Journal of Environmental Management 371 (2024) 123242

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Journal of Environmental Management

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

Research article

Nanocomposite membrane for simultaneous removal of dye and heavy

metal ions from wastewater
Fathima Arshad a,b, Delal E. Al Momani a,b , Wiebe M. de Vos c , Linda Zou a,b,*
a
Department of Civil Infrastructure and Environment Engineering, Khalifa University of Science and Technology, Abu Dhabi, PO Box 127788, United Arab Emirates
b
Research and Innovation Center for Graphene and 2D Materials (RIC2D), Khalifa University, United Arab Emirates
c
Membrane Science and Technology, University of Twente, MESA+ Institute for Nanotechnology, P.O. Box 217, 7500 AE, Enschede, the Netherlands

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

Keywords: A catalytic 2D nanocomposite membrane (CNC) was fabricated and used for the simultaneous removal of
MoS2 methylene blue (MB) and heavy metal ions in aqueous solution. Both molybdenum disulfide (MoS2) and gra­
Graphene oxide phene oxide (GO) were incorporated in a chitosan polymer matrix, and the fabricated CNC membrane exhibited
Catalytic effect
performance as a nanofiltration membrane. Here MoS2 activated H2O2 to generate very reactive oxygen species
Reactive oxygen species
(ROS), such as hydroxyl radicals, allowing the catalytic breakdown of the organic dye contaminants and reducing
Simultaneous removal
heavy metal ions. Greater than 99% efficiencies were achieved for the simultaneous removal of methylene blue
(MB) and the heavy metal Co2+. Moreover, significant removal efficiencies in the 89–96% range were demon­
strated for other heavy metal ions of Cu2+, Pb2+, and Ni2+. The generated ROS were trapped by terephthalic acid
(TA) and confirmed by fluorescence emission spectroscopy. The used membrane was regenerated and reused
with a flux recovery rate of more than 91% after 4 experimental cycles. These promising results indicated that
the novel catalytic 2D nanocomposite membrane showed a high potential for the simultaneous removal of
organic contraminants and heavy metal ions from textile industry wastewater.

1. Introduction membrane filtration, adsorption, advanced oxidation processes, and

catalytic decomposition techniques each bearing its own advantages and
The increasing global demand for clean water resources has accel­ limitations (Kumar et al., 2023). While proficient in separating con­
erated the critical need for improved wastewater treatment strategies taminants from water, membrane filtration typically leads to the for­
such as membrane filtration, adsorption, advanced oxidation processes, mation of concentrated waste streams that require further treatment (Lu
and catalytic decomposition techniques (Silva, 2023). In particular, in­ et al., 2009). Similarly, adsorption techniques face challenges associated
dustrial effluents such as textile manufacturing, metal plating, and with the regeneration of adsorbents and the disposal of residual waste
electronics production often present a multifaceted challenge, contain­ (Chai et al., 2021). Meanwhile, photocatalysts like titanium dioxide
ing diverse contaminants, including organic pollutants such as dyes and (TiO2) exhibit commendable contaminant removal capabilities. Still,
various heavy metal ions such as cobalt (Co2⁺), copper (Cu2⁺), lead they cannot function as effective separation barriers and typically
(Pb2⁺), and nickel (Ni2⁺), (Azimi et al., 2017; Kumar et al., 2023; Tariq require high-energy inputs such as ultraviolet (UV) irradiation
et al., 2006). For example, the wastewater from textile industries not (Al-Mamun et al., 2019).
only contains synthetic dye chemicals but also contains toxic metals Considering these challenges, the integration of hierarchical nano­
such as Co2⁺, Cu2⁺, Pb2⁺, Ni2⁺, and Cr2+ (Ajiboye et al., 2021; Velusamy materials, namely molybdenum disulfide (MoS2) and graphene oxide
et al., 2021). These ions are particularly concerning due to their (GO) into polymer membranes, provides a new opportunity to address
non-biodegradable nature and ability to bioaccumulate in the environ­ the contaminants in wastewater (Kurian, 2021; Mao et al., 2023; Tian
ment, which pose a significant threat to surface water and can harm et al., 2021). MoS2 is well-known as a layered 2D transition metal
human health (Safiul et al., 2020). dichalcogenide (TMDC). Still, its redox catalytic properties, i.e., when
Conventional methods to remove these contaminants include combined with hydrogen peroxide (H2O2) (Li et al., 2020) to generate

* Corresponding author. Department of Civil Infrastructure and Environment Engineering, Khalifa University of Science and Technology, Abu Dhabi, PO Box
127788, United Arab Emirates.
E-mail address: [email protected] (L. Zou).

https://doi.org/10.1016/j.jenvman.2024.123242
Received 22 April 2024; Received in revised form 5 August 2024; Accepted 2 November 2024
Available online 4 November 2024
0301-4797/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
F. Arshad et al. Journal of Environmental Management 371 (2024) 123242

highly reactive radicals to break down recalcitrant contaminants, are 2. Methodology

