membranes

Article
Polydimethylsiloxane/Magnesium Oxide Nanosheet Mixed
Matrix Membrane for CO2 Separation Application
Muhd Izzudin Fikry Zainuddin 1 , Abdul Latif Ahmad 1, * and Meor Muhammad Hafiz Shah Buddin 2

1 School of Chemical Engineering, Universiti Sains Malaysia Engineering Campus,

Nibong Tebal 14300, Pulau Pinang, Malaysia
2 School of Chemical Engineering, College of Engineering, Universiti Teknologi MARA,
Shah Alam 40450, Selangor, Malaysia
* Correspondence: [email protected]

Abstract: Carbon dioxide (CO2 ) concentration is now 50% higher than in the preindustrial period
and efforts to reduce CO2 emission through carbon capture and utilization (CCU) are blooming.
Membranes are one of the attractive alternatives for such application. In this study, a rubbery
polymer polydimethylsiloxane (PDMS) membrane is incorporated with magnesium oxide (MgO) with
a hierarchically two-dimensional (2D) nanosheet shape for CO2 separation. The average thickness
of the synthesized MgO nanosheet in this study is 35.3 ± 1.5 nm. Based on the pure gas separation
performance, the optimal loading obtained is at 1 wt.% where there is no observable significant
agglomeration. CO2 permeability was reduced from 2382 Barrer to 1929 Barrer while CO2 /N2
selectivity increased from only 11.4 to 12.7, and CO2 /CH4 remained relatively constant when the
MMM was operated at 2 bar and 25 ◦ C. Sedimentation of the filler was observed when the loading
was further increased to 5 wt.%, forming interfacial defects on the bottom side of the membrane and
causing increased CO2 gas permeability from 1929 Barrer to 2104 Barrer as compared to filler loading
at 1 wt.%, whereas the CO2 /N2 ideal selectivity increased from 12.1 to 15.0. Additionally, this study
shows that there was no significant impact of pressure on separation performance. There was a linear
decline of CO2 permeability with increasing upstream pressure while there were no changes to the
CO2 /N2 and CO2 /CH4 selectivity.
Citation: Zainuddin, M.I.F.; Ahmad,
A.L.; Shah Buddin, M.M.H. Keywords: gas separation; mixed matrix membrane; magnesium oxide; nanosheet filler; CO2 capture
Polydimethylsiloxane/Magnesium
Oxide Nanosheet Mixed Matrix
Membrane for CO2 Separation
Application. Membranes 2023, 13, 337. 1. Introduction
https://doi.org/10.3390/
Sustainable Development Goal 13 (SDG 13) addressed the importance of climate ac-
membranes13030337
tion, which aims to take urgent action in order to combat climate change. Achieving carbon
Academic Editor: Alexander Toikka neutrality in order to mitigate climate change has become a crucial objective as carbon
dioxide (CO2 ) keeps on increasing with no sign of stopping. Currently, the CO2 concen-
Received: 1 February 2023
tration is 50% higher compared to that in the preindustrial era, and it is still increasing
Revised: 2 March 2023
at an alarming rate due to the advancement of the industrial sector [1,2]. Various carbon
Accepted: 8 March 2023
Published: 14 March 2023
capture and utilization (CCU) strategies have been developed, such as cryogenic distil-
lation, pressure-swing adsorption, and chemical absorption to minimize CO2 emissions
into the atmosphere. Even so, these processes have economical drawbacks. For instance,
cryogenic distillation needs to operate at extremely low temperature and high pressure;
Copyright: © 2023 by the authors. pressure-swing adsorption requires the use of effective adsorbents such as zeolites, which
Licensee MDPI, Basel, Switzerland. requires adsorbent regeneration; and chemical absorption involves the use of CO2 -philic
This article is an open access article chemicals that are normally amine-based, which need to be treated before being discharged.
distributed under the terms and In general, these processes are energy intensive, require large capital investment, have
conditions of the Creative Commons high operating costs, have large carbon footprints, and require complex process [3]. As
Attribution (CC BY) license (https://
such, membranes have become an interesting alternative choice for CO2 capture due to less
creativecommons.org/licenses/by/
energy consumption, simplicity of operation, and smaller carbon footprint [4].
4.0/).

Membranes 2023, 13, 337. https://doi.org/10.3390/membranes13030337 https://www.mdpi.com/journal/membranes

Membranes 2023, 13, 337 2 of 21

Polymeric membranes can be classified into two main categories namely glassy and
rubbery polymers. Glassy polymers have rigid and stiff polymer chains that act as obstacles
for gas to pass through, thus exhibiting high gas selectivity with low permeability in
addition to higher mechanical strength relative to rubbery polymer. On the other hand,
rubbery polymers have a flexible and fluidic polymeric backbone chain, which cause them
to have high gas permeance and low selectivity along with relatively lower mechanical
strength as compared to glassy polymers [5]. The phase inversion technique is often
utilized in the fabrication of polymeric membranes. However, the performance of pristine
gas separation membranes is limited by the balance between the dissolution–diffusion
process, which gives rise to Robeson’s upper bound [6,7]. Although, some polymeric
material, such as tricyptene-based polymer of intrinsic microporosity (PIM) or thermally-
rearranged (TR) polymer, could surpass the upper bound [8–10]. Various strategies such as
polymer blending, mixed matrix membrane (MMM) fabrication, and thin film composite
have been utilized to further maximize the separation performance of pristine polymeric
materials [11–13]. MMM, especially, received attention due to its simplicity of fabrication
and promising improvement in separation performance.
Tantekin-Ersolmaz [14] fabricated PDMS/zeolite 5A with different particle sizes of
zeolite 5A. Their result shows that particle size plays a role in improving the permeability of
the gas, while the ideal selectivity on the other hand was not greatly influenced. MMM with
larger zeolite 5A led to higher permeability improvement compared to MMM with smaller
zeolite 5A. This was ascribed to the difficulties of gas permeation due to the enhanced
surface area and improved zeolite–polymer interface in the case of smaller zeolite 5A.
Madaeni et al. [15] also embedded titanium dioxide (TiO2 ) nanoparticles into a PDMS
coating layer supported by porous PES for CO2 separation. Their study revealed that there
is no major improvement offered by the PDMS/TiO2 due to the simultaneous occurrence
of copolymerization between Si-OH and PDMS molecules and self-condensation of the
polymer chain. As such, the presence of TiO2 does not improve the free fractional volume
of the PDMS coating to enhance the gas separation performance. Nour et al. [16] blended
multiwalled carbon nanotubes (MWCNT) with PDMS for hydrogen purification, and they
observed that increasing MWCNT loading from 1 wt% to 10 wt% into PDMS increased H2
selectivity due to efficient blocking of CH4 . Furthermore, they also discovered that the Si-
CH3 Si-O bond was reduced with the presence of MWCNT, which caused the reduction of
CH4 permeability. Metal organic framework (MOF) UiO-66 embedded in PDMS at 40 wt%
increased CO2 permeability and CO2 /N2 selectivity 0.7 times and 1.3 times, respectively, as
compared to the base PDMS membrane in a study by Wang et al. [17] Most of the literature
describes utilizing PDMS as the membrane and the polymer matrix to form MMM for
CO2 capture using either fillers with nanorod or nanospherical shaped particles. Recently,
two-dimensional (2D) materials have received increasing attention in MMM fabrication
due to their potential of exhibiting barrier properties when they are horizontally aligned,
thus improving the selectivity of the MMM [18,19]. However, aligning the 2D nanosheet
inside the polymer membrane matrix fabricated through typical physical blending still
remains a challenge [20].
Zahri et al. [21] incorporated graphene oxide (GO) into a polysulfone hollow fibre
membrane, and they reported that the presence of GO inside the polysulfone hollow fibre
membrane matrix disrupted the polymer chain packing and increased the tortuosity of the
membrane, thus hindering diffusion of gas molecules with larger kinetic diameter, such
as nitrogen (N2 ) and methane (CH4 ), while facilitating diffusion of CO2 gas through the
selective layer, improving CO2 /N2 and CO2 /CH4 gas selectivity. Yang et al. [22] fabricated
asymmetric Matrimid polyimide with nitrogen-doped graphene nanosheet MMM with
low filler loading (<0.1 wt%). Even with extremely low loading, substantial improvement
of gas selectivity was observed; it improved CO2 /N2 selectivity by 45.8% as compared to
pristine asymmetric Matrimid membrane with a slight reduction in CO2 permeance. The
observation was attributed to the increased tortuous path induced by the presence nitrogen-
doped graphene in the dense selective layer of Matrimid membrane. Similar observations
Membranes 2023, 13, 337 3 of 21

