA
layer) displayed improved hydrophilicity (lower water contact angle), > 94.5 % rejection of cationic dye
(Methylene blue), > 91 % rejection of inorganic salt (CaSO4) with an 80 % flux recovery after long-term
filtration. The LDH holds an auspicious potential to tune the properties of UF and NF membranes to be used
in the treatment of industrial effluents.

1. Introduction high cost of recovery of the nanoparticles used in the adsorption or

In India, groundwater provides 80 % of drinking water and two-
thirds of its irrigation needs. A sharp rise in the number of industries –
textile, petrochemical, food, pharmaceuticals, paper, and pulp, etc.
contributes to contamination of the groundwater resources [1]. Textile
effluents contain organic pollutants, toxic dyes, inorganic compounds,
and heavy metals, which, when discharged to the environment, can
directly harm the ecosystem and diminish the quality of human life [1,
3]. Methylene blue is a cationic dye that is widely used in several ap­
plications (medicinal, dying, etc.) and, when discharged into waste­
water, can pose a significant burden to the environment [2]. Calcium
sulphate used in primary water treatment In addition to these, the
presence of proteins in the effluents can pose a threat if not treated
before discharge [5].
Conventional technologies such as adsorption, coagulation, bio-
mediated process, advanced oxidation processes (photocatalysis) have
been explored for the removal of these contaminants. However, (i)
limited efficiency, (ii) inability to degrade or remove all classes of the
contaminants, (iii) creation of sludge/secondary pollutants, and (iv)
photocatalysis severely limit their largescale application [6]. For the
removal of these contaminants, membrane-based separations are being
widely accepted over other competing technologies due to their attri­
butes such as higher efficiency, ability to be scaled up and integrated
into existing systems, cost-effectiveness, robustness, no/low require­
ment of chemicals, etc. [7]. Highly selective, low-pressure membrane
processes such as ultrafiltration (UF) and nanofiltration (NF) play a vital
role in the recovery and reuse of water to alleviate the current water
stress [8].
Nanomaterials have been widely used in the preparation of ultrafil­
tration membranes, and this class of membranes is referred to as mixed
matrix membranes/nanocomposite membranes. These mixed matrix
membranes are employed for the separation of humic substances, pro­
teins, oil-water emulsion, and other macromolecular substances [9,10].
Recent reports on mixed matrix membranes show that nanomaterials
viz. multi-walled carbon nanotubes [11], graphene oxide [12], percar­
boxylic acid-functionalized SiO2 bound Fe3O4 nanoparticle [13], MIL-53
[14], ZnO [15] have been incorporated into the polymer matrix to
improve the antifouling property, provide adsorption sites, aid in

* Corresponding author.
E-mail addresses: noeljacob89@gmail.com, noel@nitc.ac.in (N.J. Kaleekkal).

