Fathima Arshad1, Cyril Aubry2, Linda Zou1. 1. Department of Civil Infrastructure and Environment Engineering, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates. 2. Department of Research Laboratories Operations, Khalifa University of Science and Technology, Abu Dhabi 127788, United Arab Emirates.
Abstract
MoS2 nanosheets were synthesized by a bottom-up green chemical process where l-cysteine was used as a sulfur precursor. With specific concentrations, molar ratio of reactants, and pre-mixing conditions, MoS2 nanosheets of 200-300 nm in size and 4.2 nm in average thickness were successfully obtained. Porous membranes were then prepared by depositing the MoS2 nanosheet suspension on a 0.1 μm pore size poly(vinylidene difluoride) membrane filter in a multiple batch procedure. The membrane deposited with 12 batches of MoS2 nanosheets achieved 93.78% removal of bovine serum albumin. Acid red removal of 95.65% was also achieved after the second filtration pass. The porous MoS2 nanosheet membrane also demonstrated a high water flux of 182 ± 2.0 L/(m2 h). This result overcame the trade-off between selectivity and permeability faced by polymeric ultrafiltration membranes. The MoS2 nanosheets as building blocks formed not only intersheet slit pores with a narrow half-width to restrict the passage of organic molecules but also macro-channels allowing easy passage of water. The assembled MoS2 nanosheet membrane delivered promising separation of protein molecules and a high flux, attributing to its porous nanostructure, and could be a potential membrane for various water applications.
MoS2 nanosheets were synthesized by a bottom-up green chemical process where l-cysteine was used as a sulfur precursor. With specific concentrations, molar ratio of reactants, and pre-mixing conditions, MoS2 nanosheets of 200-300 nm in size and 4.2 nm in average thickness were successfully obtained. Porous membranes were then prepared by depositing the MoS2 nanosheet suspension on a 0.1 μm pore size poly(vinylidene difluoride) membrane filter in a multiple batch procedure. The membrane deposited with 12 batches of MoS2 nanosheets achieved 93.78% removal of bovine serum albumin. Acid red removal of 95.65% was also achieved after the second filtration pass. The porous MoS2 nanosheet membrane also demonstrated a high water flux of 182 ± 2.0 L/(m2 h). This result overcame the trade-off between selectivity and permeability faced by polymeric ultrafiltration membranes. The MoS2 nanosheets as building blocks formed not only intersheet slit pores with a narrow half-width to restrict the passage of organic molecules but also macro-channels allowing easy passage of water. The assembled MoS2 nanosheet membrane delivered promising separation of protein molecules and a high flux, attributing to its porous nanostructure, and could be a potential membrane for various water applications.
The rapid development
of the bio-therapeutics industry for both
treatment and prevention of disease purposes often involves biomass
concentration, protein purification, biomass clarification, and biomolecule
concentration. The availability of suitable membranes that can attain
excellent separation while maintaining very high permeability is critical.[1] The existing polymeric-based ultrafiltration
(UF) membranes have shortcomings of the trade-off between membrane
selectivity and membrane permeability.[2] This means that if the membrane selectivity is increased due to
a smaller pore size, then membrane permeability will be reduced and
vice versa.[3−5] Other problems to be addressed include pore blockage
by suspended solids[2] or the lack of chemical
stability to solvents.[6] However, the nanomaterial-assisted
porous MoS2 nanosheet membrane reported in this work could
offer a solution as a new type of low-pressure membrane addressing
the above issues by delivering both high rejection of protein molecules
and maintaining a very high flux. A combination of factors like slit
pore geometry and intermolecular interactions induced by nanomaterials
such as van der Waals forces makes such membranes a promising candidate
for bioprocessing applications (Figure ).
Figure 1
Illustration of the porous MoS2 nanosheet membrane
concept.