were also made by Feijani et al. [23]. Furthermore, Asim et al. [24] incorporated a range
of 1 wt.% to 10 wt.% of 2D graphitic-Polytriaminopyrimidine (g-PTAP) into Pebax-1657
membrane. The optimum 2D g-PTAP loading they obtained based on the gas separation
performance was at 2.5 wt.%, whereby they observed a simultaneous improvement of CO2
permeability from 82.3 to 154.6 barrier with CO2 /N2 selectivity improved from 549.5 to
83.5. To conclude, the inclusion of inorganic filler inside a glassy polymeric membrane led
to the disruption of the polymeric chain, which resulted in an increased tortuosity path
of the gas molecule traveling between the retentate and permeate sides, thus improving
the selectivity of the gas. Other than graphene oxide, other porous 2D-based material
from zeolites, metal organic framework (MOF), MXene, covalent organic framework (COF),
and layered-double hydroxide were also studied for MMM fabrication in gas separation
application [25,26]. Nevertheless, literature regarding PDMS MMM utilizing 2D nanosheet
filler for CO2 capture is scarce. For instance, there are several studies that already utilized
2D nanosheet fillers to fabricate PDMS MMM, albeit for other separation applications.
Gou et al. [27] incorporated MFI zeolite nanosheets into PDMS membranes for butane
isomer separation application, in which they discovered that the presence of the open-
pore MFI zeolite nanosheet enhanced both n-butane permeability and n-butane/i-butane
ideal selectivity. Shen et al. [28] utilized GO in PDMS for a propane recovery application.
Jafari et al. utilized reduced graphene oxide (rGO) functionalized with octadecylamine for
toluene removal using pervaporation [29]. Based on our literature study, we believe that
PDMS MMM utilizing 2D nanosheet metal oxide filler is yet to be reported exclusively for
CO2 /N2 and CO2 /CH4 separation application.
Magnesium oxide (MgO) has been studied and used as adsorbent, as it has been
shown to have affinity towards CO2 gases, which can be adsorbed onto the surface of the
MgO [30–32]. Previous work utilizing MgO nanoparticles as a dispersed phase to form
MMM using glassy polymer showed improved gas permeability with slightly reduced
gas selectivity, which could be ascribed to the increased formation of free volume in the
polymer [33,34]. The focus of this work is to determine the effect of MgO exhibiting
hierarchically porous 2D nanosheets with a PDMS matrix. According to Li et al. [35], such
2D porous nanosheet configurations having high surface area, open pore structure, and
well-dispersed fine MgO nanoparticles are favourable for CO2 gas sorption. Additionally,
MgO could potentially facilitate CO2 transport through the membrane via Lewis acid–
base mechanism, as explained in previous literature [36–38], which may contribute to the
improvement of the gas separation performance. Secondly, as far as the fabrication of
ultra-thin defect-free asymmetric membrane is concerned, they are really challenging, as
they have many factors to be considered [39]. Typically, an asymmetric membrane with
a thin skin layer experiences incomplete polymer coalescence with pinhole formation,
thus reducing the gas selectivity [40], and these defects are commonly sealed with highly
permeable rubbery polydimethylsiloxane (PDMS) [41]. Rubbery polymer transports the gas
penetrant using gas solubility rather than gas diffusivity through the polymer, as in glassy
polymer, due to the flexible polymeric chain backbone of the rubbery polymer [42]. Hence,
rubbery polymer exhibits much higher permeability towards the gas penetrant as compared
to glassy polymer. However, the balance of solution–dissolution process causes rubbery
polymer to show relatively lower selectivity as compared to glassy polymer, which causes
it to perform more poorly than the upper bound [7]. PDMS is a rubbery polymer with
high permeability towards CO2 gas and with considerably good ideal selectivity against
CO2 /N2 and CO2 /CH4 . It is also cheap and readily available in the market [43,44]. It was
hypothesized that inorganic filler with nanosheet structure gives rise to barrier properties,
which can enhance gas separation properties [45]. As such, it is expected that the inclusion
of 2D nanosheets into rubbery polymers can improve the selectivity of the membrane
while achieving high permeability of the gas penetrant. Moreover, the fabrication of
asymmetric MMM with inorganic fillers also gives rise to wasteful distribution of the filler
in the porous substructure, which does not contribute to the separation process, since the
process is dominated by the dense skin layer. Hence, mixed matrix thin film composite
Membranes 2023, 13, 337 4 of 21

(MMTFC) membranes with secondary selective layers made from other highly permeable
polymeric materials embedded with inorganic filler appear to be more viable [46]. However,
Henis and Tripodi [47] proved that the coating layer does not play a significant role in
separation of gas; the separation performance is ultimately dictated by the integral skin
layer of the asymmetric membrane. Henceforth, in this study, we focus on determining the
effectiveness of PDMS MMM in TFC by fabricating an MMM consisting of self-standing
PDMS and MgO nanosheet to elucidate the intrinsic separation performance of PDMS
MMM for CO2 capture application in flue gas or natural gas separation to determine
whether the PDMS MMM coating plays a role in the MMTFC configuration membrane.
Moreover, to the best of our knowledge, no literature has reported the use of PDMS with
an MgO nanosheet for CO2 /N2 and CO2 /CH4 separation application. PDMS is chosen as
the membrane matrix material in this study for its readiness in forming dense membrane
and as it is a highly permeable polymer towards CO2 .

2. Materials and Methods

2.1. Materials
PDMSs (Sylgard-184) were procured from Dow Corning (USA). They consist of two
components: elastomer and curing agent. In accordance with the recommendation by the
manufacturer, the elastomer and curing agent were mixed at the ratio of 10:1 for membrane
fabrication. The n-pentane (>96 wt% purity) was purchased from Merck (Germany) was
used as the solvent for membrane fabrication. Sodium hydrogen carbonate, NaHCO3 ,
and magnesium chloride, MgCl2 (anhydrous) precursors, were purchased from Merck
(Germany) for the fabrication of magnesium oxide nanosheets. Ethanol, C2 H5 OH (99.5 wt%
purity), was purchased from Merck (Germany). All materials procured were used as
received without further purification.

2.2. Membrane Fabrication

Dense PDMS membranes were fabricated with a solvent evaporation method [48].
PDMS elastomers were dissolved with a magnetic stirrer for 15 min in n-pentane to form
10 wt% PDMS solution at room temperature. After the solution became homogenous,
the curing agent was added and further stirred for 1 h at room temperature to ensure
complete dissolution of solution. A fixed volume of the homogenous solution was poured
into a levelled Petri dish with a fixed size and heated at 35 ◦ C for 2 h to allow complete
solvent evaporation. The rate of solvent evaporation was kept slow to prevent formation of
pores or pinholes. The formed membranes were then placed in a vacuum oven at 120 ◦ C
overnight before use.