https://doi.org/10.1016/j.cep.2020.108191
Received 6 June 2020; Received in revised form 10 September 2020; Accepted 15 October 2020
Available online 19 October 2020
0255-2701/© 2020 Elsevier B.V. All rights reserved.
Y. Mutharasi et al.
catalytic degradation, and improve membrane longevity, etc.
Nanofiltration (NF) membranes possessing smaller pore sizes (0.5
− 2 nm) have also received widespread attention owing to their ability to
remove low molecular weight organic compounds (dyes, etc.) as well as
dissolved divalent/trivalent salts and having a lower energy require­
ment [16]. However, adsorption of dyes can cause potential fouling due
to hydrophobic interactions and electrostatic interactions [17]. New
generation NF membranes are fabricated by an in-situ interfacial poly­
merization forming an ultrathin polyamide (PA) layer on the base
UF/MF membrane. However, producing membranes with superior
water permeability with a high rejection remains a challenging task
[18]. In this case, the introduction of nanomaterials into the PA active
layer is a promising direction of research to prepare thin-film nano­
composite membranes (TFNs) with superior separation ability. The
addition of functional materials possessing a variety of characteristics
can tune the membrane surface property by introducing- hydrophilicity,
antifouling ability, surface charge, surface roughness, antibacterial
property, photocatalytic ability, etc. [19]. Nanomaterials such as CeO2,
TiO2, Ag, GO, CNTs have been explored for their potential to impart
antifouling property to the membrane surface, and these membranes
have been explored for the removal of various contaminants from
aqueous streams [20].
Two-dimensional (2D) nanomaterials obtained popularity with the
application and versatility of graphene/graphene oxide sheets. Some of
the other classes of 2D materials actively being explored are 2D metal-
organic frameworks, MXenes, layered metal carbide/nitride, layered
dichalcogenides, and layered double hydroxides [21]. Layered double
hydroxides are a class of two dimensional (2D) nanomaterials commonly
referred to as hydrotalcite-like compounds with flexibility in composi­
tion, low manufacturing cost, and ease of preparation. These are anionic
layered materials composing of brucite like 2D sheets with alternating
divalent and trivalent cations possessing an exchangeable anion with
water molecules in the interlayer spaces [22]. These LDH have atomic
layer thickness, which (1) the cation layers can be tuned easily, (ii) can
host a variety of anions by intercalation, and (iii) has a distinctive
memory effect [23]. There is an increase in the number of reports of LDH
being employed for the removal of contaminants from aqueous systems:
for adsorption for phosphate recovery from urine [24], removal of tar­
trazine dye from aqueous solutions [25], nanofillers for preparing TFN
membranes [26], antibacterial and photocatalytic microfiltration
membranes [27].
In this study, a layered anionic clay Zinc -Aluminium LDH possessing
dual functionality – hydrophilicity and photocatalytic ability is explored
as nanofillers to tailor the performance of UF and NF polyetherimide
(PEI) membranes. PEI is a hydrophobic polymer having excellent film-
forming properties, possessing high mechanical strength/ chemical
resistance, and is available commercially at competitive prices [28].
Moreover, PEI is a UV resistant polymer which is attributed to the high
dissociation energy of the C– – C (145 Kcal/mol) and C–– O (84 Kcal/mol)
bonds present in the polymer backbone [29].
The Zn/Al LDH possesses − OH groups at its surface, which impart
hydrophilicity, and the positive charge can be traced to the isomorphous
substitution of the divalent cations by the trivalent ones [30]. The
photocatalytic ability of the LDH can be associated with the − OH−
groups of the brucite layer, which combine with the valence band holes
yielding hydroxyl radicals. Moreover, the presence of a suitable anion
(here NO−3 ) in the interlamellar space quenches the rate of charge
recombination as a result of interaction between the photo-generated
charge carrier and the anion [31]. Introducing a photocatalytic nano­
material can not only improve the membrane antifouling ability but also
enhances the catalytic degradation of the adsorbed organic foulants,
improving the lifetime of the membrane. This could impart a
self-cleaning property to the membrane, thereby reducing the time and
solvents needed for backwash and membrane regeneration [32].
The synthesized LDH is characterized extensively by XRD, FTIR,
TGA, SEM, TEM, etc. Mixed matrix membranes (MMMs) were fabricated
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Chemical Engineering and Processing - Process Intensification 158 (2020) 108191
by incorporating LDH into the polyetherimide (PEI) matrix, which, to
the best of our knowledge, has not been reported earlier. The MMMs
were characterized using FTIR, TGA, AFM, SEM, Tensile strength, Water
contact angle, etc. The protein rejection and antifouling ability of the
MMMs were evaluated. Further, the photocatalytic degradation of
methylene blue (MB) dye using the MMMs of the membranes was
explored using a photocatalytic reactor, and the leaching of the LDH
from the membrane matrix was analyzed. Thin-film nanocomposite
membranes (TFNs) were prepared by the incorporation of the same LDH
into the polyamide (PA) layer during the interfacial polymerization
between an amine and an acyl chloride monomer on the PEI base
membrane and have not been investigated earlier. These nanofiltration
membranes were evaluated for pure water permeability, organic solute
rejection (Methylene blue dye rejection), divalent ion removal (Ca+2),
and flux recovery after long-term filtration, etc.
2. Experimental details
2.1. Materials used
Zinc nitrate hexahydrate (reagent grade, 98 %), Aluminium nitrate
nonahydrate (EMPLURA grade), Sodium hydroxide (ACS reagent, ≥97.0
%, pellets), and Sodium nitrate (99.9 % Assay) were purchased from
Merck Life Sciences Ltd for the synthesis of the hydrotalcite-like LDH.
PEI (melt index9 g/10 min (337 ◦ C/6.6 kg)) manufactured by Sigma
Aldrich was used and Solvent N-Methyl Pyrrolidone (A.R. grade) man­
ufactured by Sisco Research laboratory, India were used in the mem­
brane preparation. m-Phenylenediamine (MPD flakes, 99 %) 1,3,5-
Benzenetricarbonyl trichloride (TMC 98 %) from Sigma-Aldrich, USA,
n-Hexane (EMPLURA) from Merck was used for the interfacial poly­
merization reaction to prepare the active PA layer. Methylene Blue
(373.9 g/mol), Bovine Serum Albumin (BSA molecular biology grade),
Calcium Suphate (A.R grade, dried) were procured from Himedia Lab­
oratories, India. Deionized water (R = 18.2 MΩ cm) obtained from a
Milli-Q system was employed throughout this study.
2.2. Synthesis of Zinc-Aluminium layered double hydroxide
A facile one-pot synthesis of Zn(II) and Al (III) layered double hy­
droxide was prepared by co-precipitation followed by aging. Briefly,
aqueous solutions of Al(N03)3.9H2O (Merck, emplura) and Zn
(NO3)2.6H2O (Merck, reagent grade, 98 %) were mixed by the dropwise
addition of one solution into the other using a magnetic stirrer in an inert
(N2) atmosphere. The concentrations of the salts were calculated, such
that the molar ratio of Zn2+/Al3+ was in the ratio 2:1. To this solution,
50 mL of NaNO3 was added, followed by the dropwise addition of 1 M
NaOH. The dropwise addition of NaOH resulted in the precipitation of
the metal oxides at a pH ~10. The slurry was then transferred into a
Teflon lined autoclave and aged at 110 ⁰C for 18 h. The precipitate ob­
tained was filtered, washed with water and acetone and dried in a
vacuum oven for 48 h. The dried sample was ground and stored dry for
further use [33].
2.3. Fabrication of Low-pressure membranes (UF and NF)
2.3.1. Mixed matrix ultrafiltration (UF) membranes (MMMs)
The ultrafiltration membranes were prepared by the phase inversion
technique, in particular, the non-solvent induced phase separation
method (NIPS) using DI water as the non-solvent. The determined
quantity of LDH (Table 1) was dispersed in the solvent, n-methyl pyr­
rolidone (SRL, India) using an ultrasonic batch (40 kHz) for 30 min to
ensure complete dispersion of the nanofiller. To this, the polymer, PEI
(Sigma Aldrich, melt index9 g/10 min) was added and stirred using an
overhead mechanical stirrer for 8 h until a homogenous dope solution
was obtained. The degassed solution was cast onto a clean glass sub­
strate using a thin-film applicator (Elcometer 4340) while maintaining a
Y. Mutharasi et al. Chemical Engineering and Processing - Process Intensification 158 (2020) 108191

Table 1
Composition and Physico-chemical properties of the prepared membranes.
Porosity Mechanical Properties
Membrane Weight % of LDH used in (%) Average surface roughness Viscosity of the Casting Solution
Codes preparation Tensile Strength % Elongation at Ra (nm) (mPa.s)
(MPa) Break

Mixed matrix Ultrafiltration Membranes (16 wt.% Polyetherimide)