Illustration of the porous MoS2 nanosheet membrane
concept.Two-dimensional (2D) materials
and their derivatives have been
viewed as ideal candidate materials for next-generation separation
membranes because of their extraordinary properties of being thin,
mechanically robust, and chemically resistant. Although a large amount
of research has been conducted in developing either monolayer nanoporous
graphene membranes or rGO laminate membranes,[7] there are still many challenges that need to be tackled to achieve
ideal ion and water separation and for scaling up to large-scale applications.[8,9] These challenges present excellent opportunities for innovative
research to explore large families of 2D materials, such as transition-metal
dichalcogenides (TMDs) and MXenes. A breakthrough in designing and
developing high-performance membranes is anticipated.Among
the 2D materials families, molybdenum disulfide (MoS2)
is a TMD layer compound; its 2D nanosheets or nanoplatelets
can be obtained by either a top-down approach of exfoliation or a
bottom-up approach of chemical synthesis. The 2D crystal of MoS2 has a sulfur–molybdenum–sulfur trilayered structure
and an inorganic analogue of graphene-like nanosheets.[10] MoS2 with its extremely smooth and
low-friction surface has been recently reported as a successful fouling-resistant
membrane coating.[11] For water and environmental
applications, MoS2 nanosheets have be used in aqueous suspensions
for photocatalytic decolorization.[12] Hybrid
aerogel filters have been synthesized using immobilized MoS2 nanosheets on cellulose scaffolds[13] to
remove contaminants from water. The MoS2 shell was coated
on the CdS core by the solvothermal technique for photocatalytic hydrogen
generation.[14] In addition, MoS2 has some distinct properties such as zero swelling in water, attributed
to the balance between attractive van der Waals forces among neighboring
nanosheets and repulsive hydration forces.[15] However, in most research works MoS2 nanomaterials were
obtained by the exfoliation method, that is, the top-down strategy
for preparing the MoS2 nanosheets. In one research study,
MoS2 laminate membranes were prepared to separate different
molecules, such as organic dye molecules and cytochromes.[16] In another research project, nanoporous MoS2 nanosheets were fabricated by the cavitation process, and
the prepared membrane was used in the forward osmosis process, achieving
high salt and water separation due to the highly porous yet charged
interface that offered high permeability while achieving selectivity
simultaneously.[17] Dye-functionalized MoS2 membranes were also prepared and reported for ionic species
rejections.[18] In contrast, Lu et al.[19] discussed their findings on the stacking of
MoS2 nanosheets resulting in the formation of larger microporous
defects with significant reduction of the membrane selectivity. The
authors concluded that due to the limitations of using the top-down
approach to fabricate 2D materials, developing more refined MoS2 nanosheets is needed. This fabrication process allows carefully
tuning the 2D nanosheets as building blocks with a sufficiently defined
lamellar structure as it is critical for preparing excellent 2D water
purification membranes. This has motivated us to carefully investigate
the usage of a non-exfoliation technique. Distinct from other research
works, we have chemically synthesized MoS2 nanosheets.
By controlling the conditions affecting molecular crystallization,
we can have better control on the resultant MoS2 nanomaterials’
structures including the geometric shape, dimensional size, and nanosheet
thickness. It is interesting to study the properties and performance
of separation membranes prepared by using chemically synthesized MoS2 nanosheets.In this work, bottom-up chemical synthesis
with green precursors
and modified reaction conditions was employed to prepare MoS2 nanosheets. Our study demonstrated that the different dimensional
structures of MoS2 materials such as nanospheres, nanoplatelets,
and nanosheets can be obtained under different chemical and physical
conditions during synthesis (Figure ). Although thiourea was reported as an essential sulfur
source in the chemical synthesis of MoS2 nanosheets,[20,21] non-toxic green chemical l-cysteine was used as a precursor
in this study to synthesize MoS2 nanosheets. These small
nanosheets were detached and flexible, making them a suitable candidate
material for preparing porous MoS2 laminate membranes.
The MoS2 dispersion was filtered on the substrate batch
by batch, and this method not only increased the control in membrane
fabrication but also probed the effect of amount of nanomaterials
used on the membrane separation capability. Finally, the potential
of porous MoS2 nanosheet membranes to facilitate both a
high water flux and separation of contaminants such as the BSA protein
and dye molecule acid red was evaluated by filtration experiments.