still less recognized and reported. Utilizing the mechanism of generating
reactive oxygen species (ROS) could allow for the degradation of organic 2.1. Materials
molecules and the reduction of heavy metal ions (Chen et al., 2023). On
the other hand, GO, characterized by its two-dimensional sheet struc­ All chemicals and reagents utilized in nanoparticle synthesis, mem­
ture, offers a suitable material for facile membrane fabrication and en­ brane fabrication, characterization, and analytical investigations were
hances the overall efficacy of the treatment process (Mohammed, 2022). of high scientific purity and employed without any alterations. Specif­
Until now, there is a lack of literature regarding the fabrication of ically, L-cysteine (97%), sodium molybdate dihydrate (99%), hydro­
polymer membranes enhanced by combined MoS2 and GO as an effec­ chloric acid (37%), chitosan (MW 30000), polyethylene glycol (PEG)
tive solution for wastewater treatment. (Mn 400), methylene blue (>95% dye content), potassium permanga­
MoS2, with its catalytic properties, can generate ROS through a nate (99%), humic acid (95%), sulfuric acid (97%), nitric acid (65%),
process called photocatalysis (Li et al., 2018) that can be utilized in and sodium hydroxide (98%) were procured from Sigma-Aldrich.
mixed contaminants simultaneous removal. For example, by utilizing its Additionally, heavy metal salts, including Copper (II) chloride, Cobalt
catalytic properties, Saha et al. demonstrated the effectiveness of (II) chloride, Nickel (II) chloride, and Lead (II) chloride, were sourced
amorphous MoS2 microparticles in treating a mixture of organic dyes. from Sigma Aldrich. The solvents employed in this study, namely
The complete breakdown of dyes into CO2 and H2O was mainly caused ethanol (99.7%), acetic acid (99%), and hydrogen peroxide (35%), were
by (•OH) radicals, with some contribution from (•O -2) (Saha et al., obtained from Honeywell.
2018). The same radicals were also employed in the reduction/de­
gradation of Cr (VI) and MB by Co-doped MoS2 nanosheets (Win et al., 2.2. Nanomaterials preparation
2019). GO, on the other hand, with its abundant functional groups, can
also generate ROS through a process called Fenton-like reactions that 2.2.1. Graphene oxide
received much attention in the treatment process for different contam­ Graphene oxide synthesis in this study was conducted using the
ination degradation (Divyapriya and Nidheesh, 2020; Jain et al., 2020). Modified Hummer’s Method (Al Suwaidi et al., 2019). This process
There is an absence of studies utilizing catalytic 2D nanocomposite began with 1 g graphite flakes, which were carefully mixed into 120 mL
membranes for the simultaneous removal of both dyes and heavy sulfuric acid (H2SO4) and sodium nitrate (NaNO3) solution. 6 g of po­
metals. tassium permanganate (KMnO4) was then added ensuring the mixture’s
In this study, MoS2 and GO were employed as nanomaterial additives temperature was controlled to remain below 10 ◦ C using an ice bath. The
into a chitosan polymer matrix to fabricate a novel catalytic two- solution was stirred continuously at 35 ◦ C for 2 h using a magnetic
dimensional nanocomposite membrane (CNC). Chitosan is a poly­ stirrer, allowing further oxidation. The mixture was then with H2O2
saccharide biopolymer and is considered a green polymer material. It solution and then filtered under a vacuum condition to separate the solid
was chosen because of its high solubility in an aqueous solution and its components from the liquid. The resulting GO was washed by HCl so­
compatibility with water-based MoS2 nanoparticle dispersion and GO lution and DI water, to obain thewell-exfoliated nanosheets. 1 g of
dispersion. It was reported that when MoS2 interacted with H2O2, it led graphite flakes yielded 2 g of GO.
to the generation of ROS such as hydroxyl radicals (•OH) and singlet
oxygen (1O₂) (Saha et al., 2018). In contrast, GO acted as catalyst sup­ 2.2.2. MoS2 nanospheres and MoS2 nanoplatelets
port, increasing both the stability and efficiency of MoS2 in generating Spherical MoS2 nanostructures were fabricated utilizing the hydro­
ROS. These ROS allowed the simultaneous degradation of dyes and thermal method through a bottom-up approach. The environmentally
reduction of heavy metals present in wastewater. The combination of friendly reagent, L-cysteine, served as the sulfide precursor. For the
MoS2 and GO enhanced this mechanism by providing a synergistic effect synthesis of MoS2 nanospheres, 5 mmol of L-cysteine was completely
(Peng and Weng, 2017). Previously, MoS2 and GO were employed as dissolved in 10 mL deionized (DI) water, followed by the gradual
nanoparticles rather than in the form of membranes, resulting in chal­ addition of 5 mL of 10M HCl with continuous stirring. Subsequently, a
lenges associated with their removal from the solution post-treatment. solution containing 0.29 g of Na2MoO4⋅2H2O was introduced and stirred
By embedding them in a CNC membrane, these challenges can be at room temperature for 30 min, ensuring homogeneity. The pH of the
overcome. Fig. 1 depicts the innovative concept introduced in this study. resulting solution was carefully maintained below 1. The mixture un­
derwent autoclaving at 200 ◦ C for 30 h. The resultant solution exhibited
a dark coloration and was thoroughly washed with water and ethanol
before being stored in a water medium (Al Momani et al., 2024). The
MoS2 nanoplatelets were synthesized by a procedure akin to that of the
nanospheres, except maintaining the pH of the final solution at 2. This
green synthesis approach, employing L-cysteine as the sulfide precursor,
demonstrated its efficacy in producing high-quality MoS2 nano­
structures suitable for various applications. The utilization of non-toxic
precursors aligned well with the growing emphasis on sustainable and
environmentally conscious synthesis methods in nanomaterial research
(Arshad et al., 2021).