2.3. Synthesis of Magnesium Oxide Nanosheet

A facile nonhydrothermal method was utilized to fabricate the MgO nanosheets that
were previously studied for solar cell application [49] and olefin/paraffin separation [50].
Briefly, 0.32 g of NaHCO3 were dissolved with a magnetic stirrer in a mixture of 100 mL of
ethanol and 45 mL of ultrapure water (18.2 MΩ-cm). After all the solids were completely
dissolved, 0.1 g of MgCl2 were added to the solution and were left for about 3 h to allow
complete reaction. The solution was then purged with N2 gas at 1 atm and heated to
70 ◦ C for two hours with a plate heater. A white solid formed, and magnesium carbonate
(MgCO3 ) was retrieved and centrifuged several times (with 2:1 ratio of ethanol/ultrapure
water) to remove residual unreacted reactant. The retrieved white solids were vacuum
filtered on filter paper and dried at room temperature before being calcined at 400 ◦ C for
2 h to decompose the MgCO3 into MgO. The furnace was ramped at 5 ◦ C min−1 . The
surface area of the synthesized MgO nanosheet particles was characterized by Brunauer–
Emmett–Teller (BET) method using Micromeritics ASAP 2020 (Micromeritics Instrument
Corp., Georgia, USA). The weighed samples (~0.10 g ± 0.01 g) were vacuumed and heated
to 300 ◦ C for 16 h to completely remove any adsorbed moisture on the surface of the
synthesized MgO nanosheets.
 2 h to decompose the MgCO3 into MgO. The furnace was ramped at 5 °C min−1. The surface
area of the synthesized MgO nanosheet particles was characterized by Brunauer–
Emmett–Teller (BET) method using Micromeritics ASAP 2020 (Micromeritics Instrument
Corp., Georgia, USA). The weighed samples (~0.10 g ± 0.01 g) were vacuumed and heated
Membranes 2023, 13, 337 to 300 °C for 16 h to completely remove any adsorbed moisture on the surface of 5 ofthe
21
synthesized MgO nanosheets.

2.4. Mixed Matrix Membrane Fabrication

2.4. Mixed Matrix Membrane Fabrication
The fabrication of the mixed matrix membrane was similar to the steps reported in
The fabrication of the mixed matrix membrane was similar to the steps reported in
Section 2.2. After 1 h stirring at room temperature, and with the addition of curing agent,
Section 2.2. After 1 h stirring at room temperature, and with the addition of curing agent,
precalculated MgO nanosheets with various loadings (0, 0.25, 0.5, 1.0, 2.5, 5.0 wt%) with
precalculated MgO nanosheets with various loadings (0, 0.25, 0.5, 1.0, 2.5, 5.0 wt%) with
PDMS mass basis were added to the solution under stirring conditions using Equation (1).
PDMS mass basis were added to the solution under stirring conditions using Equation (1).
The mixture was then stirred for another hour and sonicated for 15 min to ensure good
The mixture was then stirred for another hour and sonicated for 15 min to ensure good
dispersion of the filler inside the solution. A fixed volume of the solution was then poured
dispersion of the filler inside the solution. A fixed volume of the solution was then
to a fixed-size Petri dish and heated at 35 °C to allow complete evaporation of the solvent.
poured to a fixed-size Petri dish and heated at 35 ◦ C to allow complete evaporation of the
The membranes were then heated at 120 °C for 24 h before being tested using a gas
solvent. The membranes were then heated at 120 ◦ C for 24 h before being tested using
aseparation test. test.
gas separation Preparations of neat
Preparations andand
of neat MMM MMM PDMSs
PDMSs areareshown
shownininFigure
Figure 1. The
1. The
fabricated membranes
fabricated membranes were were denoted
denoted M1
M1 to
to M6,
M6, where
where the
the mass
mass component
component ofof each
each MMM
MMM
is shown in Table
is shown in Table 1. 1.

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑀𝑔𝑂
Mass𝑔o f MgO( g)
𝐹𝑖𝑙𝑙𝑒𝑟 % Filler
= (%) = (1)
(1)
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑃𝐷𝑀𝑆
Mass o𝑔f PDMS
𝑀𝑎𝑠𝑠( g𝑜𝑓
) +𝑀𝑔𝑂
Mass𝑔o f MgO( g)

Figure 1. Schematic representation

Figure 1. representation of
of membrane
membrane preparation.
preparation.

Table1.1. Mass
Table Mass composition
compositionof
ofthe
theprepared
preparedmembrane.
membrane.

Membrane Elastomer to Curing

Elastomer to Mass of MgO
Membrane Mass of Mass
Massof Curing Mass of Mass of
of Mass of Curing Mass
n- of MgO Nanosheet
Sample Agent Ratio Curing
PDMS (g) Agent Agent (g) n-Pentane (g) (PDMSNanosheet (PDMS
Mass Basis) (g)
Sample PDMS (g) Agent (g) Pentane (g)
M1 10:1 Ratio
2 0.2 19.8 Mass
0 Basis) (g)
M2 10:1 M1 10:1
2 2
0.2 0.2 19.8 19.8 0.005010
M3 10:1 M2 2
10:1 0.2
2 0.2 19.8 19.8 0.01005
0.00501
M4 10:1 M3 2
10:1 0.2
2 0.2 19.8 19.8 0.02020
0.01005
M5 10:1 2 0.2 19.8 0.05128
M6 10:1
M4 10:1
2
2
0.2
0.2 19.8
19.8 0.02020
0.10526
M5 10:1 2 0.2 19.8 0.05128
M6 10:1 2 0.2 19.8 0.10526
2.5. Membrane Characterization
The surface
2.5. Membrane and cross-sectional area of the fabricated membranes were observed using
Characterization
tabletop scanning electron microscopy (SEM) (TM3000, Hitachi Ltd., Tokyo, Japan) to
study the distribution of the fillers. A water contact angle (CA) measurement was made
using a goniometer (Rame’-Hart Instrument Co., Succasunna, NJ, USA), with a sessile drop
method to study the surface properties of the membranes. A constant volume of deionized
(DI) water was dropped on the membranes at five different locations at room temperature
to obtain the average values. Average values of five readings are reported for the CA
measurement. Fourier transform infrared (FTIR-ATR) (Perkin Elmer, Waltham, MA, USA)
was used to study the bonds present inside the membranes and to confirm the presence of
magnesium oxide nanosheet fillers. Brunauer–Emmett–Teller (BET) analysis was performed
Membranes 2023, 13, 337 6 of 21

on the fabricated MgO nanosheets to determine the isotherm and surface area. Thermal
analysis of the fabricated membranes was performed using thermal gravimetric analysis
(TGA) (STA6000, Perkin Elmer, USA) and differential scanning calorimetry (DSC) (DSC4000,
Perkin Elmer, USA) to determine the change in the physical or thermal transition of the
fabricated membranes to further elucidate the interaction between PDMS and MgO. For
TGA, the samples were heated at a rate of 10 ◦ C/min from 25 ◦ C to 800 ◦ C under inert
nitrogen atmosphere condition while for DSC analysis, the samples were heated at a rate of
10 ◦ C/min from 25 ◦ C to 400 ◦ C.

2.6. Gas Separation Performance

The gas performance set-up and its schematic diagram has been described elsewhere [44].
Pure gas separation performance was conducted at pressure ranging from 2 to 5 bar at
room temperature conditions using a constant-volume variable pressure method. All the
gas used was of high purity (>99.995 wt%). The flat sheet PDMS membrane samples were
fixed to a module with an effective permeation area of 3.142 cm2 . The pure gases were
fed in the following sequence: N2 , followed by CH4 , and lastly CO2 . The upstream was
purged with targeted test gas before commencing the test, and all the data were taken at
least twice to ensure consistency. The permeability of the individual gas was calculated
using Equation (2):
273.15 × 1010 × V × l dp
 
P= 760AT ( Po ×76)
(2)
dt
14.696

where P is the gas permeability in unit Barrer (1 Barrer = 1 × 10−10 cm3 (STP)·cm/cm2 ·s·cmHg),
V is the volume of gas permeate in the downstream chamber (12 cm3 ), l is thickness of
the effective skin layer (cm), A is the effective permeation area (cm2 ), Po is the upstream
pressure (psi), and dp/dt is the pressure gradient (psia/s). The gas ideal selectivity is then
calculated using Equation (3):
P
αi,j = i (3)
Pj
where α is the ideal gas selectivity (ratio of individual gas permeability), and P is the
permeability of the individual gas calculated using Equation (2). The subscripts I and j
correspond to the gas penetrant species.