Figure 2
Synthesis
of MoS2 nanospheres, MoS2 nanoplatelets,
and MoS2 nanosheets.
Synthesis
of MoS2 nanospheres, MoS2 nanoplatelets,
and MoS2 nanosheets.
Methodology
Materials
All
chemicals and reagents
used for nanoparticle synthesis, characterization, and analytical
studies were of scientific grade and used as received with no modification.
The support filter used for membrane fabrications was a 0.1 μm
Durapore filter from Merck. Sodium molybdate dihydrate (Na2MoO4) (purity ≥ 99%), l-cysteine (purity
= 97%), and 1 M hydrochloric acid (HCl) from Sigma Aldrich were used
in synthesizing the MoS2 nanoparticles. The chemicals used
for the analytical studies were bovine serum albumin (BSA) (lyophilized
powder with purity ≥ 96% with a molecular weight of 66 000
g/mol) from Sigma Life Science and Acid Red 1 (with 60% dye content
and a molecular weight of 509.42 g/mol) from Sigma Aldrich.
Synthesis of MoS2 Nanoparticles
In order
to obtain the thin MoS2 nanosheets suitable
for membrane preparation, multiple trials have been conducted in this
study. In each trial, the experiment conditions and reactant quantity
were varied, which affected the morphology of the synthesized product. Figure illustrates the
difference in reaction conditions and the MoS2 obtained
for each condition. Trial 1 led to the formation of MoS2 nanospheres, and trial 2 resulted in flat and thick nanoplatelets.
Trial 3 successfully produced MoS2 nanosheet with the desired
morphology for membrane. To
synthesize MoS2 nanosheets; 0.1005 g of l-cystein
and 0.0485 g of sodium molybdate dihydrate (molar ratio 1.5:1) were
each dissolved in 30 mL of water. The solutions were combined and
mixed vigorously at 90 °C, and the pH was adjusted to 2 using
1 M HCl before being transferred to a hydrothermal reactor. The reactor
was kept at 210 °C for 24 h. The final product obtained after
24 h was a gray-colored solution with uniformly suspended particles
throughout the solution. The solutions were well sonicated before
the membrane fabrication procedure. Figure illustrates the procedure involved in MoS2 synthesis.
Characterization
Scanning electron
microscopy (SEM, Quanta 250, FEI Company) coupled with energy-dispersive
X-ray (EDX) spectrometry and transmission electron microscopy (TEM,
Tecnai from FEI Company operating at 200 KV) were employed to examine
the sample’s morphology, nanostructure, and elemental compositions.
To obtain surface topographical information such as thickness of the
MoS2 nanosheets, an atomic force microscope from Concept
Scientific Instrument (France) was used. X-ray diffraction (XRD) measurements
of the MoS2 nanosheets were carried out using a Panalytical
Rayons-X XRD spectrometer with Cu Kα radiation and scanned from
20 to 80°.
Membrane Fabrication
The porous MoS2 nanosheet membrane was prepared by the
deposition of the
as-synthesized MoS2 nanosheets onto a commercial 0.1 μm
Durapore membrane filter from Merck. The diluted MoS2 solution
was poured onto the filter kept in a vacuum filter apparatus, and
it was let to sit for 2 h under gravity so that a stable layer of
MoS2 is formed on the support. After 2 h, the vacuum pump
was switched on, and the permeate was allowed to flow through the
membrane. The obtained wet membrane was dried in an oven at 35 °C
for 18 h to evaporate loosely adsorbed water. The procedure was repeated
batch by batch until 12 layers of MoS2 were deposited on
the membrane.