M0 0 53.6 ± 3.0 3.55 (±0.01) 6.7 (±2.00) 46 ± 12 862.4
M-1 1 68.4 ± 2.4 3.61 (±0.05) 12.4 (±1.80) 131 ± 29 1024.6
M-2 1.5 62.5 ± 1.8 3.68 (±0.07) 15.8 (±2.15) 86 ± 29 1261.5

Thin-film nanocomposite membranes (16 wt.% Polyetherimide +1 wt. % PVP K-90)

MT 0 28.2 ± 1.4 6.21 (±1.05) 8.2 (±0.55) 72 ± 4 3340.1a
MT-1 0.2 36.4 ± 2.5 6.18 (±0.05) 11.6 (±2.00) 81.5 ± 3 3340.1a
MT-2 0.4 35.3 ± 1.2 5.89 (±1.00) 9.8 (±1.20) 88 ± 5 3340.1a
a
Viscosity of the base membrane.

thickness of 150 ± 5 μm. The glass substrate with the polymer solution
was immediately immersed in DI water (non-solvent) to obtain the
polymeric membrane.
2.4. Thin-film nanocomposite (TFN) nanofiltration (NF) membranes
The pristine PEI UF membranes fabricated (as discussed previously)
was used as the base membrane for the preparation of the thin-film
nanocomposite membranes. The polyamide layer was prepared by the
in-situ interfacial polymerization (IP) of m-Phenylenediamine (MPD,
Sigma, 99 %) with 1,3,5-Benzenetricarbonyl trichloride (TMC, Sigma,
98 %) [34]. The base membrane was affixed onto an acrylic frame with
the top layer facing upwards. Briefly, 100 mL of 1 wt.% aqueous MPD
solution with LDH was poured onto the membrane surface and held for
120 s to ensure maximum penetration into the pores, after which the
excess solution was removed using filter paper and a rubber roller. A
0.1 wt. % solution of TMC dissolved in n-hexane was then poured over
the membrane surface and held for 60 s to aid in the polycondensation
reaction between the monomers. The excess, unreacted monomers were
removed by rinsing using DI water, and membranes were dried at 60 ⁰C
for 20 min for curing to stop the reaction altogether. The membranes
(Table 1) were stored in DI water until further use.
2.5. Characterizations
The X-ray diffraction patterns of the LDH were obtained from
2Θ = 3− 90◦ using Rigaku Miniflex 600; Japan operated at 40 kV and
15 mA with CuKαas, the radiation source. Attenuated total reflectance-
Fourier transform infrared spectroscopy (ATR-FTIR/FTIR) spectra in
the range of 4000–400 cm− 1 were recorded using an Agilent Technol­
ogies Cary 630, USAFTIR Spectrometer. The cross-sectional and top
surface morphology of the membranes were investigated using Scanning
Electron Microscopy (Hitachi SU6600, Japan) and atomic force micro­
scopy (Park Systems XE-100, Korea). Transmission electron microscopy
(TEM) equipped with an Energy Dispersive X-Ray Spectroscopy (EDS)
was done using the FEI-Tecnai G2 20 Twin instrument. The thermo­
grams were realized using a thermogravimetric analyzer (Hitachi
STA7200), and the samples were scanned from room temperature to
800 ◦ C at a rate of 10 ◦ C/min. The surface area and porosity of the LDH
were calculated from the BET equation using Belsorp Max (Japan) in­
strument. The tensile strength was obtained using the Universal Testing
Machine (UTM), Shimadzu AG-X plus, Japan at 10 kN, and a draw rate
of 0.5 mm/min (n = 3). The water contact angle was determined by the
sessile drop method (GBX technologies, Germany) using a volume of
5 μL, and measurement was carried out on at least 5 different locations
on the membrane sample.
2.6. Membrane performance evaluation
2.6.1. Performance evaluation of the mixed matrix ultrafiltration
membranes
The filtration experiments were carried out in a self-designed cross-
flow filtration set up using a test cell (Sterlitech Corporation, USA)
having an effective membrane area of 42 cm2. The MMMs were com­
pacted at 5 bar for 2 h before carrying out the filtrations at an operating
pressure of 3 bar.
The pure water flux and the solution flux of the membranes were
evaluated at 25 ⁰C using:
V
J (LMH) = (1)
A ×t
where V is the volume of permeate in Litres, A is the effective area of the
membrane used (m2), and t is the time taken to collect permeate in
hours.
The protein BSA (1000 mg/l), MB dye (20 mg/l) were used as feed
solutions to investigate the rejection performance of the MMMs (pH ~
7.5). The concentrations of BSA and MB dye were A UV–vis spectro­
photometer (PerkinElmer-Lambda 650) at a wavelength of 280 nm and
665 nm, respectively, using the following equation
[ ]
Rejection (%) = 1 −
Cpermeate
× 100 (2)
Cfeed
The antifouling properties of the membranes were determined, as
discussed in previous reports. Initially, the pure water flux of the
membrane (Jw1) was determined using DI water as feed at an operating
pressure of 3 bar for 60 min using eq (1). An aqueous solution of BSA was
used as the feed solution, and the filtration was carried out under the
same pressure for 60 min. The membrane was backwashed and then
flushed with DI water for 10 min. The PWF of the cleaned membrane
(Jw2) was determined similarly. The experiment was repeated for a total
of 3 cycles, and the flux recovery ratio (FRR) was determined using the
given equation
FRR(%) =
JW2
× 100 (3)
JW1
These experiments were repeated for 3 such runs, and the FRR values
for each run is determined.
2.6.2. Photocatalytic degradation of methylene blue using the mixed matrix
membranes
Initially, the adsorption efficiency of the pristine PEI and MMMs
were evaluated by placing a 10 × 15 cm membrane sample into a
400 mL solution of Methylene Blue dye (MB, 20 mg/L). The adsorption
experiment was carried out under dark conditions for 120 min, and a
2 mL aliquot was collected every 10 min for analysis. The concentration
of the dye was calculated using a UV–vis Spectrophotometer (664 nm).