2.3. Catalytic nanocomposite membrane fabrication

To fabricate the catalytic 2D nanocomposite (CNC) membrane, the

polymer solution was first prepared by adding 1.6 g chitosan to 30 mL
10 wt% acetic acid solution. PEG was added to this solution with 1.6 g of
the pore-forming agent and mixed well until fully dissolved. In the next
step, MoS2 nanosphere (about 0.3 g of dry MoS2) along with 2 mL of 10
mg/mL GO nanosheets (total volume of the mixture <5.0 mL) were
Fig. 1. Illustration of catalytic nanocomposite membrane (CNC) showing added to 30 mL of the polymer solution and stirred under heat followed
simultaneous dye and heavy metal removal. by sonication to get a thoroughly dispersed polymer-nanomaterials

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F. Arshad et al. Journal of Environmental Management 371 (2024) 123242

mixture with no air bubbles. The polymer-nanomaterials solution was crystallinity of MoS2 nanoparticles. The membrane samples’ surface
then cast uniformly into a membrane using a 110 mm film casting knife topography and height profiles were evaluated using atomic force mi­
from MTI Corporation, USA. The knife gap was adjusted to get mem­ croscopy (AFM) from Concept Scientific Instrument (France).
branes of 210 μm thickness. The above polymer solution, which was
devoid of nanomaterials, was also cast to fabricate a neat membrane.
2.5. Membrane perforamnce
The casted membrane was air dried for 30 min, followed by oven drying
until completely dried. As the membrane was fabricated by dissolving
2.5.1. Flux study
chitosan polymer under acidic conditions, the dried membrane was
The membrane was cut into a circle of area 1.96 x 10− 3 m2 and
soaked in a 2M NaOH solution to neutralize the acid and stabilize the
assembled at the bottom of an HP-4750 dead-end stirred cell. The
membrane. The NaOH neutralization aimed to remove the acidic residue
pressure required to achieve a stable permeate flow was recorded. The
of acetic acid from the membrane casting solution, to stabilize the
duration required to filter 50 mL of deionized (DI) water under 12 bars
fabricated membrane (Al Momani et al., 2024). The neutralized mem­
was documented. Flux, JW was then calculated for the neat control
brane was visibly stable and peeled off the glass slide. The
membrane and the CNC membrane using equation (1),
alkaline-treated membrane was intact and showed robustness and sta­
bility after use. The membrane was then rinsed with DI water. Finally, V
Flux JW = (1)
MoS2 nanoplatelets were used to coat the top surface of the CNC At
membrane, where 200 mL of MoS2 nanoplatelet dispersion was filtered
under gravity. The fabricated membranes were soaked in water until Where Jw is the permeation flux (Lm− 2 h− 1), V is the total volume of the
further use. A schematic diagram of the membrane fabrication process is permeated water (L) in the time duration t (h), and A is the membrane
shown in Fig. 2. surface area (m2).
Also, membrane resistance Rm (m− 1), which represents the intrinsic
resistance of the new membrane, was calculated by the following for­
2.4. Characterization of membranes mula (Piry et al., 2012)
ΔP
Various analytical techniques characterized the fabricated mem­ Membrane Resistance RM = (2)
μ0 J0
branes. Scanning electron microscopy (SEM) of the FEI Nova Nano SEM
650 model was employed for detailed morphological and nanostructural where J0 is the distilled water flux of the new membrane (L m− 2 − 1
s ),
examination; a specific focus was on cross-sectional imaging to observe and μ0 is the viscosity of water (Pa s).
the internal structures of the nanocomposite membranes. The areal
porosity was estimated from SEM images of the membrane using the 2.5.2. Simultaneous dye and heavy metal removal
open-source software ImageJ. Energy dispersive X-ray (EDX) elemental The simultaneous removal of both dye and heavy metal was evalu­
mapping was also performed using the JEOL JSM-7610F FEG-SEM to ated by conducting cyclic filtration experiments following the same
ascertain the chemical compositions and their distributions. Further­ protocol outlined in section 2.5.1. The feed solutions were a mixture of
more, X-ray diffraction (XRD) analysis, conducted via an XRD PAN­ methylene blue dye (5 ppm) and one of the heavy metal ions (5 ppm) of
alytical Empyrean diffractometer, confirmed the presence and Cu2+, Ni2+, Co2+, and Pb2+, respectively. At the beginning of the
experiment, 30 mmol H2O2 was introduced to the 50 mL feed to interact
with the MoS2 and generate ROS. In each trial, 50 mL of the feed solution
passed through the membrane in multiple filtration cycles, in which the
obtained permeate was recycled as the feed for the subsequent cycle.
The experimental procedure lasted a total of 9 h, during which permeate
samples were periodically collected. All permeated samples were ob­
tained under constant flux at 12 bars. Methylene blue (MB) concentra­
tions in both the feed and permeate were assessed through UV–vis
spectroscopy (PerkinElmer Lambda 35 UV–vis spectrometer) at a
wavelength of 665 nm, as well as using a total organic carbon (TOC)
analyzer, specifically a Sievers InnovOx analyzer equipped with a GE
autosampler. The same samples were also subjected to ICP-OES analysis
to determine the heavy metal concentrations in both the feed and
permeate samples by the Thermo Scientific iCAP 7600.

2.5.3. Membrane regeneration

Chemical cleaning was done by adding hydrogen peroxide (H2O2) in
the filtration solution to remove the deposited heavy metals from the
membrane surface as well as from the pores of the membrane. At the end
of each dye and heavy metal treatment experiment, a 200 mL cleaning
solution containing 30 mmol of H2O2 was circulated through the
membrane using the dead-end cell setup, followed by a thorough rinse
with DI water. This ensured that the membrane was effectively regen­
erated and ready for reuse in the subsequent filtration tests. The cleaned
membranes were subjected to a flux test, and the flux recovery rate (FRR
%) was calculated by equation (3);
Jwr
FRR (%) = x 100 (3)
Jwi

Fig. 2. Schematic diagram of the nanomaterial’s synthesis and membrane Jwi is the initial pure water flux, and Jwr is the water flux obtained
fabrication process. after the cleaning procedure of the used membrane. The flux recovery

