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org Article

Electrospun Polyurethane Nanofiber Membranes for Microplastic

and Nanoplastic Separation
Kandiyil Juraij, Saeed Punnoli Ammed, C Chingakham, Brindha Ramasubramanian,
Seeram Ramakrishna, Suni Vasudevan, and Athiyanathil Sujith*
Cite This: ACS Appl. Nano Mater. 2023, 6, 4636−4650 Read Online

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ABSTRACT: Multifunctional materials for industrial wastewater

treatment are in high demand due to the contamination of micro-
and nanoplastics (MNPs) and dyes. Herein, we demonstrate a
polyurethane-based (PU) electrospun composite membrane for
MNP separation and selective methylene blue (MB) adsorption.
The optimized 20 wt % graphene oxide-montmorillonite (GO-
Mt)-loaded nanofibrous composite membrane (20-PGT) exhibited
its superhydrophilicity with a water contact angle of 0° and high
water flux. It displayed a maximum pressure-driven water flow of
8163 L m−2 h−1 and a gravity-driven water flux of 793 L m−2 h−1.
Three model MNPs, such as acrylonitrile butadiene styrene (ABS),
polystyrene (PS), and poly(methyl methacrylate) (PMMA) with
various sizes, have been demonstrated. The adsorptive separation
and size-exclusive interception mechanisms were observed for nanoplastics (NPs) and microplastics (MPs), respectively. Cake
formation, intermediate blocking, and standard blocking mechanisms were followed during the filtration of ABS MPs, PMMA NPs,
and PS NPs, respectively. Additionally, the composite membrane exhibited selective MB adsorption from the mixture of dyes, with a
maximum adsorption capacity of 417 mg g−1. Langmuir adsorption isotherm and pseudo-second-order kinetics define the adsorption
isotherm and adsorption kinetics, respectively. The fabricated, robust fibrous composite membrane opens a wider door for the
removal of MNPs and MB from contaminated water.
KEYWORDS: polyurethane, graphene oxide-montmorillonite, electrospun membranes, micro- and nanoplastic separation, dye adsorption,
fouling mechanisms, gravity-driven flux

1. INTRODUCTION Approximately 1,000,000 tons of dyes are consumed world-

Plastic pollution is becoming a severe threat to the environ- wide by industries such as tanneries, food, cosmetics, textiles,
ment on a global scale due to its widespread use in large and medicine.10 As a result, non-biodegradable dye molecules
quantities and slow decomposition.1,2 In fact, the escalating exist in the environment, developing environmental risks.11
Thus, it is imperative to eliminate dye molecules from
usage of plastics is developing a greater menace, especially
wastewater before discharging them into the environment.
concerning microplastic (MP) or nanoplastic (NP) contam-
Various separation techniques have been used to remove
ination.3,4 These micro- and nanoplastics (MNPs) enter the
dyes and MNPs from the water, such as chemical, physical, and
ecosystem through various channels. For instance, the
biological methods.12 Among all, adsorption and filtration were
degradation of existing plastic waste, accumulation of waste
reported as top-quality treatment procedures for removing
from the plastic industry, and food chain transfer may
dissolved organic pollutants from industrial wastewater.13
contribute to the spread of MNPs.5 In this regard, poly(methyl
Organic, inorganic, hybrid functional materials or metal−
methacrylate) (PMMA), acrylonitrile butadiene styrene
organic frameworks (MOFs) have recently been used for dye
(ABS), and polystyrene (PS) are widely used polymers for a
adsorption and wastewater treatment applications.14,15 Gra-
variety of applications including electronic applications, optical
applications, building materials, protective materials, and food
packaging materials.6,7 These polymers can persist as MNPs in Received: January 9, 2023
the environment for extended periods, which poses a risk to Accepted: March 1, 2023
both humans and the environment.8,9 Therefore, it is essential Published: March 13, 2023
to remove from the environment and water resources. Besides
the MNP issues, the presence of coloring dyes in the water
stream affects the life expectancy of aquatic organisms.