3. Results and Discussions

3.1. Characterization of MgO Nanosheet Filler
The as-synthesized mesoporous MgO nanosheets were characterized using SEM imag-
ing and N2 adsorption isotherm using the BET method presented in Figure 2. From the
SEM images, the as-synthesized MgO nanoparticle exhibited a hierarchically nanosheet-
like structure. It was further analysed with N2 adsorption–desorption isotherm, where
the N2 adsorption isotherm exhibited a type IV isotherm with a hysteresis loop charac-
teristic showing the synthesized MgO nanosheet exhibiting multi-modal pores [50]. The
isotherm also showed a steep rise at P/P0 = 1, indicating the presence of pores due to
the voidage between the aggregated MgO nanosheet particles [51]. The BET surface area
of the synthesized MgO nanosheets obtained in this study is 270 m2 /g, slightly higher
than the BET value reported by Qureshi et al. [49], which is at 216 m2 /g. The pore size
distribution of MgO nanosheets was determined using the Barrett–Joyner–Halender (BJH)
curve as shown in the inset of Figure 2. The synthesized MgO nanosheet exhibited four
different maximum points of pore distribution at 2.6 nm, 8.9 nm, 74.7 nm, and 117.1 nm,
with broad pore distribution between 30 and 95 nm based on the BJH pore distribution
curve indicating a hierarchically arranged three-dimensional structure. These values were
close to those from a previous study by Park et al. [50] who used the MgO nanosheet for an
olefin/paraffin separation process, although it is slightly differs from Qureshi et al. [49],
who achieved only a single maximum peak in the range of approximately 10–15 nm. The
average thickness of the synthesized MgO nanosheet was estimated based on FESEM. The
 different maximum points of pore distribution at 2.6 nm, 8.9 nm, 74.7 nm, and 117.1 nm,
with broad pore distribution between 30 and 95 nm based on the BJH pore distribution
curve indicating a hierarchically arranged three-dimensional structure. These values were
close to those from a previous study by Park et al. [50] who used the MgO nanosheet for
Membranes 2023, 13, 337 an olefin/paraffin separation process, although it is slightly differs from Qureshi et al.7[49],
of 21
who achieved only a single maximum peak in the range of approximately 10–15 nm. The
average thickness of the synthesized MgO nanosheet was estimated based on FESEM. The
average thickness was taken from four different places. A sample image of the thickness
average thickness was taken from four different places. A sample image of the thickness
measurement is shown in Figure S1(see Supplementary Materials).
measurement is shown in Figure S1(see Supplementary Materials).

Figure 2. SEM image of MgO nanosheet at (a) 5000× magnification and (b) 10,000× magnification.
(c) N2 adsorption–desorption isotherm of synthesized MgO nanosheet. The inset shows the BJH pore
distribution curve of the MgO nanosheet.

3.2. Morphology of PDMS and PDMS/MgO Membrane

The cross-sectional and surface morphology of the fabricated membranes were exam-
ined using SEM images, as are shown in Figure 3, to study the effect of the presence of MgO
nanosheets on membrane structure. The surface of the M1 to M6 membranes appeared
dense with no sign of pinhole formations. When lower loading of MgO was embedded into
the PDMS matrix, some of the MgO was observed on the surface of the membrane (M2, M3,
and M4). Meanwhile, when the loading was higher, more of the MgO particle appeared
on the top surface (M5 and M6). To see whether this phenomenon affected the surface
properties of the membrane, water CA of the membranes were measured. For a pristine
Membranes 2023, 13, 337 8 of 21

M1 membrane, the water CA obtained was 105.2◦ , which falls in the hydrophobic category.
The value obtained was also close to that of other reported literature [52,53]. MgO is known
to be hydrophilic [54]. The presence of MgO filler in MMM slightly altered the CA of the
MMM, as some part of this filler appeared on the surface of the MMM. The CA of M2 was
essentially similar to M1, as the MgO loading was very low (0.25 wt%). However, the CA
started to reduce when the loading was further increased. Regardless, the difference of the
CA values was not significant, even though it appeared to drop with increasing MgO load-
ing. Based on the observation of the cross-sectional morphology, all membranes exhibited
a dense layer across the cross section of the membrane. The rate of liquid–liquid demixing
from the polymer–solvent–nonsolvent system determined the structure of the fabricated
membrane. Slow liquid–liquid demixing will lead to a dense or spongy structure while
fast liquid–liquid demixing will lead to an elongated, finger-like structure. In this study, all
membranes were fabricated using the solvent evaporation method. The solvent used to
dissolve the PDMS precursor in this study, n-pentane, is a volatile solvent. When a dope
solution is poured into a Petri dish of a fixed size, n-pentane will gradually evaporate
from the polymer–solvent system, thus leaving only PDMS in the petri dish. The PDMS
polymer solution also gradually becomes more concentrated until all n-pentane eventually
evaporates out. Hence, the PDMS polymer has sufficient time to rearrange itself neatly,
forming a dense PDMS membrane. The thickness of the fabricated membranes is listed in
Table S1. The thickness of M1 and M6 varied slightly compared to the other membranes,
which could be due to the error introduced when levelling the Petri dish during solvent
evaporation. However, it is important to note that the thickness of the membrane may
affect the gas permeance, but it does not affect the permeability values of the membrane,
as permeability is an intrinsic property of the membrane. However, in the case of a thin
membrane (<200 nm), it is reported that permeability and selectivity of the PDMS mem-
brane become thickness-dependent [55,56]. Moreover, the thickness of the membranes
fabricated in this study were greater than 250 µm. Hence, it is expected that a slightly
varied membrane thickness will not affect permeability and selectivity of the membranes in
this study. Furthermore, the surface of neat PDMS (M1) appeared smooth and defect-free,
without formation of pinholes, showing that dense PDMS membrane was successfully
fabricated with 10 wt.% PDMS solution in n-pentane with the solvent evaporation method.
For MMM fabrication, there are several important factors that must be considered,
such as the compatibility between polymer and filler, their interaction, and the dispersion
of the filler inside the polymeric membrane matrix. The inorganic fillers need to be evenly
distributed throughout the polymeric matrix to ensure that there is no local agglomeration
inside the membrane, which can create voids and form nonselective channels, which is not
favourable for gas separation as it will affect gas selectivity. Based on the cross-sectional
image of M2 and M3, there was no sign of aggregation of the filler, and the filler appears
to be well dispersed. The surfaces of the M2 and M3 membranes also appeared smooth,
which means that the MgO nanosheet did not migrate and protrude to the surface, forming
nonselective voids. However, in M4 with 1 wt.% of MgO loading in PDMS, there appeared
to be some aggregate of the inorganic filler inside the polymer matrix (circled in yellow),
although the agglomeration was not really severe to the point where they stacked with
each other in a manner that could form a visible nonselective void. The phenomena also
occurred in M5, where there were more agglomerates of MgO nanosheets observed. The
agglomeration of nanoparticles often happened at high loading, as they possess high surface
energy. The interaction between filler due to Van der Waals or other interaction [57,58]
became more dominant than the interaction between the filler and polymer matrix at high
filler loading, thus forming an agglomerate of fillers, which may lead to the formation of
a nonselective void.
Membranes 2023, 13, 337 9 of 21
Membranes 2023, 13, x FOR PEER REVIEW 10 of 23

Figure 3. Surface and cross-sectional morphology of PDMS and PDMS/MgO membranes at various
loading. The inset of the surface morphology shows the water CA obtained from five average values.
The inset in cross-sectional area of M6 shows the sedimentation of MgO nanosheet at the bottom of
the membrane matrix.