Separation and Filtration
Experiments
The as-prepared porous MoS2 nanosheet
membranes were subjected
to separation experiments using 1 g/L BSA[22] and 10 mg/L acid red dye. To test the BSA rejection of the membrane,
the BSA feed solution was passed through the membrane, and the permeate
samples were analyzed using an ultraviolet–visible (UV–vis)
spectrophotometer (PerkinElmer Lambda 35) to quantitatively determine
the concentration of BSA remaining in the permeate after passing through
the membrane. The experiment was repeated thrice, and the average
value was taken for removal measurements. The acid red dye removal
by the membrane was done in a similar manner, and the percentage removal
was calculated using eq (23)Here, C is the concentration
in g/L.The filtration experiments of the MoS2 nanosheet
membranes were carried out in a lab-scale setup using a Convergence
Inspector (Convergence, Netherlands). A feed pressure of 1 bar and
a flow rate of 5 L/h were maintained. After the initial water flux
was measured, the filtration of 0.1 g/L BSA solution was carried out
for 30 min. The fouled membrane was then washed thoroughly using DI
water for 1 h. After washing, the water flux was measured again, and
the flux was recorded. The flux recovery rate (FRR) was calculated
using eq where J0 is the
initial flux and Jf is the recovered flux
after washing the fouled membrane.
Results
and Discussion
Bottom-Up Synthesis of
MoS2 Nanosheets
In this green chemical synthesis
route, a safe and non-toxic amino
acid, l-cysteine,[20] was employed
as a sulfur precursor to substitute toxic thiourea. As depicted in Figure , a series of trials
have been conducted to finally obtain thin MoS2 nanosheets
that were suitable for membrane preparation. It was found that different
reaction conditions, including the concentration of the reactants,
hydrothermal reaction temperature and time, and pre-mixing conditions,
led to the resultant MoS2 products with different dimensional
structures. MoS2 nanospheres synthesized from trial 1 had
a round morphology and MoS2 nanoplatelets obtained from
trial 2 were too thick, so both materials were rejected. Finally,
thin MoS2 nanosheets were successfully obtained in trial
3 and used in the membrane assembly. The chemical reactions involved
in the synthesis of MoS2 nanoparticles are given below[24]In trial 3, after the
24 h hydrothermal reaction at 210 °C, a gray-colored translucent
dispersion with uniformly suspended black particles was obtained.
The black particles remained suspended in the solution without precipitation
overnight. SEM and TEM analysis had confirmed them as detached thin
MoS2 nanosheets. The amount of MoS2 produced
per batch was estimated to be 0.03217 g. In contrast, when nanospheres
and nanoplatelets were obtained under different conditions as described
above (Figure ), their
final solutions displayed a very dense black color and precipitation
occurred quickly.SEM imaging (Figure ) of the vacuum-dried sample was conducted
to examine and confirm
the microscopic structure of MoS2 as nanosheets. At a lower
magnification (Figure a), the SEM image depicted platelet-like structures and were stacked
together. The individual sizes of sheets were observed in the range
of 200–300 nm, and these more flat sheet-like morphologies
were different from previously reported densely arranged randomly
oriented “flower-like” sheets in the literature.[25] On increasing the magnification, flat sheets
of MoS2 were observed. At a 500 nm scale, the thin sheet
structure of the MoS2 nanoparticles became evident (Figure c–e). Folded
edges with wrinkles found in high-magnification images revealed that
they were flexible thin sheets. The morphology of the synthesized
MoS2 can be thus elaborated as thin wrinkled nanosheets.
In Figure f, the characteristic
peaks of MoS2 nanosheets were observed at 33.69° (100)
and 59.51° (110), and the broad and weak peaks indicated that
the resultant MoS2 materials were few-layer nanosheets.[26]
Figure 3
(a–e) SEM images of MoS2 nanosheets
at low, medium,
and high magnifications and (f) XRD spectra of MoS2 nanosheets.
(a–e) SEM images of MoS2 nanosheets
at low, medium,
and high magnifications and (f) XRD spectra of MoS2 nanosheets.TEM analysis was carried out to further verify
the sheet-like structures
of the synthesized MoS2. Figure a–c illustrates that the MoS2 samples were aggregated thin sheets. In addition, higher-magnification
TEM images in Figure d–f show the well-stacked layers of MoS2 nanosheets
with a visible interlayer distance.