© 2023 American Chemical Society https://doi.org/10.1021/acsanm.3c00112

4636 ACS Appl. Nano Mater. 2023, 6, 4636−4650
ACS Applied Nano Materials
Figure 1. Schematic representation of the preparation of the PGT electrospun composite membrane and sample composition.
phene oxide (GO) is a versatile material for water filtration and
dye adsorption applications due to its increased equilibrium
rate and adsorption capacity.16 Due to several oxygen-
containing functional groups, it is a superhydrophilic,
negatively charged, and efficient electrostatic stacking materi-
al.17 On the other hand, montmorillonite clay (Mt)
[(Na,Ca)0.33(Al,Mg)2(Si4O10)] is a naturally occurring effec-
tive sorbent material for the cationic dye removal from
wastewater.18 Its layered structure with exchangeable ions
serves as a host for adsorbates and counter ions.19 The hybrid
nanofiller of GO and Mt, stabilized via hydrogen bonding and
electrostatic interaction, has great potential in dye removal and
MNPs due to its functional and structural stability.20
Application of pristine GO and Mt alone for water treatment
is limited due to their poor flexibility and processability.
Electrospun composite membranes have gained significant
attention in dye adsorption and MNP separation because of
their tunable porosity, high surface area, controllable surface
charge, ease of surface functionalization, and flexibility.21 Faris
et al.22 developed a polystyrene-based fibrous membrane with
GO functionalization using plasma treatment for MB
adsorption with an MB adsorption capacity of 114 mg g−1.
Xiaolong Ma et al.23 developed a sodium alginate/β-cyclo-
dextrin electrospun composite membrane to remove toxic dyes
from contaminated water. It showed a high adsorption capacity
of 2776 mg g−1. Only a few studies have been carried out on
MNP separation using electrospun membranes. Hongyi et al.24
fabricated an electrospun material by electrospinning quater-
nary ammonium functional group grafted polyvinylidene
fluoride (PVDF) on a polyethylene terephthalate (PET)
nonwoven substrate for the filtration of polystyrene NPs (PS
NPs). The PET substrate provided the mechanical support to
the electrospun PVDF during filtration. Under gravity-driven
filtration, 92% of PS NPs were separated from the water. Wang
et al.25 developed an electrospun polyacrylonitrile (PAN)-
based material by a layer-by-layer assembly strategy to remove
polystyrene microspheres with a retention rate of NPs in the
range of 92−99%.
Though few studies have reported MNP removal using
electrospun membranes, none of them have explored the dual
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functionality of an electrospun composite membrane in MNP
separation and dye adsorption from wastewater. Here, for the
first time, we are exploring polyurethane-based electrospun
composite membranes with the advantages of their dual
functionality in the removal of MNPs and dyes from
wastewater. A polyurethane/graphene oxide-montmorillonite
electrospun composite membrane (PGT) was developed using
the electrospinning method without any supporting substrates.
The developed membrane exhibited favorable properties such
as microfiltration (MF) pore size, superhydrophilicity, and
negative surface charge for MNPs and MB removal from
wastewater. The model MNPs for the filtration study were
prepared using ABS, PMMA, and PS polymers with different
dimensions of 825, 190, and 90 nm, respectively. The
developed membrane showed significant MNP removal from
MNP suspensions and high MB adsorption capacity from the
methyl orange/methylene blue (MO/MB) mixture. Thus, the
primary purpose of this research is to create a multifunctional,
mechanically strong PU-based nanofibrous composite mem-
brane for the removal of MNPs from contaminated water and
the selective adsorption of MB from the MO/MB dye mixture.
2. EXPERIMENTAL SECTION
2.1. Materials. Thermoplastic polyurethane (TPU, TECOFLEX
EG-85A grade, MW ≈ 1,20,604 g/mol) was supplied by Lubrizol
Advanced Materials, USA. The ABS polymer (Starex SD-0150) was
purchased from Samsung SDI Co., Ltd., Korea. Methyl methacrylate
(MMA), styrene, and 2,2′-azobis(2-methylpropionamidine) dihydro-
chloride (AIBA) were bought from Sigma-Aldrich. The modified
Hummer’s method was employed to prepare graphene oxide (GO).
Detailed preparation is given in Supporting Information S1. Sigma-
Aldrich Chemical Pvt. Ltd., India, provided montmorillonite clay
(Mt) (25 μm). Sisco Research Laboratories Pvt. Ltd., India, supplied
methyl orange and MB dyes. Tetrahydrofuran (THF), 99.5%, and
dimethylformamide (DMF), 99%, were supplied by Avra Chemicals,
India. MNPs such as ABS, PMMA, and PS were prepared in the
laboratory, and detailed procedures are discussed in Supporting
Information S2.
2.2. Preparation of the GO-Mt Hybrid Nanofiller. The
graphene oxide-montmorillonite (GO-Mt) hybrid filler was synthe-
sized by simple ultrasound treatment.20 5 g of Mt was added into 200
https://doi.org/10.1021/acsanm.3c00112
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mL of deionized (DI) water and made into a fine dispersion using a used to measure the conductivity of the PU and PGT homogeneous
probe sonicator (130 W, 20 kHz, 40% amplitude) by sonicating for 5 solutions.
h. GO (1.25 g) was added to 200 mL of DI water and subjected to the 2.5. Porosity and Pore Size Measurement. By using eq 1, the
same ultrasonication treatment for 5 h. The fine dispersions of GO porosity (ε%) of electrospun samples was estimated.26
and Mt were mixed together and further sonicated for an additional 5
h. The resulting suspension was subjected to stirring for 24 h at 400 (Ww Wd)/ w
= × 100
rpm. The obtained GO-Mt composite was then collected by (Ww Wd)/ w + (Wd / PU ) (1)
centrifugation at 4000 rpm for 30 min. Finally, GO-Mt was
vacuum-dried at 60 °C for 24 h. Basic material characterizations of where Ww (g) and Wd (g) denote the mass of wet nanofibrous
GO-Mt are given in Supporting Information S3. membranes and the dry fibrous membrane, respectively. The ρw and
2.3. Preparation of Nanofibrous Composite Membranes. ρpu represent the densities (g/cm3) of deionized water and PU (ρpu =
Different weight percents of the GO-Mt hybrid filler were initially 1.05 g/cm3), respectively.
dispersed in the THF/DMF mixture (3 mL DMF and 7 mL THF) Using eq 2, the pore size (r) of the fibrous membranes was
and sonicated with a probe sonicator for 15 min. An appropriate estimated.27
quantity of the PU polymer was added to the GO-Mt dispersion and
ij yz
kept on the stirrer for 6 h to ensure complete dissolution. Sample jj zz
r= jj 1zzzd
composition is depicted in Figure 1. A 10 mL syringe was filled with j
the prepared PGT spinning solutions. The syringe was equipped with 4 jjj 2 log
(1) zz
z
k { (2)
a spinneret (metallic needle) of 21 gauge having an inner diameter of
0.514 mm. Then, the syringe was placed on a syringe pump, and the where ε and d are the porosity (%) and the average fiber diameter
spinneret was connected to a high-voltage supply electrode (0−30 kV, (nm), respectively.
HO-NFES-041 Holmarc, India). With the voltage supply, a Taylor 2.6. Water Flux, Microplastic Filtration Efficiency, and
cone was initially formed, followed by fibers with various aspect ratios Fouling Models. A self-designed glass apparatus of 5.7 cm2 cross-
being deposited over the mandrel at a 500 rpm rotational speed. The sectional area was used to investigate the gravity-driven water flux.24
electrospinning parameters were optimized, such as working distance The electrospun membrane was sandwiched between the upper and
(16 cm), flow rate (1 mL/h), and applied voltage (16 kV), and it was lower portions of the glass apparatus without any support. The
fixed for the entire composite fabrication process. To obtain the pressure was calculated as 0.135 psi (931 Pa) during the gravity-
required membrane thickness, the electrospinning process was driven flux. For the investigation of the pressure-driven water flux, an
extended for 10 h. After collecting the electrospun mat from the ultrafiltration stirred cell with a 4.1 cm2 cross-sectional area was used.
collector, it was placed in a vacuum oven to remove surplus solvents 1000 mL of distilled water was supplied to the reservoir to facilitate
for 24 h. Figure 1 shows the schematic diagram for electrospinning. flux measurements. To maintain the proper pressure during the
2.4. Material Characterization. Using the Fourier transform experiment, N2 gas was supplied. The pressure-driven (1 to 6 psi) and
infrared spectroscopy (FT-IR) (Jasco FT/IR-4700) in the ATR gravity-driven water flux (J) were evaluated using the following
mode, bonding properties were examined. For each sample, three formula.28
scans in the 4000−400 cm−1 range were carried out with base V
correction. At an accelerating voltage of 5 kV, a Zeiss, Ultra 55 field J=
A× t (3)
emission scanning electron microscope (FE-SEM) equipped with an
energy-dispersive X-ray spectroscopy (EDS) of the 10 mm SDD where V is the permeating water volume in liters, A stands for the
detector was used to examine the morphology, elemental mapping, membrane area (m2), and Δt stands for the operation time (h).
and elemental compositions of each sample. The average fiber Gravity-driven and pressure-driven filtrations have been utilized to
diameter was calculated using Image J software. From each investigate the separation efficiency of MNPs from water.24,29,30 MNP
membrane, 50 fiber locations were randomly chosen for getting suspensions were prepared by the ultrasonication pathway. The
different fiber diameter values. Raman spectroscopy confirmed the prepared suspension of ABS, PMMA, and PS MNPs (10 ppm) was
formation of GO from graphite and the functionalization of PGT by filled in the reservoir separately. During the pressure-driven study,
GO (Horiba LabRam Confocal Raman Spectrometer, 532 nm laser). sufficient pressure (1−6 psi) was applied using the N2 gas pressure
It is a mirror-based spectrometer with a scanning range of 50−4000 controller. Flux was calculated using eq 3. An UV−visible
cm−1 and an 800 mm focal length (600 holographic gratings, 1800 spectrophotometer was used to measure the amount of MNPs in
grooves/mm). Using thermogravimetric analysis (TGA), the thermal permeates. Standard dispersions (0−50 ppm) were made, and the
properties of samples were examined (TGA Q-50, TA instruments). A absorbance of standard ABS, PMMA, and PS suspensions at 244, 286,
scan rate of 5 °C/min between 25 and 600 °C was used. To examine and 233 nm, respectively, were measured to find out the unknown
the mechanical strength of samples, a Universal Testing Machine concentration of permeate during MNP separation.31 After MNP
(UTM, AG-Xplus series, Schimadzu Autograph) with a 10N applied suspension filtration, the membrane was completely cleaned with
stress was employed. By using an X-ray diffraction (XRD) (Miniflex distilled water, and the efficiency of the membrane was assessed by
600 Rigaku X-ray generator, Cu Kα radiation with λ = 1.5406 Å) testing the pure water flux once more. Parameters such as percentage
experiment, the crystalline property was examined. The wettability of rejection, flux recovery ratio (FRR), and relative flux decay (RFD)
the membrane was assessed using a GBX Digidrop goniometer. A were utilized to investigate the MNP separation performance. The
non-contact mode atomic force microscope (AFM) was employed to removal of MNPs was expressed by removal efficiency (%), and it was
monitor the surface roughness of the membranes (AFM, Park system calculated using the following equation.24
XE 100). Using an UV−visible spectrophotometer, the removal of Cf Cp
MNPs from water and the adsorption of MB and MNPs were studied Removal efficiency(%) = × 100
(UV-2600 Shimadzu). A home-built gravity-driven water flux Cf (4)
apparatus and stirred ultrafiltration cell (Amicon 8010, Pmax = 75
psi) were used for water flux, MNP filtration, and dynamic MB where Cp and Cf represent the permeate and feed concentrations
filtration experiments. Using the Zetasizer equipment, the ζ potentials (ppm), respectively.
of the PMMA, PS NPs, and GO-Mt composite membrane were Equation 5 was used to calculate the FRR of nanofibrous
membranes.32
examined (Zetasizer nano, Malvern Instruments). The TOC analyzer
(TOC-L, Shimadzu) was used to evaluate the total organic carbon JW2
(TOC) of all permeates. At room temperature, a laboratory-type FRR(%) = × 100
conductivity meter (Systronics, conductivity meter 304, India) was JW1 (5)