3
Y. Mutharasi et al.
To carry out the photocatalytic degradation study, a photocatalytic
reactor (Lelesil innovative systems, India) was employed, which uses a
125 W medium pressure mercury lamp as a UV-source placed in the
inner-well. A 400 mL of dye solution was placed in the outer well
equipped with a cooling jacket. Fresh membrane samples with an
exposed area of 150 cm2 were introduced into the outer well containing
the dye solution. The solution with the MMMs was stirred using a
magnetic stirrer and kept in the dark for 30 min to allow it to reach
adsorption equilibrium before the UV lamp was turned on. 2 mL aliquot
were collected every 10 min until the end of the experiment (120 min)
using a silicon tube connected to a disposable syringe. The concentration
of the MB dye in the solution was measured as before. The membranes
were tested for 2 such runs.
2.6.3. Performance evaluation of the thin-film nanocomposite (TFN)
nanofiltration membranes
The same experimental set-up was used to carry out the nano­
filtration experiments at an operating pressure of 6 bar, and these TFN
membranes were pre-compacted at 10 bar for 2 h before the start of the
experiments. The pure water flux and the solution flux of the membranes
were evaluated at 25 ⁰C using eq (1).
MB dye (20 mg/l) and CaSO4 (1200 mg/l) were used as feed solu­
tions to investigate the rejection performance of the membranes. The
Fig. 1. X-ray diffraction spectra (a), FT-IR spectra (b), TGA curve (c), SEM image (d) and TEM images (e,f) of the Zinc-Aluminium layered double hydroxide.
4
Chemical Engineering and Processing - Process Intensification 158 (2020) 108191
concentrations of MB dye and CaSO4 was analyzed using a UV–vis
spectrophotometer (λmax =665 nm) and conductivity meter (Systronics-
304, India) respectively, using eq (2).
The flux recovery after long-term use was carried using CaSO4 feed
solution for a total of 12 h with a 10 min backwash after 6 h.
3. Results and discussion
3.1. Characterization of the zinc-aluminium layered double hydroxide
The XRD diffraction pattern of the Zn/Al LDH synthesized by a one-
pot co-precipitation technique is shown in Fig. 1a. The sharp diffraction
peaks were indexed to a hexagonal lattice with rhombohedral 3R sym­
metry as expected for these ionic class of solids (JCPDS 48–1023). The
basal peaks at 11.54◦ , 23.39◦ can be indexed to the (003) and (006)
which provides the evidence of parallel orientation of the nanosheets.
The non-basal peaks (012), (015), (018), (110), (113) are observed at
36.23◦ , 39.17◦ , 47.55◦ , 56.63◦ and 67.97◦ , respectively. The (003) re­
flections can be attributed to the anion present in the interlayer of the
LDH incorporated [33]. The first peak of the doublet at a 2Θ of around
60◦ is because of the alignment of the (110) planes, which matches with
the closest interatomic distance in the brucite-like layers. The average
size of the particle is calculated using Bragg’s equation and found to be
Y. Mutharasi et al. Chemical Engineering and Processing - Process Intensification 158 (2020) 108191

60 nm.
Fig. 1b displays the FTIR spectrum of the prepared LDH and confirms
the presence of the absorption bands inherent in hydrotalcite com­
pounds. The broad distinct band at 3400 cm− 1 can be assigned to the
O–H stretching vibration of the interlamellar H2O moieties. The weak
band at 1680 cm− 1 can be assigned to the distorting vibration of the
interlayer water [35]. The bands recorded at 460, 550, and 790 cm− 1
can be attributed to the Al-O condensed groups, the Zn/Al− OH trans­
lation, and the Al− OH deformation, respectively. The well-defined ab­
sorption peak at 1385 cm− 1 confirms the stretching vibration of the
anion, and the weak band at 765 cm− 1 is another stretching mode of the
nitrate anion.
The total mass loss of 22.5 % was calculated from the thermogram
(Fig. 1c); when the LDH was heated to 800 ◦ C. The weight loss at <
100 ◦ C can be attributed to the removal of the physisorbed water mol­
ecules. Two distinct losses of removal of bound water and interlamellar
water molecules can be observed at 180 ◦ C and 200 ◦ C [35]. The
noticeable mass loss from 300− 450 ◦ C could be explained by the
dehydroxylation of the metal oxide layers and degradation of the
anionic (NO−3 1) interlayers.
SEM and TEM images confirm the morphology of the prepared LDH.
SEM images display agglomeration of flake-like crystallites in Fig. 1d.
The expected 2-D sheets having a hexagonal structure with well-defined
edges can be confirmed from the TEM images (Fig. 1e,f).