Figure 4
(a–c) TEM images of MoS2 nanosheets and (d–f)
stacked layers of MoS2 nanosheets.
(a–c) TEM images of MoS2 nanosheets and (d–f)
stacked layers of MoS2 nanosheets.In order to determine the thickness of MoS2 nanosheets,
atomic force microscopy (AFM) profiling was conducted by scanning
the surface of the MoS2 nanosheets. Figure shows the height profiles of four individual
sheets. The thickness of the sheets was in the range 3.6 to 5.0 nm
with an average thickness of 4.2 nm.They further confirmed that the
synthesized MoS2 nanosheets were of 200–300 nm dimensions
and a few nanometer thickness. This thickness information was not
available in previously reported works.[27]
Figure 5
AFM
height profiles probing the MoS2 nanosheet thickness.
AFM
height profiles probing the MoS2 nanosheet thickness.
Deposited Porous MoS2 Nanosheet
Membrane
After confirming their thin sheet-like structure,
the synthesized MoS2 nanosheets were then used in membrane
fabrication. The light-gray solution containing uniformly suspended
MoS2 nanosheets was poured carefully onto a 0.1 μm
Durapore filter support that was placed on a vacuum filtration assembly.
The detailed procedure is explained in the “Methodology” section. Figure a shows the membrane layers formed after
pouring one batch of the MoS2 solution, named M1. A light-gray-colored
film was seen on the membrane, and the prepared membrane was then
placed in an oven at 35 °C for 18 h to remove the excess water.
The coated MoS2 membrane was stable and showed no color
change or particle detachment when immersed in water. Multiple batches
of MoS2 nanosheet solutions prepared by the same hydrothermal
process were poured onto the same substrate in a batch-by-batch manner.
The membrane surface appearance after the second batch (M2) is shown
in Figure b. It can
be seen that the membrane surface displayed a darker shade of gray
after the second batch of MoS2. The above process was repeated
for multiple batches, and more MoS2 nanosheets were deposited
on the built membrane surface. Each batch resulted in a darker membrane
than the previous batch until 12 batches (M12) of MoS2 nanosheets
were deposited. The quantity of permeate passing through the membrane
layers also became noticeably slower than the previous batch. This
was due to the increase in the thickness of the MoS2 sheet
layers. Figure c shows
the image of the membrane after the eighth batch. As is seen, the
membrane surface was uniform and smooth with a dark color, associated
with the amount of the deposited MoS2 nanosheets. The MoS2 nanosheet membrane was stable without any physical change
both in water and under dry conditions. Thus, a stable porous membrane
consisting of multilayers of MoS2 nanosheets was fabricated.
Figure 6
(a–c)
Membrane surfaces deposited with different batches
of MoS2 nanosheets and (d–f) cross-sectional SEM
images of MoS2 nanosheet membrane layers deposited on the
polymer support at different magnifications.
(a–c)
Membrane surfaces deposited with different batches
of MoS2 nanosheets and (d–f) cross-sectional SEM
images of MoS2 nanosheet membrane layers deposited on the
polymer support at different magnifications.Figure d–f
shows the cross-sectional images of the MoS2 nanosheet
membrane at different magnifications. Distinct sections of the polymer
substrate and MoS2 layers are clearly seen. The arrows
in Figure d indicate
about a 25–30 μm thickness of deposited MoS2 membrane layers. In addition, these images displayed the porous
nature of the membrane layers built by deposited MoS2 nanosheets.