However, M6 does not only have an agglomerated filler, but the membrane also
exhibits significant sedimentation of MgO nanosheet filler on the bottom side of the mem-
brane, as shown in Figure 3 (inset cross-sectional image of M6). The excessive loading of
the MgO nanosheet filler inside the polymer matrix may have restricted the homogeneity of
the dope solution, thus preventing the filler from being well dispersed inside the polymer
matrix. The same phenomenon can be observed in another study by Jusoh et al. [59],
where it was observed that the zeolite T filler started to form sedimentation at the bottom
of the membrane at higher zeolite T loading. Inadequate strong adhesion between the
MgO nanosheet filler and the PDMS polymer chain may also have contributed to the
sedimentation of the filler as well. According to Chang Y.-W. and Chang B.K. [60], another
Membranes 2023, 13, 337 10 of 21

aspect to be considered for the sedimentation phenomena is the viscosity of the polymer
dope. Sedimentation easily occurs with lower polymer dope viscosity as it is not enough
to keep the filler suspended during phase separation. On the other hand, it is harder for
filler inside a more viscous polymer dope to experience sedimentation due to competing
forces between gravitational pull and hindrance from the viscosity of the polymer dope.
In the context of this study, the PDMS concentration was maintained at 10 wt.% for all
fabricated membranes. As such, at lower filler concentration, the viscosity of the polymer
dope solution was sufficient to ensure that the filler be suspended during phase separation.
While at higher filler concentration, the influence of viscosity becomes less significant,
and the effect of gravitational force acting on the filler becomes dominant, thus leading to
sedimentation. As such, it can be concluded that the combined effect of the weak adhesion
between MgO the nanosheet filler and the PDMS polymer chain and the dominating effect
of gravitational pull on the filler at higher loading leads to sedimentation of the filler. The
opposing nature of hydrophobic solvent (n-pentane) and hydrophilic fillers (MgO) may
or may not contribute to the sedimentation of the fillers. The sedimentation issue may be
mitigated by increasing the polymer dope solution, which in turn increases the viscosity
of the polymer solution, as it is known that viscosity of a polymer is a function of its
concentration [44,61,62]; hence, the higher polymer viscosity may keep higher filler loading
suspended during phase separation. However, this will also lead to thicker membrane
formation, which in turn will lower the gas permeance due to the increased resistance from
the membrane’s thickness. Therefore, in this study we did not further increase the polymer
concentration. Hence, it is concluded that the MgO nanosheet can be dispersed effectively
in a PDMS membrane matrix up to 1 wt.% content.

3.3. FTIR Analysis

The full FTIR spectra is shown in Figure 4, while Figure S2a shows the magnified
spectra from 600 to 1700 cm−1 , and Figure S2b shows the difference in the intensity of
the peak in the region from 600 to 1700 cm−1 . For pristine PDMS, the peak at 787 cm−1
corresponds to the stretching of the -CH3 and Si-C bond in the Si-CH3 chain. The peak
from 1009 to 1061 to cm−1 shows the Si-O-Si stretching of the polymeric chain. The peak at
1255 cm−1 is assigned to the deformation of the -CH3 group in the Si-CH3 chain, and, finally,
the stretching at 2957 cm−1 is due to the asymmetric stretching of -CH3 in the polymeric
chain of the PDMS polymer [63]. A freshly prepared MgO nanosheet particle was used for
the FTIR spectra analysis. The broad peak ranging from 600 to about 800 cm−1 indicates the
Mg-O-Mg bond [64], and the characteristic peak at 850 cm−1 is ascribed to the stretching of
the Mg-O metallic bond of the MgO nanosheet particle [65,66]. Meanwhile the broad peak
at 1417 cm−1 is assigned to the stretching of symmetrical and asymmetrical carboxylate O-
C=O, which may present due to the unreacted precursors [67]. There exists a very minimal
peak in the range from 3000 to 3800 cm−1 that is attributed to the presence of the H-O-H
bond of the water molecule on the surface of the MgO nanosheet nanoparticle [68]. It is
known that MgO is highly hygroscopic; thus, the moisture from the atmosphere may readily
adsorb onto the surface of the MgO nanoparticle [31,69]. Additionally, no further peak
emerged from the spectra analysis in MMM, showing that there was no chemical interaction
between PDMS and MgO nanosheets other than the slight differences in the intensity of
the peak at 850 cm−1 and 1417 cm−1 , which corresponds to the amount of MgO present in
the fabricated MMM. The FTIR spectra also confirmed that there is no presence of residual
n-pentane solvent in the fabricated membrane using the solvent evaporation method.
 nanoparticle [31,69]. Additionally, no further peak emerged from the spectra analysis in
MMM, showing that there was no chemical interaction between PDMS and MgO
nanosheets other than the slight differences in the intensity of the peak at 850 cm−1 and
1417 cm−1, which corresponds to the amount of MgO present in the fabricated MMM. The
Membranes 2023, 13, 337 FTIR spectra also confirmed that there is no presence of residual n-pentane solvent 11
inofthe
21
fabricated membrane using the solvent evaporation method.

Transmittance (a.u)
M1
M2
M3
M4
M5
M6
MgO

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Figure 4. FTIR spectra analysis of PDMS and PDMS/MgO membrane.

Figure 4. FTIR spectra analysis of PDMS and PDMS/MgO membrane.
3.4. Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC)
The thermal stability of PDMS and PDMS/MgO membranes was studied by analysing
the thermal decomposition of the membrane with TGA and DTG curves, as shown in
Figure 5. For MgO nanosheet powder, the temperature loss at the 200 ◦ C to 300 ◦ C region
could be ascribed to the loss of the water moisture that may have physically or chemically
adsorbed on the surface of the MgO nanosheet powder upon long storage [69,70]. For
pristine PDMS membranes, the first on-set temperature ranged from approximately 300 ◦ C
to 400 ◦ C, which is due to the typical loss of water moisture and physical adsorbed layer [71]
as well as removal of lateral groups from the main chain of PDMS, while the mass reduction
from around 450 to 600 is ascribed to the breakdown of the PDMS chain [48]. The weight
loss for M4 and M6 was less than that of M1 based on the TGA and DTG curves in Figure 5.
The final residues remaining on M1, M4, and M6 were 55%, 66%, and 68%, respectively.
This could be ascribed to the amount of MgO nanosheet filler present in each membrane,
whereby M6 had the highest MgO nanosheet loading, contributing to more residual mass
compared to M4 and M1. The initial thermal decomposition of PDMS/MgO MMM 393
shifted to 501 ◦ C for both M4 and M6 as compared to the pristine M1 membrane, which
could be ascribed to the disruption of the polymeric matrix by the MgO nanosheet lowering
the polymer chain’s mobility [72]. The thermal stability between M4 and M6 does not differ
significantly, albeit the MgO nanosheet content in M6 is about five times higher than in M4.
Both M4 and M6 exhibited almost similar TGA curves. However, based on the DTG curves,
M4 showed a slightly higher rate of mass loss at 509 ◦ C (−0.964%) and 635 ◦ C (−1.25%) as
compared to the rate of mass loss for M6 at 512 ◦ C (0.818%) and 659 ◦ C (−0.752). Hence, the
improvement of thermal stability of the membrane with MgO nanosheet loading beyond
1 wt.% was not significant. Therefore, it can be concluded that the presence of the MgO
nanosheet inside the PDMS matrix enhanced the thermal stability of the membrane. The
MgO nanosheet prevented volatile movement of volatiles during thermal treatment. When
the samples were further heated, M1 showed significant mass loss when the temperature
was approximately 598 ◦ C. Meanwhile, for M4 and M6, the second thermal decomposition
shifted to 636 ◦ C and 656 ◦ C, respectively. Lastly, the increase in mass residue of the samples
could be attributed to the presence of inorganic MgO nanosheet filler that sustains even at
high temperature.
Membranes 2023,13,
Membranes2023, 13,337
x FOR PEER REVIEW 12 of
13 of 21
23

Figure 5. Thermal gravimetric analysis (TGA) and derivative thermogravimetric (DTG) curves of
Figure 5. Thermal gravimetric analysis (TGA) and derivative thermogravimetric (DTG) curves of
PDMS
PDMSand
andPDMS/MgO
PDMS/MgO membranes.
membranes.
Membranes 2023, 13, 337 Membranes 2023, 13, x FOR PEER REVIEW 13 of 21 14 of 23