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Figure 2. FE-SEM images and fiber diameter distribution of (a) pristine electrospun PU, (b) 5-PGT, (c) 10-PGT, (d) 15-PGT, (e) 20-PGT, and
(f) curve showing the variation of fiber diameter and EDS spectrum of (g) electrospun PU and (h) 20-PGT electrospun composite.

where JW1 is the pure water flux (L m−2 h−1) before the MNP membrane surface. The intermediate blocking model (m = 1)
suspension filtration study and JW2 is the pure water flux (L m−2 h−1) describes the fouling mechanism by the chance of pores being blocked
after the MNP suspension filtration study. by foulants or their deposition in the barrier-free area of the
The RFD was calculated by the following equation.33 membrane. According to the standard blocking model (m = 1.5),
J0 JP foulant particles are adsorbed on the sides of the pores. Pores are
RFD(%) = × 100 being completely blocked by foulants in accordance with the complete
J0 (6) blocking model (m = 2).35
−2 −1
where J0 is the pure water flux (L m h ) and Jp is the flux of MNP 2.7. Methylene Blue Batch Adsorption and Desorption
Studies. To analyze the selective adsorption process, batch
suspension in L m−2 h−1.
The fouling mechanism was studied during the flux of various experiments were used.36 Factors such as MB contact time and dye
MNP suspensions (ABS, PMMA, and PS) at 5 psi pressure for 1 h. concentration were thoroughly studied. In a batch experiment, 10 mL
Hermia enunciated different fouling mechanisms responsible for flux of an equimolar mixture (50 ppm) of MO and MB solutions was
decline under constant pressure. Equation 7 represents the flux added together, and the dried PGT electrospun composite membrane
decline under constant pressure.34 having a specific mass was added and placed under continuous
m
agitation at 500 rpm. An adsorption isotherm was investigated by
d2t ij dt yz measuring the MB adsorption capacity at different MB initial
2 = kj
j zz
dV k dV { (7) concentrations (10−50 ppm). The adsorption capacity of the 50
ppm MB solution was monitored at different time intervals to assess
where t represents the filtration time (h), V is the volume (liter), m is
the fouling model constant, and k stands for the resistance coefficient. the adsorption kinetics, and it was evaluated by monitoring the
The linear equations of the Hermia model were used to evaluate absorbance at 664 nm. The adsorbed amount of MB at time t
the exact fouling mechanisms of electrospun PU and nanofibrous (adsorption capacity (Qt); mg g−1) and the amount of dye adsorbed
PGT composite samples (Table S1). In accordance with the cake at equilibrium [equilibrium adsorption capacity (Qe); mg g−1] on
filtration model (m = 0), the foulant diameter is greater than the electrospun membranes were calculated using eqs 8 and 9,
pores, which causes the formation of a multilayer of foulants on the respectively.37,38

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Figure 3. (a) SEM image of 20-PGT from where EDS was carried out and elemental mapping of (b) carbon, (c) oxygen, (d) nitrogen, (e) silicon,
(f) magnesium, (g) aluminum, (h) iron, and (i) sodium.