As explained above, these porous characteristics of membrane layers
consisting of numerous slit pores form intersheets, contributed to
enhanced selectivity while retaining the high flux, in comparison
to the classic cylindrical pores in the polymeric matrix. These images
further illustrated that the synthesized MoS2 nanosheets
were curled up to form a porous structure as macro-channels for water
molecule passage (Figure f). At the same time, the unique slit pores formed by the
assembly of detached few nanometer thin MoS2 nanosheets
enabled the narrow and uniform half-width h to exhibit an excellent
sieving effect and high selectivity. The advantages of nanosheets
as building blocks of the membrane offering both macro-channels and
intersheets slit pores are confirmed in a later section. Elemental
mapping using EDX analysis was performed on the MoS2 nanosheets
(Figure ). The identified
sulfur layer clearly confirmed the presence and thickness of MoS2 nanosheet membrane layers. Mo mapping is not visible here
due to detection interference. The filter support made from the poly(vinylidene
difluoride) (PVDF) polymer used for MoS2 nanosheet membrane
fabrication explained the presence of fluorine and carbon in the elemental
mapping.
Figure 7
(a) Cross-sectional SEM image of MoS2 nanosheet membrane
layers deposited on the PVDF support and elemental mapping showing
(b) sulfur, (c) fluorine, and (d) carbon.
(a) Cross-sectional SEM image of MoS2 nanosheet membrane
layers deposited on the PVDF support and elemental mapping showing
(b) sulfur, (c) fluorine, and (d) carbon.
Separation of BSA Protein Molecules by Porous
MoS2 Nanosheet Membrane Layers
Figure a illustrates the batch-by-batch
procedure used in the membrane fabrication. After each batch deposition
of MoS2 nanosheets, the separation characteristics of membrane
layers were evaluated by measuring the BSA protein molecule rejection.
The 1 g/L BSA feed solution was filtered through the membrane, and
the permeate was collected and quantitatively analyzed using a UV–vis
spectrophotometer. The difference in BSA concentrations in the feed
and the permeate gave the percentage of BSA rejected by the membrane
layers. Rejection was measured using eq . The experiment was repeated thrice, and the average
value was taken for rejection measurements. Figure b describes the change in BSA rejections
with the increase amount of MoS2 nanosheets, with each
bar chart representing that the rejection percentage of BSA corresponds
to the different batches in preparing the membrane. M1 depicts the
percentage rejection of BSA by the first batch of MoS2 nanosheet
deposition, which shows a rejection of 60% BSA. Similarly, M2, M3...M12
bars show the rejection percentage of BSA by 2nd batches to 12th batches
of MoS2 nanosheets deposited on the membrane. It can be
seen from Figure b
that there was a linear increase in the rejection percentage of BSA
with an increase in the nanosheet thickness on the membrane. After
the seventh batch, a rejection higher than 90% was accomplished. With
a total of 12 batches of thin MoS2 nanosheets deposited
on the membrane layers, as high as 93.78% rejection of BSA was achieved. Figure c shows the UV absorbance
curve obtained. More the MoS2 nanosheets deposited on the
membrane, lesser the absorbance intensity of the permeate sample,
that is, less BSA molecules in the permeate. In a total of 12 batches,
the absorbance curve was almost flat, indicating the efficient removal
of BSA molecules. As the UF membrane was normally characterized by
the membrane’s nominal molecular weight cutoff, which is typically
defined as the molecular weight of a solute that has a rejection of
90%,[28] our MoS2 nanosheet membrane
layers have met this requirement and can be used for the successful
separation of BSA from water.
Figure 8
(a) Illustration of the batch-by-batch approach
to build MoS2 nanosheet membrane layers; (b) increase in
BSA removal with
the increase of MoS2 nanosheet quantity; and (c) UV–vis
absorbance of BSA for membrane layers M1 to M12.
(a) Illustration of the batch-by-batch approach
to build MoS2 nanosheet membrane layers; (b) increase in
BSA removal with
the increase of MoS2 nanosheet quantity; and (c) UV–vis
absorbance of BSA for membrane layers M1 to M12.
Highly Permeable Porous MoS2 Nanosheet
Membrane
It is interesting to investigate if this porous
MoS2 nanosheet membrane can achieve both high selectivity
and high flux and overcome the trade-off problem faced by the classic
UF membranes. Filtration experiments were carried out using a low-pressure
filtration setup as shown in Figure a. The initial water flux was obtained as 182 ±
2.0 L/(m2 h) (Figure b), which was higher than most of the reported UF membranes.
Then, the filtration of BSA solution was carried out, followed by
thorough washing by water. The recovered water flux of 156 ±
1.5 L/(m2 h) was obtained, and a flux recovery rate of
85.7% by water washing was obtained using eq . The unique nanomaterial-assisted porous
membrane structure had a significant impact on the separation mechanism.