3.2. Characterization of the UF mixed matrix membranes

3.2.1. Chemical structure and surface wettability

The chemical structure of the prepared MMMs can be deduced
through the FT-IR spectra displayed in Fig. 2a.The FTIR spectra of the
pristine PEI membrane (M0) displayed absorption bands at 1780 cm− 1
and 1718 cm− 1, which corresponds to the asymmetric and symmetric
– O of the imide groups. The bands at 1356 cm− 1 and
stretching of the C–
745 cm− 1 can be attributed to the C– – N stretching and bending vibra­
–
tions. The C–O–C vibrations of the PEI are ascribed to the band at
1234 cm-1 [36]. The membrane M-2 displayed all the significant peaks of
corresponding to PEI polymer and additionally exhibits an absorption
peak at 1380 cm− 1, which can be accounted for the anti-symmetric
stretching mode of the nitrate anion present in Zn-Al-NO3 layers. The
incorporation of LDH can be confirmed by the increase in the stretching
vibration of the − OH bonds at 3500 cm− 1. An increase in the intensity of
the absorption bands at 790, 460 and 550 cm-1 correspond to the Al-O
condensed groups of the LDH. As the percentage of LDH on the mem­
brane surface is quite small, no major changes in the absorption spectra
were recorded.
The droplets of DI water are dispensed onto the clean membrane
surface using a Hamilton syringe, and the average contact angle of 5
such drops was determined, and their average plotted in Fig. 2b. The
surface of the M0 membrane displayed the lowest wetting by the water Fig. 2. The surface chemical composition (a), the surface wettability (b) and
drop (high water contact angle), and this indicated a more hydrophobic the TGA (c) of the LDH incorporated polyetherimide mixed matrix membranes.
surface. Incorporation of LDH into the membrane matrix provided
greater − OH sites for the water molecules to attach via H-bonding. This and bound water molecules.M-2 displays a further weight loss between
plays an essential role in the spreading of the water droplet, as 300− 450 ◦ C could be due to the loss of anions from the interlamellar
confirmed by the lower water contact angle measured. The porosity structures of the incorporated LDH nanomaterials. A temperature
(Table 1) and chemical structure account for the decrease in WCA from greater than 450 ◦ C leads to the scissoring of polymer chains, ring fusion,
87.2◦ (±1.1) for M-0 to 60.4◦ (±2.0) for M-2. The water molecules and finally, carbonization of the polymer membrane. The thermal sta­
surrounding the membranes form H-bonding with the − OH groups of bility of the MMMs is satisfactory for them to be employed in a photo­
the LDH present in the membrane matrix. This can prevent the catalytic reactor for the degradation of the MB dye [39].
adsorption of hydrophobic foulants onto the membrane surface [37], There is only an incremental increase in the tensile strength of the
and similar results are reported when hydrophilic halloysite nano­ membranes incorporated with LDH nanoparticles (Table 1). This could
tube/Fe3O4 were incorporated into hydrophobic PVDF membranes [38]. be explained by the following factors: LDH bearing a copious number of
functional groups (OH− , NO−3 , etc.) penetrates between the polymer
3.2.2. Thermal and mechanical stability chains and produces cross-linking, which could be responsible for the
The TGA of the mixed matrix membranes is displayed in Fig. 2c. The increase in % elongation. The crystalline nanoparticles embedded
pristine and the MMMs did not show appreciable weight loss up to within the matrix improve the overall crystallinity of the mixed matrix
250 ◦ C; the small decrease in weight could be due to the loss of unbound

5
Y. Mutharasi et al.
membranes, which could be responsible for the small increase in the
tensile strength [40]. There are reports of a decrease in mechanical
properties of the membrane with the incorporation of nano-fillers due to
lower interaction between polymer and nanoparticles or inhomoge­
neous dispersion density [41]. However, in this case, this phenomenon
was not observed due to the low loading ratio of the LDH. This indicates
that LDH nanomaterial was relatively well dispersed within the mem­
brane matrix with an excellent affinity to the PEI matrix.
3.2.3. Analysis of the membrane architecture
Fig. 3 shows the top surface and cross-sectional morphologies of the
prepared MMMs. All the MMMs possess a typical asymmetric structure
with a thin top layer with surface pores and a porous sublayer. The
incorporation of the hydrophilic nanomaterial, LDH, affects the kinetics
and thermodynamics of the phase inversion process, thereby altering the
membrane vitrification pathway in the ternary phase diagram [42].
Both of these factors play opposing roles in the membrane formation
process. The pristine PEI membranes exhibited finger-like pores in the
porous sublayer and with a few surface pore openings. The top surface
image of the membrane M-1 reveals the presence of a more significant
number of pore openings on the denser top surface due to the increase in
hydrophilic content in the polymer solution. The substructure remained
Fig. 3. The cross-sectional SEM image, the top surface SEM image and the topography from AFM imaging for M0 (a, a’, a’’); M-1 (b, b’, b’’) and M-2 (c, c’, c’’)
respectively.
6
Chemical Engineering and Processing - Process Intensification 158 (2020) 108191
finger-like pores with the formation of a considerable quantity of
interconnected pores. This could explain the greater pure water flux
described in the later section. The higher viscosity of the casting solution
(Table 1) leads to a sponge-like morphology for M-2, which is distinct in
the SEM images.
The AFM was used in the non-contact mode to investigate the to­
pology of other membrane surfaces. It was observed that the average
surface roughness was most significant for the 1 wt% membrane (M-1)
followed by M-2 and least was for the pristine PEI membrane. This could
be explained as follows: the presence of LDH in the dope solution (up to
1 wt.%) could increase the rate of solvent and non-solvent exchange,
thereby giving rise to a larger number of peaks and valleys. Above this
concentration (at 1.5 wt.%), the nanomaterial increased the viscosity of
the casting solution, thereby suppressing the rate of solvent and non-
solvent exchange, leading to a surface with lower roughness (Table 1).
The increase in surface roughness can also explain improved water
permeability as it increases the number of surface pores and provides a
greater contact area (hydrophilic sites), which enhances the water pas­
sage [43].
The improvement in membrane porosity, which is evident in the SEM
and AFM images are quantified using the gravimetric technique, and the
results are given in Table 1.
Y. Mutharasi et al. Chemical Engineering and Processing - Process Intensification 158 (2020) 108191