C0 Ct spun composite membranes at four GO-Mt hybrid filler

Qt = ×V
m (8) loadings (5−20%) are given in Figure 2b−e. The average fiber
diameter is shown in Figure 2f.
C0 Ce
Qe = ×V The GO-Mt hybrid filler loadings significantly influenced
m (9)
both the morphology and the fiber diameter. The fiber
where C0 and Ce, Ct, respectively, represent the initial concentration, diameters of neat electrospun PU, 5-PGT, 10-PGT, 15-PGT,
equilibrium concentration, and concentration at time t (mg L−1), V is and 20-PGT are 780, 650, 632, 549, and 384 nm, respectively.
the volume of the MB solution in liter, and m represents the weight of This steady reduction in fiber diameter may be brought about
the adsorbent (g). by the GO-Mt-modified PU solution’s improved electrical
Reusability of the PGT electrospun composite membrane was
assessed using duplicate adsorption−desorption tests and expressed as conductivity. The electrical conductivity of PU solution and
percentage removal efficiency (R %). MB-adsorbed composite different PGT solutions is tabulated in Table S2. As the GO-
membranes were treated with 1N HCl for 5 h with 400 rpm Mt loading increased, the conductivity of the PGT polymer
continuous agitation for desorption of MB. MB desorption capacity solution also increased; hence, the charge density over the
was calculated by the following equation.39 polymer solution during electrospinning was increased. The
Cf increased conductivity was attributed to the electron transport
Q e , desorption = ×V property of GO and the ion exchangeable property of Mt in
m (10)
the GO-Mt hybrid filler.41 The polymer solution had a more
where Cf represents the MB concentration in desorption solution (mg significant charge distribution; the polymer jet elongates
L−1), V is the volume of the MB solution in liter, and m represents the during flight time with whipping motions, resulting in fibers
weight of the adsorbent (g).
The following equation was used to calculate the desorption with an optimum diameter. The enhanced electrical con-
efficiency of MB.39 ductivity of the polymer solution at higher filler loadings is the
primary reason for this whipping instability-assisted jet
Q e , desorption elongation.42 The fiber morphology significantly changed
D(%) = × 100
Q e , adsorption (11) from the beaded fiber to interconnected fiber and, finally,
rodlike thin fibers. The olive-like beaded fiber morphology in
where Qe, desorption, and Qe, adsorption, represent the MB
desorption capacity and adsorption capacity (mg g−1), respectively. 5-PGT was due to the lowest GO loading, which disappeared
The following equation was used to calculate the removal efficiency from the composites due to their higher GO-Mt loadings.43
of MB by the electrospun membrane during dynamic and batch The beaded structure was due to the jet-breaking tendency of
adsorption studies.40 polymer jets during whipping motion owing to the Rayleigh
C0 Cf instability.44 Due to the presence of beads, 5-PGT showed the
R(%) = × 100 highest fiber diameter among all electrospun composite
C0 (12) membranes. As mentioned earlier, the absence of beads in
−1
where C0 and Cf represent the MB concentration (mg L ) before the higher GO-Mt loadings in composite fibers may be due to
adsorption and after adsorption, respectively. the enhanced stretching of polymer jets during whipping
motions. As a result of jet elongation due to the improved
3. RESULTS AND DISCUSSION conductivity, 10-PGT showed interconnected random bead-
3.1. Morphology and Elemental Analysis of Electro- free fibers following a change in beaded to fine bead-free fiber
spun Composite Membranes. Figure 2a shows the SEM morphology. At more significant GO-Mt loadings, the polymer
image of pristine electrospun PU. SEM micrographs of jet was properly stretched and elongated, resulting in thin,
polyurethane/graphene oxide-montmorillonite (PGT) electro- bead-free fibers with a rodlike morphology that were seen in
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Figure 4. (a) IR spectra of GO, GO-Mt, electrospun PU, and 20-PGT and inset showing the enlarged spectrum of carbonyl stretching and (b)
enlarged spectra of −OH stretching in electrospun PU and various composites. (c) Raman spectra of GO, GO-Mt, and different electrospun
composites. (d) XRD patterns of various samples. (e) TGA curves of samples. (f) DTG curves of samples. (g) Stress−strain curves of electrospun
samples. (h) Young’s modulus and tensile strength of all samples. (i) Porosity and pore size of samples.