The macro-channels formed by curled-up thin MoS2 nanosheets
allowed easy passage of water molecules, while the microscopic slit
pores formed by intersheets restricted the passage of protein molecules
like BSA and dyes (Figure ).[11,29−31]
Figure 9
(a) Filtration experiment
setup for the flux study and (b) bar
chart showing initial and final water fluxes with percentage recovery.
(a) Filtration experiment
setup for the flux study and (b) bar
chart showing initial and final water fluxes with percentage recovery.
Removal of Acid Red Dyes
by Porous MoS2 Nanosheet Membrane Layers
The use
of polymeric membranes
for the separation of both dyes and proteins is of significant benefit.[32] Different nanoparticles have been incorporated
in the casting of polymeric nanofiltration membranes with the purpose
of enhancing resistance to foulants and the increase in dye removal.[33,34] Such nanomaterial-assisted nanofiltration membranes achieved dye
removal but at a low flux at the applied pressure. The dye molecule
separation capability of MoS2 nanosheet membranes was evaluated
next. Figure a shows
the difference in color intensity achieved by passing 10 mg/L acid
red dye solution through the MoS2 nanosheet membrane. UV–vis
spectrophotometer analysis was conducted to quantify the dye concentration
in both feed and permeate solutions. It can be seen in Figure b that after the first pass,
the acid red concentration was reduced to 2.6 mg/L (73.97% removal)
and the second pass further reduced the color concentration to 0.43
mg/L, and a total of 95.65% color removal has been achieved. These
good results were due to the highly porous nature of the membrane
that adsorbed the dye molecules inside of the membrane pores.[35] The challenging tasks of more than 90% BSA protein
rejection as well as significant dye rejection have been demonstrated
by the MoS2 nanosheet membrane.
Figure 10
(a) Photo showing the
color of initial, first pass, and second
pass acid red dye solution and (b) bar chart showing the initial concentration
and removal percentages at first and second pass.
(a) Photo showing the
color of initial, first pass, and second
pass acid red dye solution and (b) bar chart showing the initial concentration
and removal percentages at first and second pass.
Mechanism of Porous 2D MoS2 Membrane
Separation and Permeability
The performance characteristics
of different low-pressure porous membranes such as UF are the trade-off
between the membrane selectivity and membrane permeability.[2] This means that if the membrane selectivity is
increased due to a smaller pore size, then membrane permeability will
be reduced and vice versa.[3] The intrinsic
membrane transport properties, that is, the permeability and sieving
coefficient, are affected by the specific pore size characteristics
of the membrane. For classic polymeric membranes, by narrowing down
the pore size distribution during the casting step, one can achieve
limited improvement of the membrane performance characteristics, and
other factors such as pore geometry also affect the membrane trade-off
issue.According to the Hagen–Poiseuille equation, membrane
hydraulic permeability (Lp) is related differently to the radius R
of cylindrical shape pores (Figure a), which are typical in the classic polymer matrix,
and to the slit half-width h of a slit pore (Figure b) which forms between thin nanosheets,
that is, intersheet slit pores. For the same value of R and h, that
is, to reject the same-size molecules, according to eqs and 6, the
permeability is in much more in favor of the slit pores with 2.67
times (8/3) higher flux than the cylindrical pores,[36] or equivalently, under the same permeability, the slit
pore membrane displays higher selectivity. This difference is due
to combined intermolecular interactions between the membrane and solute
in the unique slit pore geometry, such as van der Waals (LW), acid–base
(AB), and electrostatic (EL) forces.[37] This
suggests that optimizing a slit pore geometry can enhance the selectivity
while retaining high permeability
Figure 11
Illustration of the (a) cylindrical pore
formed in the polymeric
matrix and (b) slit pore formed by nanosheets.