DSC was performed onto the synthesized MgO powder, PDMS, and PDMS/MgO
DSC was performed onto the synthesized MgO powder, PDMS, and PDMS/MgO
nanosheet composite membrane with temperatures ranging from 25 °C to 400 °C and is
nanosheet composite membrane with temperatures ranging from 25 ◦ C to 400 ◦ C and is
represented in Figure 6. For the MgO nanosheet powder, the broad endothermal peak in
represented in Figure 6. Forbetween
the range the MgO nanosheet
175 °C and 300 powder,
°C was thedue
broad endothermal
to the loss of waterpeak in the [66] as
moisture
range between 175 ◦ C and 300 ◦ C was due to the loss of water moisture [66] as confirmed by
confirmed by the DTG thermogram in Figure 5. Meanwhile, the first thermal transition
the DTG thermogram in Figure
was observed 5. Meanwhile,
at the region between the60
first thermal
°C and 75 °Ctransition
for M1, M4, was
andobserved at
M6. The transitional
the region between 60 ◦ C and 75 ◦ C for M1, M4, and M6. The transitional temperature did
temperature did not differ much between M1, M4, and M6, but the heat flow value
not differ much between
increasedM1,with M4, and M6,MgO
increasing but nanosheet
the heat flow value
content increased
in the with increasing
PDMS membrane. Suleman et al.
MgO nanosheet [73]contentalsoin reported
the PDMSnearly similarSuleman
membrane. first-transition temperatures
et al. [73] also reported in nearly
their studies.
Additionally,
similar first-transition the endothermic
temperatures peaks of M1,
in their studies. M4, and M6the
Additionally, in the range between
endothermic peaks375 °C and
°C were due to the loss of◦ water ◦
of M1, M4, and M6 in the range between 375 C and 400 C were due to the loss of waterfrom the
400 moisture and physical adsorbed layer
membranes,
moisture and physical adsorbedas discussed
layer fromin Figure 5. There is no
the membranes, as distinctive
discussed glass transition
in Figure temperature
5. There
(Tg) observed in Figure 6. Moreover, PDMS is one of the rubbery polymers that has the
is no distinctive glass transition temperature (Tg ) observed in Figure 6. Moreover, PDMS is
lowest Tg (~−123 °C) [74].
one of the rubbery polymers that has the lowest Tg (~−123 ◦ C) [74].
22

20
Heat Flow Endo Up (mW)

18

16

14

12

10
25 75 125 175 225 275 325 375
Temperature (°C)

M1 M4 M6 MgO

Figure 6. Differential scanning calorimetry (DSC) thermogram of MgO nanosheet powder, PDMS,
Figure 6. Differential scanning calorimetry (DSC) thermogram of MgO nanosheet powder, PDMS,
and PDMS/MgO membranes.
and PDMS/MgO membranes.

3.5. Gas Separation Performance

3.5. Gas Separation Performance
3.5.1. Effect of MgO Nanosheet Loading
3.5.1. Effect of MgO Nanosheet Loading
Single gas permeation tests are carried out on the fabricated PDMS and PDMS/MgO
Single gas permeation tests are carried out on the fabricated PDMS and PDMS/MgO
membranes to further elucidate
membranes the effectiveness
to further of MgO nanosheets
elucidate the effectiveness as fillers in
of MgO nanosheets as PDMS
fillers in PDMS
membranes. In this section, the upstream pressure was kept at 2 bar, and the permeation
membranes. In this section, the upstream pressure was kept at 2 bar, and the permeation
was carried out at room
was temperature.
carried out at roomFigure 7 shows
temperature. the CO
Figure 2 permeability
7 shows with CO2 /N
the CO2 permeability with
2 CO2/N2
and CO2 /CH4 asand idealCOselectivity of the
2/CH4 as ideal membranes
selectivity with respectwith
of the membranes to various MgO
respect to nanosheet
various MgO nanosheet
loadings. Based loadings.
on the trend,
Basedtheon CO permeability
the 2trend, did not show
the CO2 permeability didanot
linear
show trend with
a linear thewith the
trend
increase in MgOincrease
nanosheet in MgO
fillernanosheet
loading. filler
The loading.
pristineThe
PDMS pristine PDMS membrane
membrane exhibitedexhibited
2382 2382
Barrer with CO2 /NBarrer
2
with
and COCO2
2/N2 and
/CH 4
CO
ideal 2/CH4 idealof
selectivity selectivity
11.8 and of 11.8
3.2, and 3.2, respectively.
respectively. The CO 2
The CO2
permeability value of pristine PDMS reported in this study
permeability value of pristine PDMS reported in this study was slightly lower, while the was slightly lower, while the
CO 2/N2 selectivity was slightly higher as compared to other literature that used n-hexane
CO2 /N2 selectivity was slightly higher as compared to other literature that used n-hexane
to fabricate the PDMS membrane. In this study, n-pentane was used to fabricate the PDMS
to fabricate the PDMS membrane. In this study, n-pentane was used to fabricate the PDMS
membranes, compared to other studies that used n-hexane [75]. The use of different
membranes, compared to other studies that used n-hexane [75]. The use of different solvents
may have contributed to this observation. Results regarding this phenomenon have been
demonstrated in several studies that show the use of different types of solvents will lead
to varied permeability and selectivity values of the membranes due to the differences of
boiling point of the solvents and solubility parameters between the solvents used and the
polymers [75–77]. Furthermore, when MgO nanosheet filler was introduced into the PDMS
Membranes 2023, 13, 337 14 of 21

matrix at 0.25 and 0.5 wt.%, the CO2 permeability showed a declining trend accompanied
with minor improvement over CO2 /N2 and CO2 /CH4 ideal selectivity. The CO2 /N2 and
CO2 /CH4 ideal selectivity increased from 11.8 to 13.5 and from 3.2 to 3.5, respectively,
when the PDMS membrane was loaded with 0.5 wt.% filler as compared to pristine PDMS
membrane. However, upon incorporation of MgO nanosheets up to 0.5 wt.%, the CO2
permeability was reduced. Such phenomena are common in the fabrication of MMM,
where the presence of filler disrupts the polymeric chain arrangement [78]. Typically, for
glassy polymer, the presence of inorganic filler often causes disruption of the polymer
chain that leads to the increment of free fractional volume of the glassy membrane. The
case can be confirmed with increased gas permeability and selectivity in gas separation
performance of MMM as compared to a pristine glassy membrane [79,80]. However, PDMS
is a rubbery polymer with a flexible and highly mobile polymeric chain rather than a strong
and rigid polymeric chain, as possessed by glassy polymers. Similarly, the presence of MgO
nanosheets disrupts the polymeric chain of the PDMS membrane matrix. Although, rather
than increasing the free fractional volume, it impedes the mobility of the polymer chain of
PDMS membranes, thus reducing the flexibility of the polymer chain with the presence
of an MgO nanosheet inside the polymer matrix, hence, reducing the permeability of the
gas, as it is difficult for the gas penetrant to diffuse and move within the polymeric chain.
Madaeni et al. [15] suggested two mechanisms to explain the phenomena, namely the
copolymerization between Si-OH groups and PDMS molecules and the self-condensation
of polymer chains. Moreover, the enhancement of hydrophilicity of PDMS is not favourable.
As a result, the presence of hydrophilic MgO nanosheets does not improve the free volume
fraction of PDMS membranes. In tandem with the reduced gas permeability, CO2 /N2
and CO2 /CH4 ideal selectivities were observed to increase slightly, as stated previously.
It has been long postulated that nanosheet fillers with high aspect ratios of length to
thickness oriented perpendicularly to the gas diffusional path exhibit barrier properties
that could enhance gas separation performance as discussed by DeRocher et al. [81] and
Kang et al. [82]. Although in this study, the orientation of the nanosheet was not expected
to be perpendicular to the gas diffusional path as the membrane was fabricated through
the typical solvent evaporation method. The orientation was most likely randomized [20].
The high aspect ratio of the nanosheet filler increased the tortuosity of the diffusional path
for the gas penetrant to pass through the dense selective layer of the membranes. Hence,
the gas penetrant needed to cover more distance of diffusional path before it reached the
permeate side, which led to the reduction of gas permeability. Nevertheless, the formation
of these paths allowed a gas with smaller kinetic diameter, CO2 (d = 3.3 Å), to diffuse more
easily as compared to gases with larger kinetic diameters, such as N2 (d = 3.64 Å) and CH4
(d = 3.8 Å). This explained the reduction of CO2 permeability with slight improvement
towards the ideal gas selectivity similarly observed in other literature [21]. Another factor
that could possibly contribute to the reduced gas permeability with improved selectivity
could be the rigidification of the polymer chain at the polymer filler interface. As observed
in a study by Ehsani and Pakizeh [83], the trend of reduced permeability with increased
gas selectivity could either be ascribed to the rigidification of the polymer–filler interface
or due to pore blockage of the filler by the polymer. However, in this study, the reduction
of gas permeability was more likely influenced by the rigidification in the polymer–filler
interface region, as the MgO nanosheet is not a filler with porous channels. Thus, it is
not possible for pore blockage to occur. Similar trends can also be observed in a study by
Tao Li et al. [84]. Due to rigidification, the polymer–filler contact is stronger, thus restricting
the polymer chain mobility, which promotes enhancement of CO2 /N2 and CO2 /CH4 ideal
selectivity [85].
However, the CO2 permeability increased from 1544 Barrer to 1927 Barrer when the
filler loading was further increased from 0.5 wt.% to 1.0 wt.%. This could possibly be
due to the small aggregation formed on some local part of the PDMS matrix leading to
a defective area in the MMM, as shown in the inset image of the SEM in Figure 3. The
small aggregation formed may have caused the formation of small interfacial void in
Membranes 2023, 13, 337 15 of 21