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rate after each cleaning step was calculated and compared. membrane, as shown in Fig. 3(c), exhibits a dense and uniform coating
of MoS2 nanoplatelets. Upon closer inspection through high magnifica­
2.5.4. Confirmation of the generation of reactive oxygen species (ROS) tion (Fig. 3(d)), the stacked MoS2 nanoplatelets are clearly visible. Cross-
Reactive oxygen species (ROS) generated from the interaction be­ sectional images in Fig. 3(e and f) show the neat and the CNC membrane
tween the CNC membrane and H2O2 were confirmed using photo­ structures. As anticipated, the neat membrane’s cross-section reveals a
luminescence (PL) emission spectra. To detect the production of •OH dense chitosan/PEG polymer network without any incorporated nano­
radicals, terephthalic acid (TA) was employed as the probe molecule. materials. Conversely, the cross-section of the CNC membrane exhibits a
MoS2 solution was introduced to TA, thoroughly mixed, and then fol­ porous structure with embedded MoS2 nanospheres and GO nanosheets.
lowed by the addition of H2O2. A PerkinElmer LS-55 Fluorescence The higher magnification image in Fig. 3(g) highlights the presence of
Spectrometer was used with an excitation wavelength set at 330 nm. A pores and the deposition of nanomaterials within these pores.
16.2 W LED lamp served as the light source, with emission radiation Cross-sectional images of 2 different areas of the membrane were
ranging from 350 to 650 nm. To investigate the dose effect of each analyzed by the ImageJ software, and on average, 25.29% of the total
component on the •OH radical generation, the quantities of TA, MoS2, area were pore openings. Fig. S1 shows the pore and membrane wall
and H2O2 were systematically varied. Multiple scenarios were investi­ contrast in various cross-sectional areas of the membrane.
gated, altering one reactant’s amount while keeping the other two Elemental mapping was conducted on the CNC membrane, and the
constants. The influence of TA was examined over concentrations results showed an overall coverage of both Mo and S elements. The EDX
ranging from 0.25 mmol to 1 mmol. MoS2 concentrations ranged from 2 analysis of the membrane, as depicted in Fig. 4(a), reveals a composition
to 10 μL per 10 mL of TA, and H2O2 varied from 5 to 30 μL per 10 mL of of 55 wt% Mo and 40 wt% S, with trace amounts of C, O, and N origi­
TA. The production of •OH radicals by the CNC membrane was also nating from the polymer matrix of the membrane. Both results firmly
assessed by dissolving the membrane in a solution containing 10 mL of indicate the presence of MoS2 nanomaterials on the surface of the
0.5 mmol TA and 10 μL H2O2. Subsequently, the solution was analyzed membrane.
using PL after filtration (Bellardita et al., 2020). The crystallite phases of the synthesized MoS2 nanospheres incor­
porated into the membrane matrix were investigated by X-ray diffrac­
3. Results and discussions tion (XRD). As can be seen from Fig. 4(b), our MoS2 sample reveals
visible peaks at 33.6◦ and 58.7◦ , indicating the presence of specific
3.1. Membrane fabrication and characterization crystallographic planes. The peak at 33.6◦ corresponds to the (100)
plane, while the peak at 58.7◦ corresponds to the (110) plane. The lack
Fig. 3(a) shows a photograph of a fabricated membrane which can be of (002) reflections and the broadness of the peaks compared to bulk
seen to have a smooth appearance with an average thickness of 130 μm. MoS2 crystals suggest that the synthesized nanospheres are thin single-
A comprehensive analysis of the membrane’s surface and cross-section layer or few-layer sheets (Quilty et al., 2019; Veeramalai et al., 2016).
was conducted using SEM. Fig. 3(b) illustrates the membrane base, AFM images can provide valuable insights into the topography, such
primarily composed of chitosan polymer with uniformly embedded as surface roughness, height profile, and morphology. Fig. 4(c and e)
MoS2 nanospheres and GO nanosheets. The top surface of the shows the 2D images of the CNC membrane, while Fig. 4(d) is its 3D

Fig. 3. (a) Fabricated CNC membrane showcasing its uniform and smooth surface, SEM images: (b) Base of the CNC membrane highlighting the uniform distribution
of MoS2 nanospheres and GO nanosheets embedded in the chitosan polymer matrix, (c) Top surface of the CNC membrane showing a dense coating of MoS2
nanoplatelets for enhanced catalytic activity, (d) Magnified view of the CNC membrane top surface detailing the layered structure of MoS2 nanoplatelets, (e) Cross-
sectional view of neat membrane illustrating the dense chitosan/PEG polymer network without nanomaterials, (f) Cross-sectional view of CNC membrane displaying
the porous structure with embedded MoS2 nanospheres and GO nanosheets, (g) Magnified view of the CNC membrane cross-section showing pores and nanomaterial
deposition on the pores.

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Fig. 4. (a) EDX spectra of CNC membrane presenting the elemental composition with predominant Mo and S peaks, indicating the presence of MoS2, (b) XRD spectra
of the synthesized MoS2 nanosphere with visible peaks 33.6◦ aligns with the (100) plane, and the peak at 58.7◦ indicates the (110) plane of MoS2, AFM of CNC
membrane: (c) Amplitude retrace image revealing surface amplitude variations which reflect interaction strength or surface features, (d) 3D image providing a
topographical view of the membrane’s surface roughness and morphology, (e) Z-sensor retrace image showing height variations across the membrane surface which
help in assessing the topographic details of the membrane structure.