Illustration of the (a) cylindrical pore
formed in the polymeric
matrix and (b) slit pore formed by nanosheets.When the porous MoS2 nanosheet membrane was assembled
by deposition of numerous detached thin MoS2 nanosheets
into layers, a large number of slit pores were formed by intersheets
by the MoS2 nanosheets with a 200–300 nm size and
a 4.2 nm thickness. On one hand, the slit half-width h was controlled
by the uniform thickness of the MoS2 nanosheets and dictated
the sieving effect of separation. The 93.78% rejection of BSA achieved
in the experiment in Section demonstrated that the slit pores can effectively stop
the passage of BSA molecules of an estimated size of 7.5 × 6.5
× 4 nm[38] due to combined intermolecular
interactions between the membrane and solute. On the other hand, such
porous separation barriers built from numerous individual nanosheets
projected less hydraulic resistance and a much higher flux of 182
± 2.0 L/(m2 h), which were higher than all reported
MoS2-based membranes as well as all UF membranes. Although
slit pores could be formed by other types of nanosheets, the size
and flexibility of the nanosheets are critical for the success. For
example, graphene oxide has a thin layer structure; however, its size
is often in microns, and the layers are soft and wrinkle easily. Both
the factors lead to more resistance and less water passage of the
pores.
Conclusions
In this
work, MoS2 nanosheets were synthesized by a
bottom-up green chemical process where a safe and non-toxic amino
acid, l-cysteine, was employed as a sulfur precursor. With
the specific concentration of reactants and pre-mixing conditions,
MoS2 nanosheets were obtained after the 24 h hydrothermal
reaction at 210 °C. SEM and TEM analyses confirmed the wrinkled
flexible structure of the nanosheets with a 200–300 nm size.
In addition, AFM profiling provided its average thickness as 4.2 nm.
The porous MoS2 nanosheet membranes were prepared by depositing
MoS2 nanosheets in solution using a multiple batch procedure.
BSA protein filtration was carried out and the removal percentage
was measured to evaluate the separation characteristics of each membrane.
The membrane deposited with a total of 12 batches of MoS2 nanosheets achieved 93.78% removal of BSA protein. The total acid
red dye removal of 95.65% has been achieved after the second pass
of filtration. Simultaneously, a high water flux of 182 ± 2.0
L/(m2 h) was obtained, which outperformed almost all reported
UF membranes. The trade-off between selectivity and permeability faced
by classic polymeric UF membranes was overcome by this porous MoS2 nanosheet membrane. The nanosheets with a uniform thickness
affected the half-width h of the slit pores formed by intersheets,
which governed the excellent membrane selectivity to restrict the
passage of BSA and dye molecules; numerous wrinkled nanosheets curled
up to form macro-channels that allowed easy passage of water molecules.
Overall, the chemically synthesized porous MoS2 nanosheet
porous membrane can deliver both high rejection of protein molecules
and maintaining a high flux, attributing to combined factors of slit
pore geometry and less hydraulic-resistant micro-channels formed by
numerous individual nanosheets, making such membranes a promising
candidate for bioprocessing and water treatment.
Authors: Xinglin Lu; Uri R Gabinet; Cody L Ritt; Xunda Feng; Akshay Deshmukh; Kohsuke Kawabata; Masashi Kaneda; Sara M Hashmi; Chinedum O Osuji; Menachem Elimelech Journal: Environ Sci Technol Date: 2020-07-10 Impact factor: 9.028
Authors: Benjamin J Feinberg; Jeff C Hsiao; Jaehyun Park; Andrew L Zydney; William H Fissell; Shuvo Roy Journal: J Colloid Interface Sci Date: 2017-12-20 Impact factor: 8.128
Authors: Wisit Hirunpinyopas; Eric Prestat; Stephen D Worrall; Sarah J Haigh; Robert A W Dryfe; Mark A Bissett Journal: ACS Nano Date: 2017-10-16 Impact factor: 15.881