the polymer–filler interface causing the gas molecules to move through these voids, thus
contributing
Membranes 2023, to increased
13, x FOR PEER REVIEW gas permeability. Additionally, the ideal gas selectivity16 did
of 23 not

show a declining trend, as the aggregate was not so severe that it caused the formation of
nonselective voids as observed in the image. Thus, it can be said that the voids formed at
the interfacial the polymer chain mobility, which promotes enhancement of CO2/N2 and CO2/CH4 ideal
contact at the polymer–filler interface were not major and were capable of
selectivity [85].
discriminating the gas through molecular sieving [86,87].

Figure 7. Gasperformance
Figure 7. Gas separation separation performance of and
of PDMS PDMSPDMS/MgO
and PDMS/MgO withrespect
with respect totovarious
variousfiller
filler
loading at ∆P = 2 bar ◦and T = 25 °C.
loading at ∆P = 2 bar and T = 25 C.
However, the CO2 permeability increased from 1544 Barrer to 1927 Barrer when the
Lastly, when
fillerthe fillerwas
loading was further
further increased
increased from 0.5 towt.%
5 wt.%,
to 1.0 the
wt.%.gas permeability
This could possiblyincreased
be due
to 2104 Barrer.to The gas aggregation
the small separationformed performance
on some localconcurred
part of thewithPDMSthematrix
insetleading
of thetocross-
a
defectiveofarea
sectional SEM image M6inintheFigure
MMM,3, as where
shown in the inset
there image of the SEMof
is sedimentation inthe
Figure
MgO 3. The small
nanosheet
aggregation formed may have caused the formation of small interfacial void in the
at the bottom of the MMM following its complete phase separation. The deposition of the
polymer–filler interface causing the gas molecules to move through these voids, thus
MgO nanosheet at the bottom
contributing of the
to increased gasPDMS membrane
permeability. Additionally,matrix maygas
the ideal have created
selectivity did nonse-
not
lective voids inshow
theamembrane matrix that promoted the increment of CO
declining trend, as the aggregate was not so severe that it caused the2 formation of permeability.
Regardless, it can be observed
nonselective voids as from
observed Figure
in the7image.
that Thus,
the CO 2 /N
it can ideal
be2said thatselectivity doesatnot
the voids formed
drop, while CO the/CH
interfacial
idealcontact at the polymer–filler
selectivity remained interface
relatively wereconstant.
not major and were capable
Although of
sedimen-
2 4
discriminating the gas through molecular sieving [86,87].
tation of the fillersLastly,
waswhenobserved, since the fabricated membrane was fully dense, the
the filler was further increased to 5 wt.%, the gas permeability increased
interfacial voids formed
to 2104 Barrer.at The
thegassedimented filler section
separation performance at the with
concurred bottom of the
the inset membrane
of the cross-
matrix did notsectional
impedeSEM idealimageselectivity,
of M6 in as there
Figure was still
3, where therea islarge, dense selective
sedimentation of the MgO layer
nanosheet
with a distributed MgOatnanosheet
the bottom on of the
theMMM following
top part of the its membrane
complete phase separation.
matrix. The it
As such,
is inferred thatdeposition
the fillerofsediment
the MgO nanosheet at the bottom of the PDMS membrane matrix may have
provided a low resistance diffusional pathway due to
created nonselective voids in the membrane matrix that promoted the increment of CO2
interfacial voidpermeability.
formation, while the
Regardless, it can topbe layer
observed provided
from Figure a selective
7 that the COdiffusional pathway
2/N2 ideal selectivity
akin to an asymmetric membrane. However,
does not drop, while CO2/CH4 ideal selectivity the CO /N
2 remained
2 ideal relatively constant. Although the
selectivity also showed
highest error bar due to lower reproducibility.
sedimentation of the fillers was observed, since the fabricated membrane was fully dense,
the interfacial voids formed at the sedimented filler section at the bottom of the membrane
3.5.2. Effect of matrix did not
Variable impede ideal selectivity, as there was still a large, dense selective layer with
Pressure
a distributed MgO nanosheet on the top part of the membrane matrix. As such, it is
Based on inferred
the previous
that the section, the M4
filler sediment showing
provided a lowthe best separation
resistance properties
diffusional pathway with
due to
good dispersion of the MgO
interfacial nanosheets
void formation, whileinthe
MMM showing
top layer provided desirable
a selectivemorphology without
diffusional pathway
showing any signakin to
ofansignificant
asymmetric membrane. However,
agglomeration wasthe chosen
CO2/N2 ideal selectivity
to be studied alsoregarding
showed the the
highest error bar due to lower reproducibility.
effect of feed pressure on the gas separation performance in this section.
Based on the trend observed in Figure 8, when the M1 membrane (Figure 8a) was
subjected to increased upstream pressure from 2 to 5 bar, the permeability of CO2 remained
steadily constant at about 2300 Barrer, while the CO2 /N2 ideal selectivity increased slightly
from 11.4 to 12.2 and from 2 to 3 bar and dropped from 12.7 to 10.6, with CO2 /CH4 remain-
ing relatively constant with increased upstream pressure. As permeability is an intrinsic
property of the membrane, it was expected that it would not change with transmembrane
 Based on the previous section, the M4 showing the best separation properties with
good dispersion of the MgO nanosheets in MMM showing desirable morphology without
showing any sign of significant agglomeration was chosen to be studied regarding the
effect of feed pressure on the gas separation performance in this section.
Based on the trend observed in Figure 8, when the M1 membrane (Figure 8a) was
Membranes 2023, 13, 337 subjected to increased upstream pressure from 2 to 5 bar, the permeability of16CO of221
remained steadily constant at about 2300 Barrer, while the CO2/N2 ideal selectivity
increased slightly from 11.4 to 12.2 and from 2 to 3 bar and dropped from 12.7 to 10.6, with
CO2/CH4 remaining relatively constant with increased upstream pressure. As
permeability
pressure unless the membrane is an experienced
intrinsic property of the membrane,
plasticization, it wasdrastic
where expected that it would not
permeability and
change with transmembrane pressure unless the membrane experienced plasticization,
ideal selectivity reduction could be observed [88]. As for M4 (Figure 8b), which
where drastic permeability and ideal selectivity reduction could be observed [88]. As for
contained
1 wt.% of MgO nanosheet
M4 (Figure filler, CO2 permeability
8b), which contained 1 wt.% dropped
of MgOvery slightly
nanosheet from
filler, CO1929 Barrer to
2 permeability