3.3. Pure water flux and rejection studies of the MMMs %), which rapidly declined in successive cycles (Fig. 5). Membrane M-1
possessed the most excellent antifouling property evidenced by a 92 %
The pure water flux of the prepared mixed matrix membranes FRR, which showed only a small decline even after two cycles. The
(MMM) is calculated and plotted in Fig.4. The water flux was obtained membrane hydrophilicity, optimum loading, and distribution of the
using pre-compacted membranes of higher pressure to obtain consistent LDH contributed to its highest FRR. This indicates a low level of irre­
results. The pure water flux of M1 and M2 is greater than the pristine PEI versible fouling even after three cycles, which was reported with the
membrane. This could be explained as follows: the incorporation of LDH incorporation of hydrophilic filler GO in the polyethersulfone/sulfo­
containing large no. of − OH groups improve the porosity of the mem­ nated polysulfone ultrafiltration membranes [50]. During the filtration
branes due to its preferential migration towards the non-solvent (water) studies, Zn or Al was not detected (ICP-OES, Perkin Elmer Optima 5300
[44]. The addition of LDH improves the hydrophilicity of the mem­ DV) in the permeate side, indicating that the leaching of the LDH from
branes, as evident from the water contact angle results [45]. Apart from the MMMs was negligible.
this, the membrane surface roughness (rough surface of hydrophilic
membranes) provide a greater area of contact to the water molecules
and thus enhance the permeation rate. When the LDH loading was 3.5. Photocatalytic Degradation of Methylene Blue Dye using the mixed
increased to 1.5 wt%, the pure water flux decreased slightly to 77 LMH; matrix membranes
this contrast in behavior could be associated with the agglomeration or
aggregation of LDH [46], which causes blocking and channeling of the The photocatalytic degradation of the MB dye is a complex multi-
pores or the pores of smaller diameter and spongier substructure as step process involving several intermediate steps, which finally yields
confirmed by the SEM images Fig. 3 non-toxic carbon-di-oxide and water as by-products. Here the double-
The rejection of the BSA (66.5 kDa) was found to be > 85 % for the well enclosed chamber is equipped with 125-Watt high-pressure mer­
UF membranes indicating that the pore sizes had not significantly cury as a UV source to evaluate the photocatalytic degradation effi­
changed with the addition of the Zn/Al LDH. The slight increase in ciency of the prepared membranes. The MMMs containing the LDH
rejection from 85.3 % (M0) to 96 % (M-1) can be explained as follows:
above the isoelectric point, BSA is negatively charged and can be
effectively hindered due to the combination of steric effect and elec­
trostatic effects (adsorption) as observed in earlier reports [47].
The rejection of the methylene blue dye, having a molecular weight
373.9 Da, was low, as expected when filtered using ultrafiltration
membranes. There is a slight increase in rejection due to the increased
repulsion of the cationic dye with the less-negatively charged mixed
matrix membranes. However, no significant results are obtained as total
rejection is less than 20 %.

3.4. Antifouling ability and the Flux recovery ratio of the MMMs

The membranes having high rejection of BSA cause an increase in

BSA concentration at the membrane surface, which can attach to the
membrane causing an irreversible loss in permeate quantity as well as
quality [48].
The decrease in flux when the BSA solution was used can be because
of the formation of a gel layer as BSA molecules interact with the
membrane surface, thereby increasing the membrane resistance. The
presence of LDH on the surface and inside the pores of the mixed matrix
membranes improves the membrane hydrophilicity, which lowers the
rate of adsorption of the hydrophobic BSA molecules, thereby
decreasing the membrane fouling [49].
The pristine PEI membranes exhibited the least flux recovery (68.5

Fig. 4. The pure water flux and the rejection performance of the mixed ma­ Fig. 5. (a) Performance of the MMM for a single cycle and (b) Flux Recovery
trix membranes. Ratio (%) for 3 cycles.