image. Fig. 4(c) represents the amplitude retrace image, while Fig. 4(e) 3.2.2. Simultaneous dye and heavy metal removal
represents the z-sensor retrace image. Amplitude retrace images provide The CNC membrane’s treatment efficiency for the simultaneous
information about the amplitude of the oscillation of the AFM tip as it removal of dye and heavy metals was evaluated using a 50 mL feed
scans the membrane surface. Higher amplitude indicates stronger in­ containing 5 ppm MB and 5 ppm one of these metal ions (Co2+, Cu2+,
teractions or steeper surface features, while lower amplitudes suggest Pb2+, and Ni2+) in a cyclic manner for 9 h. To accurately capture the
weaker interactions or smoother surface regions. The Z-sensor retrace kinetics, a small membrane surface area of 1.96 x 10− 3 m2 was used in
image, often referred to as the height or topography image, represents the study, which affected the treatment time of the treated feed solution.
the height variations of the sample surface as probed by the AFM tip. It By using a larger membrane surface area, the treatment times could be
shows how the height of the tip changes as it scans over different regions reduced. Feed and permeate were analyzed using ICP-OES for metal ions
of the sample. The roughness of the membrane can be evaluated from and UV–Vis for MB.
the root-mean-square value (RMS). CNC membranes showed an average For the experiment of MB and Co2+ solution, as shown in Fig. 5(a), in
RMS value of 79.1 ± 1.5 nm. As seen, the membrane surface is uneven, the first filtration cycle (approximately 100 min), the membrane
such as troughs and valleys, which result from the porous polymeric exhibited a consistent 40.0 ± 0.2% removal efficiency for both MB and
substrate. Co2+, when the experiment progressed, the removal efficiency increased
and reached 99.2 ± 0.5% for Co2+ and 99.9 ± 0.01% for MB in the final
3.2. Membrane performance cycle after 540 min. Similar trends were observed for rest three exper­
iments of MB with one of the other metals, such as Cu2+, Pb2+, and Ni2+
3.2.1. Flux study (Fig. 5(b–d)), with initial removal efficiencies of 38.5 ± 0.5%, 28.4 ±
A comparative analysis of DI water flux was conducted for both neat 0.5%, and 26.4 ± 0.2% in the first cycle, respectively, then have
and CNC membranes. The neat membrane, free from nanomaterials, increased accumulatively up to 96.8 ± 0.2%, 93.2 ± 0.2%, and 89.9 ±
exhibited a notably higher flux of 95.7 ± 2.0 Lm− 2h− 1. In contrast, the 0.3%, respectively at the end of the experiment. For these three exper­
CNC membrane demonstrated a flux of 83.0 ± 1.0 Lm− 2h− 1, both iments, the simultaneous MB removal resulted in 98.8 ± 0.1%, 97.5 ±
measured at 12 bars of transmembrane pressure. The membrane resis­ 0.2%, and 97.6 ± 0.3%, respectively. Compared to reported nano­
tance (Rm) was calculated as 5.2 x1013 m-1, which is equivalent to a composite membranes, the CNC membrane exhibits superior perfor­
nanofiltration membrane performance. Incorporating MoS2 and GO into mance. For instance, a polyethersulfone (PES) membrane enhanced with
the membrane may lead to partial pore fillings and pore size reductions, a magnetic graphene oxide/metformin hybrid while achieving notable
contributing to the increased hydrodynamic resistance and consequent removal efficiencies of Cu2+ and direct red 16 rapidly reaches satura­
decreased overall flux. Additionally, the coating of MoS2 nanoplatelets tion and requires frequent regeneration due to its reliance on adsorption.
on the CNC membrane increased the membrane thickness and further In contrast, our catalytic CNC membrane maintains its efficiency over
impacted water permeability. time without the need for regular regeneration, offering a more sus­
tainable solution for continuous use (Abdi et al., 2018). Additionally,

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Fig. 5. Simultaneous MB decolorization and heavy metal removal by CNC membrane for a 5 ppm solution of MB in the presence of 5 ppm (a) Co2+, (b) Cu2+, (c)
Pb2+, (d) Ni2+. Error bars represent percentage errors.

when compared to other catalytic membranes, the CNC membrane MB was also explored based on TOC removal results. An initial solution
shows higher removal rates for heavy metals and organic contaminants. containing 5 ppm of MB and 5 ppm of one type of the studied metal ions
For example, another modification involving a PES membrane with (Co2+, Cu2+, Pb2+, and Ni2+) was subjected to multiple catalytic mem­
polydopamine-coated ferroferric oxide (Fe3O4@PDA) exhibited brane filtration cycles. After the final cycle, the TOC values of the
comparatively lower removal rates for Pb2+ (90%) and MB (98.8%), permeate and the initial feed were analyzed using a TOC analyzer. Fig. 6
even with the inclusion of H2O2 in the feed solution. (Zhang et al., 2020). showed a higher TOC reduction for the MB solution in the presence of
This underscores the CNC membrane’s enhanced performance, high­ Co2+ with a degradation efficiency of 87.1 ± 1.0%. On the other hand, a
lighting its novelty and potential for more efficient water treatment slightly lower TOC removal was observed for MB solutions containing
applications. either Cu2+ or Pb2+ at 85.6 ± 0.5% and 80.4 ± 0.5%, respectively.
The slightly higher removal efficiency of Co2+ than other metal ions Finally, the lowest TOC removal of MB solutions containing Ni2+ was
indicated that the ROS produced by the CNC membrane had a stronger measured at approximately 75.9 ± 1.0% efficiency. These results agree
capacity to react with Co2+, resulting in its higher removal efficiency. with the dye concentration data shown in Fig. 5; faster MB removal is
On the other hand, although Cu2+, Pb2+, and Ni2+ initially had slightly observed for Co2+ and slower for the other heavy metals. One possibility
lower than Co2+’s removal efficiencies, they still demonstrated contin­ is that both MB and the heavy metals compete for adsorption sites in the
uous degradation throughout the experiment. Moreover, the reduction CNC membrane, where adsorption would prolong their retention time,
potential of these metals had a major effect on their removal efficiency
and reaction rate. As Co2+ had a higher reduction potential, it tended to
have faster reaction rates during the removal process. This meant that
Co2+ reacted more quickly with the ROS than other metal ions, leading
to its higher removal efficiency than metals with lower reduction po­
tentials, such as Cu2+, Pb2+, and Ni2+(Bratsch, 1989; yardman, 1989).
These findings led to the results that the CNC membrane could achieve
better performance in removing Co2+ compared to the other metal ions.
A neat chitosan membrane without nanomaterials was fabricated
and tested to affirm the enhanced efficacy of MoS2/GO in the simulta­
neous removal of MB and metal ions. This pristine membrane underwent
the same filtration process and conditions as the CNC membrane, uti­
lizing a solution containing 5 ppm MB and 5 ppm for each type of tar­
geted metal. The results revealed that the neat membrane exhibited
limited removal efficiency for the metal ions, ranging from only 8.2 ±
0.5% to 11.2 ± 1.0%, respectively. The color removal efficiency was
also found to be significantly lower at 19.3 ± 1.0 to 21.0 ± 1.0% at the
end of each filtration process (Fig. S2). These results demonstrate the
superior performance of the CNC membrane in comparison to the pris­
tine membrane. About 10% of nanomaterials (MoS2 and GO) were
added to the polymer matrix, which only introduced a limited adsorp­
tion capacity. However, the combined adsorption and catalytic ROS
condition promoted a more efficient removal.
Besides decolorization, the CMC membrane’s ability to mineralize Fig. 6. TOC results of MB removal with standard deviations. Error bars
represent percentage errors.