15-PGT and 20-PGT. Figure 2g,h, respectively, shows
electrospun PU and 20-PGT EDS spectra. The elemental
mapping of 20-PGT is shown in Figure 3, and it shows the
uniform distribution of elements in the composite. These
confirmed the presence of Si, Mg, Al, Fe, and Na, which are the
characteristic elements of Mt. Moreover, the presence of C, O,
and N is attributed to the GO and PU backbone.
3.2. Basic Material Characterization of Electrospun
Composite Membranes. Figure 4a shows the FT-IR spectra
of various samples in the ATR mode. The GO-Mt hybrid
nanofiller showed a broad peak in the range of 3697−2370
cm−1 corresponding to the −OH vibrations from GO and the
silanol of Mt. Its intensity was increased dramatically, and it
suggested the presence of sufficient −OH from GO and silanol
and their stabilized interaction via hydrogen bonding.20 The
peak corresponding to the epoxy group in GO was not visible
in GO-Mt, whereas a strong peak was visible at 1633 cm−1,
which corresponds to the C�C vibration and −OH bending
mode. It confirmed the absence of epoxy functional groups in
GO-Mt due to the recovery of sp2-hybridized carbon during
GO-Mt composite formation.45,46 Electrospun PU showed its
prominent peak at 3325 cm−1 ascribed to the υN‑H and other
dual peaks at 1715 cm−1 and 1690 cm−1, respectively, owing to
free υC�O and intermolecular hydrogen-bonded υC�O.
Interestingly, the carbonyl stretching of 20-PGT was deformed
to a single peak at 1691 cm−1 instead of a doublet peak (inset
4641
of Figure 4a). It indicated the domination of hydrogen-bonded
C�O rather than free C�O.47 Moreover, compared to the
pristine electrospun PU, the carbonyl peak’s intensity was
higher in the electrospun composites. It was attributed to the
stabilized hydrogen bonding and ionic interactions between
the C�O group and the GO-Mt filler.48 Figure 4b shows the
−N−H and −O−H stretching spectra of all samples. All
samples showed −N−H stretching at 3324 cm−1, whereas all
PGT electrospun composites showed a broad peak in the range
of 3687−3024 cm−1. Moreover, the intensity increased as GO-
Mt loadings increased. So, the formation of PGT composites
with stabilized interaction was confirmed.
The Raman spectra of GO, the GO-Mt hybrid nanofiller,
and electrospun composite membranes (PGT) are shown in
Figure 4c. GO showed its prominent peaks at 1351 and 1592
cm−1, respectively, for the D band and G band. The GO-Mt
nanofiller and all electrospun composite samples showed the
presence of D and G bands. Compared to the pristine GO, a
significant shift in the peak position was observed. The
significant peak shift of the D band and the G band to 1343
and 1596 cm−1 indicated the interaction of Mt and GO in the
GO-Mt hybrid filler.49 The ID/IG ratio of GO and GO-Mt was
found to be 1.0774 and 0.9281, respectively. The decreased ID/
IG of GO-Mt was owing to the presence of exfoliated GO by
the ultrasonication-assisted composite formation.50 Moreover,
compared to pristine GO, the ID/IG ratio of GO-Mt was
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Figure 5. (a) Water contact angle of electrospun samples, (b) time-dependent contact angle of the 20-PGT electrospun composite membrane, (c)
pressure-driven and gravity-driven pure water flux of all samples, and (d) water flux of various samples at different operating pressures.
considerably lower, indicating a higher degree of graphitization
by repairing the defect.51 Every PGT composite sample
showed a reduced ID/IG ratio. It confirmed the presence of
hybrid GO-Mt rather than free GO in the electrospun
composite samples.
X-ray diffractograms of all samples are shown in Figure 4d.
GO-Mt showed a prominent peak ascribed to the basal spacing
of GO at 2θ equal to 11.66°. In the electrospun composites, it
was shifted to lower 2θ, which means that basal spacing was
increased considerably during composite formation.52 Mt
showed its basal peak (d100) at 2θ equal to 5.76°, but in all
electrospun composite samples, this peak was significantly
shifted to a higher 2θ value, and an increase in the intensity
was observed as the Mt loading was increased. Moreover, a
peak ascribed to the semi-crystalline nature of electrospun PU
at 2θ equal to 19.06° was shifted to higher 2θ value in all
electrospun composite samples. This further confirmed the
composite formation.
The thermal stability of electrospun PU and PGT electro-
spun composite membranes was investigated by TGA and
derivative thermogravimetric (DTG) analysis. TGA and DTG
curves of various samples are shown in Figure 4e,f, respectively.
Both electrospun PU and PGT electrospun composite
membranes showed two-step degradation. The first weight
loss was ascribed to the degradation of the hard segment’s
peptide bond, and the second weight loss was owing to the
putrefaction of the soft segment’s ether bond. All PGT
electrospun composite membranes showed better thermal
stability compared to the neat electrospun PU. The increased
onset degradation temperature of PGT composites and residue
(%) was correlated to the so-called thermal stability (Table
S3). It may be due to the proper distribution of the thermally
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stable GO-Mt filler in the PU matrix.53 So, the formation of a
thermally stable electrospun composite membrane was
confirmed.
Due to their prolonged use, mechanically strong fibrous
membranes have attracted a lot of attention in the filtration
sector. Figure 4g shows the stress−strain curves of all samples.
Electrospun PU exhibited the least tensile strength of 2.6 MPa
and the least percentage elongation of 192%. A gradual
increase in the tensile strength was observed as GO-Mt
loadings were increased (Figure 4h). 5-PGT showed the
highest percentage elongation of 362%. Even though GO-Mt
loading increased, percentage elongation dropped. It was
attributed to the increment in brittle nature as the GO-Mt
content was increased.54 The highest percentage elongation of
5-PGT was due to the existence randomly interconnected
fibers.55 Moreover, 5-PGT showed the least Young’s modulus
of 0.01 MPa. The presence of the highest percentage
elongation and the least Young’s modulus can offer better
flexibility to the composite. 20-PGT offered the highest tensile
strength of 6.6 MPa, and it was due to the proper distribution
of the mechanically reinforcing GO-Mt filler in the matrix.56
So, 20-PGT is considered as a promising candidate for
filtration applications with appreciable mechanical properties.
Porosity and pore size are important factors affecting the
filtration performance of membranes (Figure 4i). The pristine
PU membrane showed a minimum porosity of 47%. As the
GO-Mt loading increased, porosity also increased. 20-PGT
showed the highest porosity of 61%. This enhanced porosity
can offer better filtration performance for the composite
samples.26 A gradual decrease in the pore size was observed as
it moved from electrospun PU to 20-PGT. The electrospun
PU shows the largest pore size of 1309 nm, and 20-PGT
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Figure 6. (a) Home-built gravity-driven flux apparatus; (b) time-dependent gravity-driven flux of ABS, PMMA, and PS MNP suspensions through
20-PGT; and (c) RFD of 20-PGT during various MNP suspension filtrations. (d) FRR and removal efficiency of 20-PGT during various MNP
filtrations. (e) Reusability of the 20-PGT electrospun membrane for 10 filtration cycles. (f) TOC of feed and permeate for various MNP filtrations.
showed the relatively smallest pore size among all PGT
composite membranes. It helps the interception when MNPs
have a diameter greater than the pore size (dMNPs > dpore). So,
the 20-PGT electrospun composite membrane is considered a
promising material for water filtration and MNP filtration
applications.
3.4. Water Flux Evaluation. In water filtration applica-
tions, the membrane’s hydrophilicity is a critical component.
The water contact angle of various samples is shown in Figure
5a. The maximum water contact angle was recorded by
electrospun PU at 109 ± 1.2°, which can be attributed to its
hydrophobic nature and surface roughness. As GO-Mt
loadings increased, the contact angle gradually decreased. A
time-dependent contact angle was monitored to ensure the
superhydrophilic nature of 20-PGT (Figure 5b). After 10 s, 20-
PGT showed no water contact angle (0°), confirming the
sample’s superhydrophilicity. The superhydrophilicity was due