7
Y. Mutharasi et al.
when irradiated with low wavelength UV light (higher intensity than the
band gap), can engender high-energy states of electrons and hole pairs.
These electron/hole pairs function as powerful oxidizing/reduction
species or can generate new active species that can aid in the degrada­
tion of organic compounds in aqueous solutions [51].
The photolysis (photo-degradation) of the MB dye without the
MMMs is evaluated prior to the photocatalytic experiments using the
MMM. Furthermore, the removal of MB dye by adsorption is also
determined to confirm the photocatalytic property of the LDHs.
Initially, the feed solution (MB- 20 mg/mL, pH 7.5) was fed into the
photocatalytic reactor, and the chamber was closed, and the UV source
turned on. In this case, no LDH or MMMs were placed in the reactor. It
was noticed that there was no significant decrease (< 3 %) in dye con­
centration at the end of 60 min, which implies that direct photo-
degradation of MB did not occur at these conditions (A cooling water
jacket did not allow the temperature in the reactor to rise more than 4
⁰C). The irradiation of dye molecules by the photon bombardment
provided some excitation energy, and subsequent dispersion of this
energy did not decolourize the MB solution.
The absorption kinetics of M-1 (Fig.6a), carried out under dark
conditions, confirms a 25 % reduction in MB concentration. It is inter­
esting to note that the total adsorption was completed in the initial
20 min, which could be due to the affinity for the cationic dye to the
hydroxyl and nitrate anions present in the LDH. Moreover, there was no
further change in concentration, even up to 100 min [52].
After initial equilibration in dark-condition, the MB feed solution
with the MMMs immersed was placed in the photocatalytic chamber,
and the UV source turned on. The solution was continuously stirred to
provide in-situ aeration and to maintain a homogenous mixture
throughout the experiment. M-1 and M-2 membranes exhibited a dye
removal of 94 % and 92 %, respectively, during the initial run [53]. This
could be explained by the larger surface area available due to the well
dispersed LDH in the matrix, which increased the membrane surface
roughness. M-2 exhibited a decline in dye degradation during the second
run, which could be due to the larger number of LDH particles that could
irreversibly bind the dye or intermediate degradation products (Fig. 6b).
The degradation of the dye is aided by the holes (conduction band)
and hydroxyl radicals generated; the mechanism can be postulated as
follows.
LDH + h ν (<400 nm) → (e−CB)+ (h+
VB)
(h+
VB) + R → intermediates →CO2+ H2O
→ with the increase in LDH loading, from ~ 64.6◦ for the TFC membrane to
H2O + (h+
VB) OH⋅ + H
+
OH⋅+ R → intermediates → CO2+ H2O.
The ultrafiltration studies and photocatalytic experiments concluded
that M-1 (1 wt.% loading of Zn/Al LDH) displayed > 96 % BSA rejection
with a flux recovery ratio of 88 % even after 3-cycles and was able to
Fig. 6. The photocatalytic degradation a), reusability of the MMMs b) for degradation of MB dye (initial concentration 20 mg/l).
8
Chemical Engineering and Processing - Process Intensification 158 (2020) 108191
photocatalytically degrade an organic compound (Methylene Blue Dye)
under UV –light in a batch mode. M-1 holds great potential to be further
explored for UF applications and has been compared with recent liter­
ature reports (Table 2) [54–58].
3.6. Characterisation of thin-film nanocomposite NF membranes
3.6.1. SEM of TFN membranes
The cross-sectional SEM images (Fig. 7a,b,c) show a highly porous
PEI sublayer with well-developed finger-like pores having a high degree
of interconnectivity. The incorporation of 0.4 wt%. LDH is seen to lower
the thickness (300 nm) of the PA layer compared to the MT and MT-1
membranes (420 nm).
A characteristic ridge-and-valley like topography is evident in the
top-surface images of TFC as well as the nanocomposite modified
membranes (Fig. 7a’,b’,c’). The LDH increases the formation of the
nodular structures in the PA layer, which could be due to the adsorption
of water molecules during the interfacial polymerization. The hydration
of these water molecules of LDH introduced in the aqueous amine so­
lution could cause an augmentation in its size, forming the nodule-like
structure [59]. The dispersed LDH could be observed as white clusters
in the top layer of the MT-2, which was absent in the MT-1. The presence
of an optimum concentration of LDH can improve the morphology of the
membrane surface to ensure that there is no pore blocking or chan­
neling, which is present in MT-2. Even in higher loading, only a few
nanomaterial clusters can be observed as most of the particles are
embedded in the PA layer [60]. The EDX (Fig. 7d) mapping confirms the
incorporation of Zn/Al LDH on the membrane surface.
3.6.2. AFM of TFN membranes
The membrane surface roughness investigated using the AFM is
displayed in Fig. 8, and the surface roughness increased as follows:
MT < MT-1< MT-2. The higher content of the LDH in the active PA layer
was responsible for the increase in the membrane surface roughness. The
LDH can absorb water molecules and swell during the IP, leading to the
formation of nodules, as explained earlier. The increased roughness of
the membranes can also improve membrane permeability as it offers
greater contact area and more hydrophilic pathways through the PA
layer, which is also seen to impart antifouling property to the TFNs [61].
3.6.3. Surface wettability of the TFN membranes
The water contact angles (Fig. 9) measured were found to decrease
~ 52.6◦ for MT-1. An optimum concentration of hydrophilic nano­
materials in the surface is thought to be responsible for the decline in the
WCA to its due hydrogen bonding with water molecules [62]. This,
coupled with the increase in porous channels due to the LDH, can attract
water molecules to the membrane surface and improve its water
permeability. MT-2 displays a slightly higher contact angle due to the
 Y. Mutharasi et al.
Table 2
A comparison with recent state-of-the-art literature.
Mixed Matrix Ultrafiltration Membranes

Sl. Polymer (wt.%) Filler (%) PWF (LMH) @ operating pressure BSA (rejection %) FRR% Other Specific Properties Ref.
No.
1 Cellulose Acetate (10.5 PEG 316 LMH 91.9 91 – [54]
%) 5 wt% (3 bar)
2 PES 1 wt% PVP and 1 wt% PA-6 175 LMH 96 55 – [55]
(18 %) (4 bar)
3 PES (16.5 %) +PEG (8 Iron-tanin-framework 319.4 LMH 95.9 88.29 – [56]
%) (ITF) (1 bar)
0.3 wt%
4 PVDF (13.3 %) Cellulose Nanocrystal 40 LMH 88.2 80 – [57]
(0.7 wt%) (1 bar)
5 PES (15 %) Bentonite (2%) 53.6 LMH 73.7 84.6 % – [58]
(2 bar)
6 PEI (16 %) 1 % Zn-Al-LDH 89 LMH 96.5 92 Able to Photocatalytically degrade organic compounds Current
in UV-Light Work
Nanofiltration membranes
9

Sl. Base Polymer (wt.%) Monomers used in IP Nanofillers (%) PWF @ pressure Solutes removed & % Other Specific Properties Ref
No. removal
1 PolyImide (PI) MPD and TMC Carbon Quantum Dots (CQD) 42.1 LMH 93.6 % Na2SO4 Antifouling performance [68]
(6 bar)
− 6
2 Polysulfone MPD and TMC – 17.02 LMH 88.75 % rejection of Permeability coefficient of NaCl 0.98 × 10 m/s [69]