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leading to faster degradation. For Co2+, which is more quickly removed in the formation of metal hydroxides (M(OH)x), which were often
from the solution through reduction, the MB removal is also higher due insoluble in water. These insoluble reduced metals or metal hydroxides
to the lower competition. can then be easily separated from the solution, aiding in removing heavy
metals from wastewater. The organic matter was oxidized into CO2 and
3.2.3. Mechanism of ROS generation and simultaneous removal water, where the reduced heavy metal ions are deposited on the nano­
The MoS2 and GO integrated chitosan nanocomposite membrane in composite membrane’s internal surfaces, and the regeneration process
this study is expected to allow the generating of ROS and catalytic could be achieved using a desorbing agent periodically.
oxidation and reduction to achieve the simultaneous removal of both Confirming the generation of ROS such as hydroxyl radicals (•OH) is
dye molecules and heavy metal ions. In conjunction with MoS2 and GO, crucial for the validity of this research. The generated ROS are recom­
the chitosan polymer matrix provided an ideal substrate for ROS gen­ bined instantly and can be confirmed by trapping them using organic
eration. Particularly, MoS2, with its catalytic properties, promotes the scavengers like coumarin and terephthalic acid (TA). The photo­
generation of reactive oxygen species in the presence of H2O2. At the luminescence (PL) technique using TA as the probe can effectively
same time, GO, with its large surface area and abundance of functional compare the formation of •OH radicals (Bellardita et al., 2020). In this
groups, acts as a catalyst support by providing additional adsorption study, TA was used as the probe material. TA reacts with •OH to yield
sites for MB and metals. This synergistic combination enhances dye the highly fluorescent 2-hydroxy terephthalic acid (TAOH) (Chen et al.,
decolorization and heavy metal removal efficiency. 2018; Li et al., 2020; Peng and Weng, 2017). The advantage of TA is that
Within the framework of this process, it can be seen that the CNC only TAOH can be envisaged as a hydroxylation product due to the
membrane delivered dual functions of separation and degradation of the structural symmetry of TA (Žerjav et al., 2020).
contaminants by generating ROS, like hydroxyl radicals (•OH). These Fig. 7(a, c, and e) shows the fluorescence spectra obtained by the
ROS played a crucial role in the reactions for removing dyes and heavy interaction of TA, MoS2, and H2O2 systems in the 350–700 nm (only
metals from wastewater (Al Momani et al., 2023). When the dye mole­ 550–650 nm shown in the figure). The fluorescence intensity at 604 nm
cules in the wastewater came into contact with the highly reactive ROS, is the strongest in the TA/MoS2/H2O2 system, which indicates that the
they were directly oxidized when their electrons were captured by the strong interaction between MoS2 and H2O2 can generate •OH radicals.
ROS and broken down into smaller, less complex compounds to form The photoluminescence intensity was measured by altering the con­
harmless byproducts like CO2 and water. At the same time, the ROS can centrations of MoS2, TA, and H2O2 individually while keeping the
also reduce the heavy metal ions in the wastewater. The reduction re­ remaining two components constant. Fig. 7(b, d, and f) shows the in­
action between the ROS and the metal ions involves transferring elec­ crease in the intensity of the fluorescence spectra with the increase in the
trons from the ROS to the metal ions. This reduction led to insoluble concentration of the reactants and probe material. These outcomes
solid metal species forming, removing them from the solution. Overall, affirm the generation of ROS through the strong interaction between
the ROS generated by the CNC membrane acted as both electron ac­ MoS2 and H2O2. The evaluation of •OH generation in the CNC mem­
ceptors and donors in the redox reactions for simultaneous dye and brane was conducted by dissolving it in H2O2 with TA as a probe. A PL
heavy metal removal. These very reactive ROS accepted electrons from peak at 604 nm was observed (Fig. S3), providing conclusive evidence
the dye molecules to cause their oxidation into harmless carbon dioxide for the generation of ROS within the membrane. Thus, the concept of
and water; simultaneously, they donated electrons to metal ions to ROS generation by the CNC membrane for the simultaneous removal of
reduce them into solid metal precipitates (Ajiboye et al., 2021; Ye et al., the dye-heavy metal has been validated.
2021; Zou et al., 2020). The two half-reactions of the overall redox re­
actions can be presented as follows, where M2+ denotes heavy metal 3.2.4. Kinetic study
ions: The obtained degradation results were fitted with kinetic models to
investigate the degradation kinetics and the related reaction constant
MoS2 1
Half reaction : H2 O2 ̅̅̅→ 2 e− + 2 OH− + O (4) (k). It is known that the pseudo-first-order model may not be the best fit
2
for describing reaction kinetics. In fact, many studies demonstrated that
MoS2 the pseudo-second-order model provided a better fit in the catalysis
Half reaction : M2+ + 2e− ̅̅̅→ M0 (5)
process than the pseudo-first-order model (Akram et al., 2023; Khan
1 et al., 2019; Rahman et al., 2023). This finding was also confirmed by
MoS2
Redox reaction : H2 O2 + M2+ + ̅̅̅→ M0 + 2 OH− + O (6) Eddy et al. (2023). As a result, both the pseudo-first (Fig. S4) and
2
pseudo-second-order models (Fig. S5) were investigated.
In the CNC membrane, when the MoS2/GO were exposed to H2O2, it The following equations were employed in the Pseudo-first-order
functioned as a catalyst for the production of ROS, including hydroxyl (equation (7)) and Pseudo-second-order (equation (8)) kinetic analysis:
radicals (•OH) and singlet oxygen (1O₂). These ROS played a crucial role
Pseudo-first order: ln(C/Co) = kt (7)
in the redox reactions involved in the simultaneous removal of dyes and
heavy metals from wastewater (Chen et al., 2018; Peng and Weng, Pseudo-second order: − 1/(C/Co) = kt (8)
2017). The ROS mechanism initiated a cascade of oxidative reactions
that targeted the chromophores present in dyes. Chromophores were where Co is the initial concentration of MB or metal ions (mg/L), C is the
responsible for the vivid coloration of dyes and were typically composed remaining concentration after the time (t) of the experiment (mg/L), and
of conjugated double bonds, making them susceptible to attack by k is the corresponding kinetic rate constant (min− 1). It can be observed
reactive oxygen species. Hydroxyl radicals, in particular, exhibited a from Fig. S4 that the results fit well with the experimental data, and the
high reactivity towards these conjugated structures, leading to their correlation coefficients (R2) were close to 1. Thus, it could be concluded
rapid degradation. As a result, the dye molecules lose their chromo­ that the kinetic data followed the pseudo-first-order rate equation. In
phoric properties, ultimately leading to decolorization (Patel et al., essence, this indicates that the amount of available ROS was present at a
2023). On the other hand, ROS also played a vital role in the reductive relatively stable level for our reactions and that it was never limiting the
removal of heavy metals. Metal ions like Pb2⁺, Cu2⁺, Ni2⁺, and Co2⁺ were reactions. The rate constant (k) of MB/Co2+ was found to be higher
highly susceptible to reduction by ROS. This reduction process caused compared with other MB/metal ions in terms of decolorization. For
the conversion of these metal ions into less toxic low-valence forms or instance, the decolorization k value of MB in MB/Co2+ solution (0.7504
facilitated their precipitation for subsequent removal. Another pathway min− 1) is about 2 times higher than that of decolorization (0.3679
was that hydroxyl radicals (•OH) could react with metal ions, resulting min− 1, 0.3858 min− 1) in the MB/Ni2+ and MB/Pb2+ solutions, respec­
tively, and about 1.7 times higher than that of in MB/Cu2+ (0.4365