to the abundant hydrophilic functional groups such as
−COOH, and −OH, in GO-Mt, the inherent hydration
property of Mt, and the improved surface roughness of the
fibrous membrane.57
Electrospun PU showed an average surface roughness (Ra)
parameter of 25 nm (Figure S3). The roughness of the PU-
based composite fibrous membranes increased as the GO-Mt
loading increased. 5-PGT, 10-PGT, 15-PGT, and 20-PGT
showed Ra values of 31, 43, 51, and 62 nm, respectively. This
increase in surface roughness may be due to the formation of
fibers with a small diameter. According to the Wenzel model,
as surface roughness increases, the hydrophobic surface will be
more hydrophobic than the smooth surface. As surface
roughness increases, the hydrophilic surface will be more
hydrophilic compared to the smooth surface.58 So, electrospun
PU showed the highest hydrophobicity, and 20-PGT with the
highest roughness and more hydrophilic GO-Mt contents
made it superhydrophilic with a contact angle of 0°.
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When assessing the membranes’ ability to filter impure
substances from water, water flux is an essential factor to take
into account. Gravity-driven apparatus and stirred ultra-
filtration cell apparatus were used to evaluate the water flux
of various samples.25 A video of gravity-driven water flux is
given in Supporting video SV1. Figure 5c shows the gravity-
driven (0.135 psi) and pressure-driven water flux (5 psi) of
different electrospun samples. Gravity-driven water flux was
explored due to its free-energy consumption. Under gravity-
driven water flux, PU and 20-PGT showed water fluxes of 0
and 793 ± 34 L m−2 h−1, respectively. Even though PU has
significant porosity (47%) and pore size (1308 nm), it could
not show water flux. It was owing to the inherent hydrophobic
backbone of the polyurethane polymer, which can prevent the
permeation of water molecules through the pores of electro-
spun PU. Interestingly, PGT electrospun composite mem-
branes showed significant water flux compared to electrospun
PU. As the GO-Mt filler loading was increased, the pressure-
driven and gravity-driven water fluxes of the electrospun
composite membranes were increased. It was due to the
increased porosity and the enhanced hydrophilic nature of the
composite membranes. The dependency of the operating
pressure was investigated, and it is shown in Figure 5d. As the
operating pressure increased from 1 to 5 psi, the water flux of
all samples also increased. However, after 5 psi, the flux of all
samples decreased slightly. It was due to the fiber compaction
at higher pressure, which adversely affects the porosity and
pore size of the fibrous membrane. It has been reported that
commercially available Millipore MF membranes with a 0.2
μm pore size, such as PVDF and mixed cellulose esters
(MCEs), can show pure water flux at 10 psi pressure,
respectively, of 3624 and 6227 L m−2 h−1.59 The present
work reported the maximum water flux of 20-PGT as 8163 L
m−2 h−1 at 5 psi pressure, which is much higher than the
commercially available Millipore MFs. Moreover, it showed a
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ACS Applied Nano Materials
Figure 7. SEM images of MNPs and their size distribution curve before filtration. (a) ABS, (b) PMMA, and (c) PS and SEM images of MNPs on
the 20-PGT electrospun surface after filtration. (d) ABS MPs, (e) PMMA NPs, and (f) PS NPs. (g) Schematic representation of the separation
mechanism of MNPs by the 20-PGT electrospun membrane.
higher gravity-driven water flux of 793 L m−2 h−1 compared to
the recently reported studies.24 So, the 20-PGT electrospun
composite membrane has been chosen for the MNP separation
and dye adsorption studies.
3.5. MNP Separation and Mechanisms. Polymers such
as ABS, PS, and PMMA are widely used polymers that are
found in water resources in the form of MNPs.60 For MNP
separation studies, ABS nanofiber-based MPs, PMMA, and PS
NPs were prepared and made homogeneous dispersion in
water (10 ppm). MNP removal studies were carried out using
a home-built gravity-driven flux apparatus, and it is shown in
Figure 6a. The entire filtration was performed with the
optimized 20-PGT electrospun membrane without any
supporting substrate. The time-dependent gravity-driven flux
of MNP suspensions such as ABS, PMMA, and PS through 20-
PGT is shown in Figure 6b. Compared to the pure water flux,
every MNP suspension exhibited a reduced flux due to the
significant fouling from MNP foulants. The R2 values from
various fouling mechanisms of each filtration are tabulated in
Table S4. ABS MP filtration followed the cake formation
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mechanism (R 2 = 0.9997), PMMA NPs obeyed an
intermediate blocking mechanism (R2 = 0.9998), and PS
NPs best fitted the standard blocking model (R2 = 0.9907).
Since the size of ABS MPs is greater than the pore size (624
nm) of the 20-PGT electrospun composite (dMPs > dpores), MPs
were intercepted by the fibrous membrane, leading to the
origin of the cake layer. This developed cake layer on the
composite surface caused an extensive RFD of 85% during
ABS MP filtration (Figure 6c). However, the FRR of ABS
filtration was the highest (99%) (Figure 6d). Because of the
easy removal of the cake layer of ABS MPs on the membrane
in the first cycle, the original flux of water can be recovered by
rinsing the membrane with distilled water. This cake layer was
responsible for the enhanced rejection, with a removal
efficiency of 98% of ABS MPs (Figure 6d). PMMA and PS
NPs showed slightly reduced removal efficiencies of 97 and
95%, respectively. This reduced removal efficiency of NPs by
the composite fibrous membrane was due to their small size
compared to the ABS MPs. However, every NPs showed
removal efficiencies above 90%.
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Figure 8. (a) UV−visible spectra of the dye mixture during selective MB adsorption on the 20-PGT electrospun composite membrane. (b) MB
adsorption capacity of various fibrous membranes. (c) Dynamic flux of MB solution through the 20-PGT sample at different time intervals. (d) MB
removal efficiency during dynamic filtration by 20-PGT.
The filtration of PS NPs showed the least flux decay and
FRR. As seen from the fouling mechanism, filtration of PS NPs
follows the standard blocking model, in which the foulants
adhered to the inner wall of the electrospun fibers.61 Here, the
positively charged PS NPs (ζ potential of ca. +38 mV) were
adsorbed on the negatively charged electrospun composite
fibers (ζ potential of ca. −42 mV) via electrostatic attraction.
The negative charge of the GO-Mt-loaded electrospun
composite (20-PGT) was confirmed by the ζ potential
distribution curve, and it is shown in Figure S4. The adsorption
of PS on the electrospun composite was further confirmed by
UV−visible analysis, and it is shown in Figure S5a. The
absorbance of NP suspension before the adsorption study was
higher than that after the adsorption study. Even though PS
NPs were deposited on the inner wall of fibers, there would be
significant pores for water flow. As a result, it showed the
lowest RFD of 30%. However, it showed the lowest FRR
(83%) due to the presence of adsorbed PS NPs even after
washing the membrane.
PMMA NPs showed intermediate flux decay (43%) and
intermediate FRR (93%). As seen from the fouling mechanism,
the filtration of PMMA NPs followed the intermediate
blocking model. Some of the foulants were adsorbed on the
surface of the electrospun fibers, and a few foulants may have
accumulated over the adsorbed NP foulants. The adsorptive
interactions may be due to positively charged PMMA NPs (ζ
potential of ca. +41.7 mV) and the negatively charged
electrospun composite fibers (ζ potential of ca. −42 mV) via
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electrostatic attraction. The UV−visible spectra of PMMA NPs
before and after adsorption are shown in Figure S5b.
The reusability of the membrane was evaluated for 10
filtration cycles (Figure 6e). Flux during ABS MP filtration was
almost constant throughout every filtration cycle. It confirmed
the reusability of the membrane for the multi-filtration of ABS
MPs. In contrast, the flux of PMMA NP and PS NP suspension
decreased slightly to 385.87 and 395 L m−2 h−1, respectively,
for the 10th filtration. The constant flux of ABS MPs in various
filtration cycles was due to the easily removable ABS MP cake