Chemical Engineering and Processing - Process Intensification 158 (2020) 108191

(15 wt.%) (14 bar) hydroquinone
3 Polysulfone PIP and TMC ZIF-8 55.02 LMH 95 % [66]
(commercial) (6 bar) Na2SO4
4 Polysulfone PIP and TMC Graphitic carbon nitride (g-C3N4) 82 LMH 94.5 % [67]
(commercial) 16.4 μg cm− 2 g (4 bar) Na2SO4
2
and Halloysite nanotubes 19.7 μg cm−
(HNTs)
5 PAN (phase inversion) – Citric Acid and TiO2 58− 136 LMH 66− 86 % Calcium Suphate – [70]
(10 bar)
6 PEI MPD and TMC Zn-Al-LDH (0.1 wt %) MT-2 Pure water flux Antifouling property after long-term filtration (12 h) Current
18 LMH 91 % Zn/Al LDH possesses photocatalytic abilities. Work
(6 bar) Calcium Suphate
95 %
Methylene Blue Dye
Y. Mutharasi et al.
Fig. 7. Cross-Section and top Surface SEM micrographs MT (a, a’), MT-1 (b, b’), MT-2 (c, c’) and the EDX mapping of the MT-2 membrane (d).
Fig. 8. Surface roughness using atomic force microscopy of MT (a,), MT-1 (b,), MT-2 (c).
Fig. 9. The water contact angle indicating the surface wettability of the TFNs.
increase in LDH concentration, which could lead to a greater degree of
clusters being formed. The agglomeration of the nanofillers can lead to
the formation of H-bonding within itself, thus decreasing the − OH
groups available, as observed in earlier reports [63].
3.6.4. Pure water flux and MB rejection of the TFN membranes
The pure water flux of the membranes (Fig.10a) increased from 10.5
10
Chemical Engineering and Processing - Process Intensification 158 (2020) 108191
LMH in MT-0 to 26.4 LMH in MT-1. This increase is due to the incor­
poration of the hydrophilic LDH that improves the membrane porosity
and hydrophilicity. The interruption in the PA layer due to an optimum
concentration of LDH can also explain the result. A slight decrease in
PWF is observed in MT-2, which can be attributed to the agglomeration
of particles on the top surface, which causes partial or complete blocking
of pores evident in the SEM images. However, it still exhibits greater flux
than pristine TFC. The TFN membranes possess better antifouling
properties, and an increase in flux by almost 2.5 times was recorded.
The permeate flux of the MB feed solution was lower than the PWF as
expected (Fig. 10a), and the rejection of the dye is due to mainly due to
size exclusion. The presence of the LDH tunes the PA layer forming
smaller pore openings. MT-2 membranes display the most outstanding
rejection (94.5 %) (Fig. 10b) could be due to the pore-blocking, as dis­
cussed in the previous section. The LDH can act to prevent the adsorp­
tion of the cationic dye on the membrane surface due to its hydrophilic
character, and this does not allow a build-up of the dye molecule layer,
ensuring that the membranes can be used for a long time [64].
3.6.5. Rejection Studies of calcium sulphate using TFN membranes
Here, CaSO4 is chosen as a model divalent salt to investigate the
rejection performance of the nanofiltration membranes, and it could be
noted that the membranes exhibited lower salt rejection compared to
MB dye as expected due to the difference in molecular weights. An in­
crease in rejection of CaSO4 salt was observed for the TFN membranes
(Fig.10 b), which could be explained as follows- (i) the hydrated radii of
the ions was greater than the pathway formed in the PA layer due to the
Y. Mutharasi et al. Chemical Engineering and Processing - Process Intensification 158 (2020) 108191

Fig. 10. Pure water flux, solution permeate flux (a) and rejection performance (b) of the TFNs.

incorporation of LDH and (ii) the incorporation of LDH is seen to in­

crease the surface charge (less negative) [30] which improves the salt
rejection due to Donnan exclusion effect. Membrane MT-2 has greater
flux and better rejection than the pristine TFC, which is an indication
that the trade-off criterion could be surpassed by the incorporation of
Zn-Al LDH [59,65].

3.6.6. Flux recovery ratio of the TFN membranes for long-term filtration
The improvement of flux recovery is due to several factors, all
explained in previous sections. Improvement in hydrophilicity and an
increase in surface roughness prevents the molecules from adhering or
depositing to the membrane surface. The flux recovery of MT-2 (Fig. 11)
is compared to the pristine TFC membrane. The membranes were
challenged with 1200 ppm CaSO4 solution for 6 h, followed by a mem­
brane cleaning for 10 min and was repeated two times (12 h). The MT-2
membrane exhibited a flux recovery ratio of 0.8 after two successive
runs (total 12 h). The high flux recovery is attributed to the improved
surface hydrophilicity and the hydration layer formed at the membrane
interface. Our prepared TFN membranes are compared with recent
studies and given in Table 2 [66–70]. The membrane performance is Fig. 11. Flux recovery after long term filtration with 1200 ppm CaSO2 solution.
comparable to other works and holds the potential to be employed as
TFN nanofiltration membranes for the removal of dye and divalent salts. Writing - review & editing. Thanigaivelan Arumugham: Formal
analysis, Resources, Writing - original draft. Fawzi Banat: Writing -
4. Conclusion review & editing. MSR Sridhar Kapavarapu: Data curation, Investi­
gation, Validation.
Ultrafiltration using PEI mixed matrix membranes incorporated with
Zn2+/Al3+ holds the potential to be employed for pre-treatment of Declaration of Competing Interest
wastewater before the nanofiltration process. The MMMs exhibited an
impressive photocatalytic ability in addition to the antifouling ability. The authors declare that they have no known competing financial
High rejection of BSA and an excellent flux recovery after 3-cyles run interests or personal relationships that could have appeared to influence
proves that the MMMs are favorable to be used in the pre-treatment step. the work reported in this paper.
The incorporation of LDH into the active layer of the TFN membranes
produced nanofiltration membranes that displayed greater surface Acknowledgments
porosity, enhanced surface wettability, and improved antifouling abil­
ity. MT-1 displayed a 2.5 times increase in pure water flux while The authors like to acknowledge the partial financial support by the
showing no deviation in thermal or mechanical stability. However, the National Institute of Technology Calicut, India for the student innova­
optimum membrane MT-2 displayed a flux greater than the TFC with an tive project grant titled “Development of layered double hydroxide
MB dye rejection of 94.5 % and 91 % salt rejection with a modest flux incorporated PEI membranes with enhanced photocatalytic and anti­
recovery after long-term filtration studies. The results indicate that the fouling ability” to Dr. Noel Jacob Kaleekkal.
dual functionality of the Zn/Al LDH and hence these materials hold
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