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F. Arshad et al. Journal of Environmental Management 371 (2024) 123242

Fig. 7. PL spectra to confirm ROS generation (a, b) Varying MoS2 dosage, (c, d) Varying H2O2 dosage, (e, f) Varying TA dosage. Excitation wavelength 330 nm.

min− 1). faster in all solutions than that of the removing targeted metal ions,
Similar trends were observed in the case of metal ions; the rate where the rate constants of color removal ranged from 1.1 times (MB/
constant k of Co2+ also exhibited a higher value (0.5334 min− 1), which Cu2+) to 1.5 times (MB/Ni2+) higher than for metal reduction in the
was 1.2 and 1.8 times higher than that of Cu2+ and Pb2+, respectively. experiments of and, respectively. Due to both MB and the heavy metals
The lowest k value was exhibited by Ni2+ (0.2410), which was 2.2 times competing for adsorption sites in the CNC membrane, the adsorption
lower than that of Co2+. It was clear that within the same experiment, could become the limiting factor on the degradation rate. In the MB/
the kinetics of removing the color as represented by MB was slightly Co2+ solution, Co2+ with higher reduction potential could be more

8
F. Arshad et al. Journal of Environmental Management 371 (2024) 123242

quickly removed from the solution through reduction, leading to faster

MB removal due to the lower competition.