layer, and the slight flux reduction in the case of PMMA and
PS NP filtration was attributed to the adhered NPs. The
removal efficacy of MNPs was further confirmed by TOC
analysis. Figure 6f shows the TOC of the feed before filtration
and permeates after filtration for different MNP filtrations.
Every permeate showed significantly reduced TOC, conform-
ing to the effective MNP separation. Furthermore, the
separation efficiency of MNPs by the 20-PGT membrane
was compared with that of the commercial MCE membrane by
monitoring TOC (Figure S6). The 20-PGT membrane
showed better MNP separation efficiency than MCE. 20-
PGT showed efficiency in the range of 91−93%, whereas MCE
showed efficiency in the range of 83−85%. So, the developed
membrane is considered to be a better material for MNP
separation.
MNP separation efficacy by 20-PGT was further confirmed
by FE-SEM analysis. Figure 7a−c shows SEM micrographs of
prepared MNPs and their particle size distribution curves
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ACS Applied Nano Materials
before filtration. ABS nanofiber-based MPs indicated an
average fiber diameter of 825 nm and an average length of
5972 nm. The PMMA and PS NPs showed an average
diameter of 191 and 93 nm, respectively. Figure 7d−f shows
the SEM images of MNPs on the 20-PGT membrane after
filtration. Figure 7d confirms the existence of intercepted ABS
MPs on the membrane surface after filtration. From the SEM
image, 20-PGT fibers are clearly visible, and it is due to the
fairly distributed ABS MPs on the 20-PGT fiber surface
without any interaction. Figure 7e,f shows the SEM images of
PMMA NPs and PS NPs after filtration, respectively. 20-PGT
electrospun fibers were not visible due to the agglomeration of
NPs and their strong adsorptive interaction with 20-PGT
fibers. Overall, the separation mechanisms identified for ABS,
PS, and PMMA MNP separations were size-exclusive
interception by the membrane, adsorption, and a combined
effect of size-exclusive effect and adsorption phenomena,
respectively (Figure 7g).24
The stability of the membrane after MNP filtration was
investigated. FE-SEM micrographs of 20-PGT after ABS MP
filtration and thoroughly cleaned membrane after filtration are
shown in Figure S7. After ABS MP filtration, SEM showed that
ABS MPs were distributed over the membrane surface, and
after cleaning the membrane, electrospun fibers were clearly
visible. 20-PGT fibers maintained an interconnected, web-like
morphology with a significant porosity. However, a significant
change in the fiber diameter was noticed. After filtration, the
average fiber diameter changed from 384 to 746 nm. Most
likely, it is due to the swelling of fibers during MNP filtration.
The fine morphology after MNP filtration, on the other hand,
indicated its stability. So, 20-PGT is a promising material for
separating various MNPs with different dimensions from
contaminated water.
3.6. Dynamic MB Filtration and Selective MB
Adsorption. The selective adsorption of a cationic dye,
such as MB, was investigated using a MO/MB dye mixture
under batch conditions (Figure 8a). Interestingly, no
adsorption of negatively charged MO was observed. The
selective adsorption of positively charged species provided
additional evidence for the electrospun composite membrane’s
negative charge. The MB adsorption capacity (Qt; mg g−1) of
various fibrous samples is shown in Figure 8b. Electrospun PU
did not show any significant MB adsorption for 500 min,
whereas all electrospun composite samples (PGT) showed
significant MB adsorption. Complete adsorption was achieved
in three stages. At first, the adsorption capacity was increased
quickly (0 to 100 min). Second, the adsorbed amount of MB
was increased slowly between 100 and 300 min. After 300 min,
equilibrium was established. The equilibrium adsorption
capacities (Qe; mg g−1) of 5-PGT, 10-PGT, 15-PGT, and
20-PGT were 95, 146, 177, and 195 mg g−1, respectively. As
the GO-Mt loading was increased, equilibrium adsorption
capacity also increased. Electrostatic attraction and the π−π
stacking interactions between GO-Mt and MB were respon-
sible for the adsorption of MB on the fibrous membrane. The
electrostatic attraction was due to the negatively charged
carboxylate and oxide ions in graphene oxide (GO) and the
presence of the negatively charged basal layer of montmor-
illonite (Mt). The negatively charged basal layer in Mt is
generated by the cation exchange in the tetrahedral sheet (Al3+
for Si4+) and octahedral sheet (Mg2+ for Al3+).62,63 The π
electron cloud of MB and GO in the composite membrane
governs the π−π stacking interactions. Among all the
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composite membranes, 20-PGT showed the highest adsorption
capacity. So, 20-PGT has been selected for extensive
adsorption studies.
Since no adsorption was observed for MO in the batch
experiment, MB was only utilized for the dynamic filtration test
to find out the MB removal ability of the membrane during
dynamic filtration. An MB dynamic removal experiment was
performed using a stirred cell to understand the removal ability
of MB from contaminated water. The UV−visible spectra of
the feed MB solution and permeate through electrospun PU
and PGT are shown in Figure S8. Figure 8c shows the flux of
MB solution through 20-PGT at 5 psi pressure. A video
showing gravity-driven dynamic MB solution filtration and
pressure-driven dynamic MB solution filtration is given in
Supporting Video SV2. A steep decrease in the flux was
observed, and it was due to fouling. During dynamic filtration
by 20-PGT, the fouling mechanism was investigated
thoroughly (Figure S9). It followed the standard blocking
model (R2 = 0.9999), in which MB molecules were adhered on
the inner wall of the electrospun fiber. Over a 2 to 18 min time
period, dynamic MB filtration showed a constant removal
efficiency of 99%. It was determined by measuring the
absorbance of feed MB and permeate MB at 664 nm.
However, after 18 min, it started to reduce, decreasing to
95% (Figure 8d). It was owing to the MB saturation of the
composite membrane.
The reusability of the membrane was expressed by its
removal efficiency (R %). For calculating the removal efficiency
during the batch experiment, desorption studies were
conducted. The desorption efficiency (D %) during the
batch experiment is shown in Figure S10a. It showed a
desorption efficiency above 95% over six cycles. Figure S10b
shows the removal efficiency during batch adsorption for six
cycles. A slight decrease in the removal efficiency was observed
as it moved from the first cycle (98%) to the last cycle (96%).
This slight reduction in the removal efficiency may be due to
the unavailability of fiber surfaces for adsorption due to the
fractional coverage of previously adsorbed MB. The reusability
of the membrane after dynamic MB filtration was further
investigated by SEM analysis. SEM micrographs of 20-PGT
after flux and MB dynamic filtration are shown in Figure
S10c−d. It preserved an interconnected, web-like morphology
and porosity. However, a slight flattening of the fibers on the
surface was noticed, along with an increase in fiber diameter to
664 nm, probably due to the swelling of fibers during MB
adsorption and dynamic flux. However, 20-PGT is a promising
material for laboratory-scale dynamic MB removal from
contaminated water.
3.7. Adsorption Kinetics and Isotherm. Detailed
adsorption kinetic and isotherm studies were performed
under batch adsorption. The MB adsorption kinetics on 20-
PGT electrospun composite membranes was investigated using
pseudo-first-order and pseudo-second-order kinetic models.
The following formula represents the pseudo-first-order
model.64
ln(qe qt) = ln(qe) k1t (13)
where qt (gg−1) represents the adsorption capacity at t, qe
(gg−1) stands for the equilibrium adsorption capacity, and k1
represents the pseudo-first-order rate constant (min−1).
Equation 14 describes the pseudo-second-order model.64
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Table 1. Regression Coefficient, Kinetic, and Adsorption Isotherm Parameters for the MB Adsorption on the 20-PGT
Electrospun Membrane
kinetics models and parameters Adsorption isotherms
pseudo-first-order pseudo-first-order Langmuir Freundlich
qe, exp (mg g−1) 195 195 qm (mg g−1) 417 n 1.2
qe, calc (mg g−1) 175 204 KL ( L mg−1) 0.03 KF 12
k 0.02 0.0001 R2 0.9998 R2 0.9678
R2 0.9847 0.9982