1722 Barrer withdropped

no improvement
very slightlyof CO1929
from 2 /N and
Barrer
2 toCO
1722
2 /CH
Barrer4 ideal
with selectivity
no improvement as a
offunction
CO2/N2
and CO2/CH
of upstream pressure. This4 ideal selectivity as a function of upstream pressure. This behaviour can be
behaviour can be explained with the dual-sorption model,
explained with the dual-sorption model, where the sorption of gas molecule to the
where the sorption of gas molecule to the rubbery phase of polymer is governed by Henry’s
rubbery phase of polymer is governed by Henry’s law, while the adsorption of gas
law, while the adsorption
molecule in the of microvoid
gas moleculeregionin of the microvoid
the polymer regionbyofLangmuir’s
is described the polymer is de-
behaviour
scribed by Langmuir’s behaviour
[73,89]. At first, CO2 [73,89].
solubility At first, CO
increased with2 solubility
pressure in increased withHenry’s
accordance with pressurelawin
accordance with but soon became
Henry’s law but obsolete
soonatbecame
higher pressure
obsolete dueattohigher
shrinkage of the microvoid
pressure inside the
due to shrinkage
of the microvoidpolymer
insidedue the topolymer
Langmuir’sduebehaviour [90]. Additionally,
to Langmuir’s behaviour it is[90].
also possible that the it
Additionally,
presence of the MgO nanosheet increased the crystallinity of the PDMS MMM at the
is also possible that the presence of the MgO nanosheet increased the crystallinity of the
polymer–filler interface, although it is not quantified in this study. The crystalline region
PDMS MMM at at thethepolymer–filler interface,
polymer–filler interface although
exhibited reduced it is
gasnot quantified
penetrant in this
solubility and study. The
diffusivity
crystalline regionas at the polymer–filler
crystallite is impermeable, interface exhibitedtoreduced
hence contributing gas of
the reduction penetrant solubil-
gas permeability
[91,92].
ity and diffusivity Membrane-softening
as crystallite phenomenon
is impermeable, also occurred
hence with increased
contributing to the pressure.
reduction Theof
trend of our finding regarding the effect of pressure on gas permeability of MMM is also
gas permeability [91,92]. Membrane-softening phenomenon also occurred with increased
in line with several published studies [93,94]. Table 2 shows the comparison of membrane
pressure. The trend of our finding
performances based onregarding
PDMS MMMthe effect
in this studyofandpressure onstudies.
with other gas permeability of
MMM is also in line with several published studies [93,94]. Table 2 shows the comparison
of membrane performances based on PDMS MMM in this study and with other studies.

(a) 3000 14.0

12.0
2500
CO2 Permeability (Barrer)

Ideal Selectivity, α (Pi/Pj)

10.0
2000

8.0
1500
6.0

1000
4.0

500
2.0

Membranes 2023, 13, x FOR PEER REVIEW 18 of 23

0 0.0
2 3 4 5
Upstream Pressure (bar)
(b) 2500 16.0

14.0
2000
12.0
CO2 Permeability (Barrer)

Ideal Selectivity, α (Pi/Pj)

10.0
1500

8.0

1000
6.0

4.0
500
2.0

0 0.0
2 3 4 5
Upstream Pressure (bar)
CO2 (Barrer) CO2/N2 CO2/CH4

Figure 8.performance
Figure 8. Gas separation Gas separation performance of (a)(b)
of (a) M1 and M1 M4
and at
(b) various
M4 at various pressures
pressures ranging from
ranging from 2 2toto
5 bar at room temperature (T = 25 °C).
5 bar at room temperature (T = 25 ◦ C).
Table 2. Gas performance comparison of PDMS MMM with other studies.

Gas Pair Selectivity 2

Filler Condition 1 CO2 Permeability (Barrer) Reference
CO2/N2 CO2/CH4
Mg-MOF-74
1608 17.6 -
(0.46 mmol)
Mn-MOF-74
Membranes 2023, 13, 337 17 of 21

Table 2. Gas performance comparison of PDMS MMM with other studies.

CO2 Permeability Gas Pair Selectivity 2

Filler Condition 1 (Barrer) CO2 /N2 CO2 /CH4
Reference

Mg-MOF-74
1608 17.6 -
(0.46 mmol)
4 bar
Mn-MOF-74 [38]
30 ◦ C 1466 18 -
(0.46 mmol)
Co-MOF-74
1508 17.9 -
(0.46 mmol)
Ni-MOF-74
1502 14.5 -
(0.46 mmol)
MWCNT
14 psi 1500 11.83 2.73 [48]
(1 wt.%)
ZSM-5
- 11648 11.1 4.36 [95]
(66 wt.%)
SAPO-34 20 bar 5753 31 4.92 [72]
Zeolite 3A
3125 - 2.95
(40 wt.%) 5 bar
[96]
Zeolite 4A 35 ◦ C
3208 - 3.09
(40 wt.%)
Zeolite 5A
3137 - 2.97
(40 wt.%)
2 bar 1929 12.7 3.4
MgO nanosheet 3 bar 1822 12.6 3.6
This work
(1 wt.%) 4 bar 1782 12.6 3.7
5 bar 1722 12.5 3.6
1 All tests are conducted at 25 ◦ C unless stated otherwise. 2 The reported gas selectivity is for single gas permeation
(ideal selectivity).

4. Conclusions
PDMS embedded with MgO nanosheets to form MMM was successfully fabricated and
tested for CO2 separation application. MgO nanosheets were fabricated using
a nonhydrothermal method with cheap precursors. The MgO nanosheets showed good
dispersion inside the PDMS polymer matrix up to 0.5 wt.%. At 1 wt.%, there was small,
local aggregation, although it did not agglomerate and form nonselective voids. Sedimenta-
tion of MgO nanosheets was observed at 5 wt.% due to the significant difference of physical
properties between the filler and the polymer dope suspension. The incorporation of MgO
nanosheets into the PDMS matrix showed improved ideal selectivity as compared to the
base PDMS membrane. The presence of MgO nanosheets disrupted the polymer chains and
increased the tortuous path of gas penetrant, thus resulting in reduced gas permeability
with increased ideal selectivity. PDMS is commonly used to seal the defective surfaces
of hollow fibre membranes. As such, we believe that the hybrid PDMS/MgO membrane
may be an interesting choice to be used as a coating to further improve the gas separation
performance of a mixed matrix thin film composite hollow fibre membrane, although the
improvement brought about by the PDMS/MgO layer is marginal. Nevertheless, single
gas permeation is not sufficient to justify the performance of the membrane in the real
plant condition. Hence, for future work, mixed gas permeation performance would be
more useful to determine the effectiveness of MgO nanosheets in improving the separation
performance of PDMS membranes.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/membranes13030337/s1, Figure S1: Average thickness of synthe-
sized MgO nanosheet estimated from FESEM images; Figure S2: (a) Magnified spectra from 600 to
1700 cm−1 (b) difference in the intensity of the peak in the region from 600 to 1700 cm−1 ; Table S1:
Thickness of the membranes fabricated by solvent evaporation method.
Membranes 2023, 13, 337 18 of 21

Author Contributions: Conceptualization, M.I.F.Z., M.M.H.S.B., and A.L.A.; methodology, M.I.F.Z.

and M.M.H.S.B.; validation, M.M.H.S.B. and A.L.A.; formal analysis, M.I.F.Z. and A.L.A.; investi-
gation, M.I.F.Z. and M.M.H.S.B.; resources, A.L.A.; writing—original draft preparation, M.I.F.Z.;
writing—review and editing, M.I.F.Z. and M.M.H.S.B.; visualization, M.I.F.Z.; supervision, A.L.A.;
project administration, A.L.A., funding acquisition, A.L.A. All authors have read and agreed to the
published version of the manuscript.
Funding: The authors acknowledge the financial assistance and facilities provided by Universiti
Sains Malaysia and Fundamental Research Grant Scheme by Ministry of Higher Education Malaysia
(FRGS/1/2020/TK0/USM/01/4, 203.PJKIMIA.6071484).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare that there are no conflict of interest.

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