3.2.5. Membrane regeneration

The reusability of the CNC membrane was evaluated through mul­
tiple filtration cycles, with each cycle followed by a regeneration process
using 30 mmol H2O2 and DI water. After the initial filtration experiment
of simultaneous dye-heavy metal removal, the CNC membrane was
chemically regenerated using 30 mmol H2O2 and DI water. It was reused
multiple times in the subsequent experiments. The same membrane was
consistently used throughout the entire study. Fig. 8 depicts the
observed flux recovery trend in the membrane following each regener­
ation and reuse.
The initial water flux of the CNC membrane was recorded as 83.0 ±
1.0 Lm− 2h− 1. Notably, no substantial reduction in flux was observed
throughout the entire duration of the study. After subjecting the CNC
membrane to the first dye (MB) and heavy metal removal experiment for
9 h, it was regenerated and cleaned, and the recovered flux was recorded
as 80.0 ± 1.5 Lm− 2h− 1. Similarly, the second, third, and fourth flux was
recorded as 77.0 ± 1.0 Lm− 2h− 1, 76.5 ± 1.0 Lm− 2h− 1, and 76.0 ± 1.0
Lm− 2h− 1, respectively. Thus, a flux recovery of 96.4 ± 1.0%, 92.8 ±
0.5%, 92.1 ± 1.0 %, and 91.6 ± 1.0% was obtained, respectively. A 95% Fig. 8. Flux recovery trends with standard deviations observed in the CNC
confidence interval was calculated with a z value of 1.96 for the water membrane after multiple uses. Error bars represent percentage errors.
flux recovery rates, and our readings fell within this interval across
multiple trials, affirming the consistency and reliability of the mem­ were measured by fluorescence emission spectroscopy. This redox cat­
brane’s performance. These values validated the membrane’s stability alytic process not only showcased high removal efficiency for both dye
and reusability over a longer term. Even after repeated chemical molecules and heavy metal ions but also contributed to the membrane’s
cleanings and reuse, the membrane integrity was well intact, and it regeneration and reuse evidenced by a high flux recovery rate of more
remained mechanically robust and visually free from wear and tear. than 91% after multiple uses. The introduction of 2D nanomaterial-
enhanced composite membranes offers several advantages over con­
4. Conclusion ventional RO and NF membranes: MoS2 and GO incorporation provides
unique catalytic properties not typically available in conventional
This study successfully developed a catalytic nanocomposite mem­ polymeric membranes, enhanced the overall treatment effectiveness;
brane and tested its performance in addressing the multiple challenges the nanocomposite membranes can operate at lower pressures than RO
faced in treating industrial wastewater. The catalytic 2D nanocomposite and reduces energy demands, making the process more sustainable and
membrane (CNC), based on sustainable components such as Chitosan cost-effective; both the 2D nanomaterials and polymer chitosan used in
and L-cysteine, offered an efficient approach for the simultaneous these nanocomposite membranes were derived from abundant or sus­
removal of dye and heavy metal ions from wastewater. Incorporating tainable sources, as well as were feasible to be scaled up. The above
MoS2 and GO into a chitosan polymer matrix resulted in an integrated highlights positioned the nanocomposite membrane in a good place to
porous membrane structure, as evidenced by complementary charac­ treat the actual complex wastewater from industrial sources such as
terizations. The resultant CNC membrane showed water flux similar to textile/leather, petroleum/refineries, paint industries, pesticides in­
the nanofiltration membrane. The synergistic effects of MoS2 and H2O2 dustries, metal smelting industries, and petroleum refineries where both
generated very reactive oxygen species, such as hydroxyl radicals. They organic and heavy metal contaminants co-existed.
allowed the breakdown of the organic dye contaminants and reduced
heavy metal ions into no-soluble metals, ensuring effective wastewater CRediT authorship contribution statement
treatment.
The CNC membrane demonstrated excellent efficiency in the Fathima Arshad: Writing – original draft, Validation, Investigation,
simultaneous removal of methylene blue (MB) and heavy metal ions Formal analysis. Delal E. Al Momani: Writing – original draft, Valida­
(Co2+, Cu2+, Pb2+, and Ni2+). The accumulative removal efficiency tion, Methodology, Investigation, Formal analysis. Wiebe M. de Vos:
reached 99.2 ± 0.5% for Co2+ and 99.9 ± 0.01% for MB, and 99.2 ± Writing – review & editing, Validation, Formal analysis. Linda Zou:
0.5% and 99.9 ± 0.01% for Co2+and MB, respectively. Similar trends Writing – review & editing, Supervision, Project administration, Meth­
were observed for other metals, reaching 96.8 ± 0.2%, 93.2 ± 0.2%, odology, Investigation, Funding acquisition, Formal analysis,
and 89.9 ± 0.3%. The ROS allowed for a faster reduction of Co2+, Conceptualization.
resulting in the highest removal percentage. Although Cu2+, Pb2+, and
Ni2+ had slightly lower removal efficiencies than Co2+’s, they were still Declaration of competing interest
continuously removed to a high extent throughout the experiment. The
color removal results were confirmed by TOC analysis. In comparison, a The authors declare that they have no known competing financial
neat chitosan membrane in the absence of nanomaterials exhibited interests or personal relationships that could have appeared to influence
much lower efficiencies, with only 19.3 ± 1.0 to 21.0 ± 1.0% for color the work reported in this paper.
removal and with only 8.2 ± 0.5% to 11.2 ± 1.0% for heavy metal ions
removal. The overall positive results highlight the membrane’s superior Acknowledgments
performance in simultaneous dye and heavy metal removal. MoS2’s
catalytic property was activated by H2O2 and generated reactive oxygen Authors acknowledge the funding and support by the Directed
species, while GO, with its abundance of functional groups, acts as a Research Projects DP5-8434000504 project grant of the Research and
catalyst support. The generation of ROS was confirmed by trapping them Innovation Center for Graphene and 2D materials (RIC2D) of Khalifa
using radical scavengers terephthalic acid (TA), and the formed species University; the PhD scholarship provided by Khalifa University for Ms.

9
F. Arshad et al. Journal of Environmental Management 371 (2024) 123242

Delal E. Al Momani is also acknowledged. We also thank Dr Cyril Aubry, Kumar, A., Thakur, A., Panesar, P.S., 2023. A review on the industrial wastewater with
the efficient treatment techniques. Chem. Pap. 77 (5), 4131–4163. https://doi.org/
Ms. Tharalekshmi Anjana, Dr. Nurlan Akhmetov and Dr. Faheem for
10.1007/s11696-023-02779-3.
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