Table 2. Comparison of Various Membranes Used for MNP Separation and Dye Adsorption with the Present Studya
water flux (L m−2h−1)
membrane application MPs/NPs gravity-driven pressure-driven qm (mg/g) ref
24
PVDF-PET NPs removal only PS NPs 109 N/A N/A
68
PS-MOF MPs and dye removal PE and PVC MPs N/A 72 (at 43.5 psi) N/A
69
OPASS-U dye adsorption only N/A N/A N/A 53 (MB)
70
PVDF/PDA/β-CD MB and PHP adsorption N/A N/A N/A 188 (MB)
204 (PHP)
25
PAN NPs removal only PS NPs N/A 861 (at 0.6 psi) N/A
PU/GO-Mt (PGT) MNP separation and selective dye ABS, PMMA, and PS 793 8163 (at 5 psi) 417 (MB) this study
adsorption MNPs
a
Note: MPs: microplastics; NPs: nanoplastics; MNPs: micro- and nanoplastics; qm: adsorption capacity; MB: methylene blue; PHP:
phenolphthalein; and N/A: not available.

t 1 t value and isotherm parameters are shown in Table 1. The

= +
qt 2
k 2qe qe
where k2 denotes the pseudo-second-order rate constant (gg−1
min−1), qe (gg−1) represents the adsorption capacity at
equilibrium condition, and qt (gg−1) represents the adsorption
capacity at time t.
Figure S11a,b, respectively, shows the pseudo-first-order and
pseudo-second-order kinetic models for MB adsorption on the
20-PGT fibrous composite membrane during a batch experi-
ment. The kinetic parameters and correlation coefficient (R2)
for the adsorption process are shown in Table 1. The R2 value
for the pseudo-second-order kinetic model is closer to unity,
and the estimated adsorption capacity at equilibrium (qe,
calcd) is in good agreement with the experimental data. The
MB adsorption by the 20-PGT electrospun composite
membrane was thus determined to be a kinetic process
involving the pseudo-second-order kinetic mechanism.
The Freundlich and Langmuir adsorption isotherms were
used to investigate the MB adsorption isotherm on 20-PGT.
The following equation represents the Langmuir adsorption
isotherm.65
Ce C 1 from the water. The UV−visible spectra of feed solution and
= e +
qe qm KLqm
where Ce (mg L−1) is the equilibrium concentration of MB, qe
(mg g−1) represents the equilibrium adsorption capacity, KL (L
mg−1) is the Langmuir adsorption equilibrium constant, and
qm (mg g−1) represents the maximum adsorption capacity.
The following formula represents the Freundlich adsorption
isotherm.65
1
log qe = log Ce + log KF
n (16)
where KF (L mg−1) is the Freundlich constant, C is the
concentration (mg L−1), and n is the empirical parameter.
The Freundlich and Langmuir isotherms of MB adsorption
on 20-PGT are shown in Figure S11c,d, respectively. The R2
(14)
Langmuir adsorption isotherm’s R2 value is closer to one. As a
result, the MB adsorption on the 20-PGT electrospun
composite membrane satisfied the Langmuir adsorption
isotherm. During adsorption, MB has been adsorbed in a
monolayer on the nanofibrous composite membrane. The
maximum adsorption capacity was 417 mgg−1. The “RL” value
of the adsorption was found to be 0.4, indicating that the
reaction was favorable (0 < RL < 1).
Even though GO has attractive properties, it poses some
nanotoxicity to the human body.66 As a result, we attempted to
reduce the GO content by creating a GO-Mt hybrid filler
without compromising the dye adsorption property. A GO-
modified polyurethane-based electrospun composite mem-
brane showed a 109 mg/g adsorption capacity toward MB.67
In the present work, 20-PGT showed an MB adsorption
capacity of 417 mg/g. So, GO-Mt-modified electrospun
membranes can be considered a better material for dye
adsorption than the GO-modified electrospun membrane.
Furthermore, a preliminary simultaneous filtration of MB and
MNPs has been performed to verify the efficacy of the
membrane in the simultaneous filtration of MB and MNPs
permeate are shown in Figure S12. It showed 98% removal
(15) efficiency during filtration. A comparative study of the present
work with various reports related to dye adsorption and MNP
separation is tabulated in Table 2. The present work has a dual
effect on MB dye adsorption and MNP separation from
wastewater with high gravity-driven and pressure-driven water
flux and significant MB adsorption capacity. So, the developed
membrane can open a spectrum of opportunities in the
filtration sector.
4. CONCLUSIONS
Dual functional PU-based electrospun composite membranes
were successfully fabricated, with effective MNP separation
and selective MB adsorption from wastewater. GO-Mt-
modified electrospun composite membranes showed super-
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ACS Applied Nano Materials
hydrophilicity, outstanding gravity-driven water flux (793 L
m−2 h−1), and pressure-driven water flux (8163 L m−2 h−1). It
outperformed electrospun PU in mechanical and thermal
properties. Using an optimized 20-PGT electrospun composite
membrane, three types of model MNPs, such as ABS, PMMA,
and PS, were effectively removed from water in the gravity-
driven mode. Since the pressure was much lower than the
operating pressure of the MF/UF membranes, it was
considered an energy-saving method to separate MNPs.
During filtration, the MPs (ABS) were removed by the
membrane based on the size-exclusive effect, whereas the NPs
(PMMA and PS) were separated by adsorption. The ABS,
PMMA, and PS MNPs followed cake formation, intermediate
blocking, and standard blocking fouling mechanisms, respec-
tively. It confirmed the separation of MNPs by the electrospun
composite membrane. The electrospun composite membrane
showed a significant selective MB adsorption capacity of 417
mg g −1 from the MB/MO mixture. The adsorption
phenomenon follows a second-order kinetic model and a
Langmuir adsorption isotherm. So, the 20-PGT electrospun
composite membrane is a potential candidate for the removal
of MNPs and MB dye from contaminated water and can open
up a new spectrum of opportunities in the field of MF.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsanm.3c00112.
Preparation of graphene oxide, preparation of micro-
plastics and nanoplastics, property evaluation of the GO-
Mt hybrid filler, conductivity of PGT solution, Hermia
fouling models, TGA parameters, AFM images, ζ
potential curve, UV−visible spectra of MNP adsorption,
efficiency comparison with MCE, SEM image showing
stability, UV−visible spectra of MB adsorption, fouling
mechanism during MNP filtration, efficiency and
reusability, adsorption isotherm and kinetics, and the
UV−visible spectra of simultaneous filtration (PDF)
Gravity-driven water flux (MP4)
Dynamic MB filtration (MP4)
■ AUTHOR INFORMATION
Corresponding Author
Athiyanathil Sujith − Materials Research Laboratory,
Department of Chemistry, National Institute of Technology
Calicut, Kozhikode 673601 Kerala, India; orcid.org/
0000-0003-3278-5343; Phone: +91 9846475675;
Email: athiyanathil.sujith@gmail.com, sujith@nitc.ac.in
Authors
Kandiyil Juraij − Materials Research Laboratory, Department
of Chemistry, National Institute of Technology Calicut,
Kozhikode 673601 Kerala, India; orcid.org/0000-0002-
3196-5759
Saeed Punnoli Ammed − Materials Research Laboratory,
Department of Chemistry, National Institute of Technology
Calicut, Kozhikode 673601 Kerala, India; Department of
Chemistry, Government Engineering College Wayanad,
Wayanad 670644 Kerala, India
C Chingakham − Materials Research Laboratory, Department
of Chemistry, National Institute of Technology Calicut,
Kozhikode 673601 Kerala, India; Department of Chemistry,
4648
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National University of Singapore, Singapore 117543,
Singapore
Brindha Ramasubramanian − Center for Nanotechnology and
Sustainability, Department of Mechanical Engineering,
College of Design and Engineering, National University of
Singapore, Singapore 117575, Singapore
Seeram Ramakrishna − Center for Nanotechnology and
Sustainability, Department of Mechanical Engineering,
College of Design and Engineering, National University of
Singapore, Singapore 117575, Singapore
Suni Vasudevan − Materials Research Laboratory,
Department of Chemistry, National Institute of Technology
Calicut, Kozhikode 673601 Kerala, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.3c00112
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledge center for Raman analysis,
NIT Calicut, and CeNSE Bangalore for FESEM analysis.
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