Open Chemistry 2021; 19: 307–321
Research Article
Witri Wahyu Lestari*, Robiah Al Adawiyah, Moh Ali Khafidhin, Rika Wijiyanti, Nurul Widiastuti,
Desi Suci Handayani
CO2 gas separation using mixed matrix
membranes based on polyethersulfone/
MIL-100(Al)
https://doi.org/10.1515/chem-2021-0033
received November 21, 2019; accepted February 9, 2021
Abstract: The excessive use of natural gas and other fossil
fuels by the industrial sector leads to the production of
great quantities of gas pollutants, including CO2, SO2, and
NOx. Consequently, these gases increase the temperature
of the earth, producing global warming. Different strategies
have been developed to help overcome this problem,
including the utilization of separation membrane tech-
nology. Mixed matrix membranes (MMMs) are hybrid
membranes that combine an organic polymer as a matrix
and an inorganic compound as a filler. In this study,
MMMs were prepared based on polyethersulfone (PES)
and a type of metal–organic framework (MOF), Materials
of Institute Lavoisier (MIL)-100(Al) [Al3O(H2O)2(OH)(BTC)2]
(BTC: benzene 1,3,5-tricarboxylate) using a phase inversion
method. The influence on the properties of the produced
membranes by addition of 5, 10, 20, and 30% MIL-100(Al)
(w/w) to the PES was also investigated. Fourier-transform
infrared spectroscopy (FTIR) analysis indicated that no che-
mical interactions occurred between PES and MIL-100(Al).
Scanning electron microscope (SEM) images showed agglom-
eration at PES/MIL-100(Al) 30% (w/w) and that the thickness
of the dense layer increased up to 3.70 µm. After the

* Corresponding author: Witri Wahyu Lestari, Department of
Chemistry, Faculty of Mathematics and Natural Sciences,
Universitas Sebelas Maret, Jl. Ir Sutami No. 36A, Kentingan-Jebres,
Surakarta, Central Java, 57126, Indonesia, e-mail: witri@mipa.uns.
ac.id, tel: +62-271-663375, fax: +62-271-663375,
Hp: +62-82227833424
Robiah Al Adawiyah, Moh Ali Khafidhin, Desi Suci Handayani:
Department of Chemistry, Faculty of Mathematics and Natural
Sciences, Universitas Sebelas Maret, Jl. Ir Sutami No. 36A,
Kentingan-Jebres, Surakarta, Central Java, 57126, Indonesia
Rika Wijiyanti: Master of Applied in Medical Science, National
Intelligence College, Sumur Batu, Babakan Madang, Bogor, 16810,
Indonesia
Nurul Widiastuti: Department of Chemistry, Faculty of Science,
Institut Teknologi Sepuluh Nopember, Surabaya, 60111, Indonesia
Open Access. © 2021 Witri Wahyu Lestari et al., published by De Gruyter.
International License.
addition of MIL-100(Al) of 30% (w/w), the permeability
of the MMMs for CO2, O2, and N2 gases was enhanced
by approximately 16, 26, and 14 times, respectively, as
compared with a neat PES membrane. The addition of
MIL-100(Al) to PES increased the thermal stability of
the membranes, reaching 40°C as indicated by thermo-
gravimetry analysis (TGA). An addition of 20% MIL-
100(Al) (w/w) increased membrane selectivity for CO2/O2
from 2.67 to 4.49 (approximately 68.5%), and the addition
of 10% MIL-100(Al) increased membrane selectivity for
CO2/N2 from 1.01 to 2.12 (approximately 110.1%).
Keywords: CO2, MMMs, MIL-100(Al), PES
1 Introduction
The consumption of energy continues to increase with
population growth and further technological development.
The most widely used energy sources are natural gas
(53.3%) and coal (26.3%) [1]. The worldwide consumption
of natural gas has reached 100 trillion ft3 in 2018 and is
estimated to increase to 160 trillion ft3 in 2035. In Indonesia,
natural gas is the most widely used energy source after
petroleum and coal. Natural gas consists of hydrocarbon
compounds and gas pollutants, such as carbon dioxide
(CO2), nitrogen (N2), sulfur dioxide (SO2), and hydrogen
sulfide (H2S) [2]. The emission factor of CO2 from various
energy sources is very high as compared to other gases [1].
As an acid gas, CO2 is corrosive to gas pipelines and
reduces heating value. Furthermore, an increase in CO2
gas in the atmosphere increases the earth’s temperature,
leading to climate change and global warming [3]. CO2 pol-
lutants also make an impact on human health and contribute
to asthma and other respiratory diseases that can potentially
cause cardiovascular disease and cancer [4]; therefore, a sig-
nificant effort must be made to reduce CO2 emissions.
In general, CO2 gas emissions can be reduced through
its absorption, adsorption, cryogenic distillation, and
This work is licensed under the Creative Commons Attribution 4.0
308  Witri Wahyu Lestari et al.
separation with membranes [5]. CO2 separation by the
absorption method can be done using monoethanolamine
[6,7]. The absorption method for CO2 gas separation has
advantages because it requires less energy, has high
absorption capacity, and is flexible; however, the use
of this method requires high costs and an appropriate
solvent [5]. Adsorption methods for CO2 gas separation
can use physical or chemical adsorbents. The adsorbents
that have been investigated for CO2 separation include
Zeolite CaX [8] and Zeolite Ceca 13X [9]. Songolzadeh
et al. stated that, while the adsorption method requires
little energy, adsorption capacity is low, the process of
regenerating adsorbents is difficult, and further research
is required to find new adsorbents [5]. Gas separation by
a cryogenic distillation method has been investigated
by Li et al. and includes technology that is relatively easy
to produce and can be used on an industrial scale. In
addition, this method does not use solvents or produce
liquid CO2. However, the amount of energy required for
cooling and compacting the CO2 at low temperatures is
great, which can cause other operational problems [10].
Gas separation using membrane technology depends on
gas pressure. This technology has advantages over other
CO2 gas separation techniques for reasons such as its use
of simple tools, clear processes, high permeability and
selectivity, high thermal and chemical stability, resistance
to plasticization, and low production costs [5].
Membrane technology for gas separation is highly
developed in the industry because it can be easily applied
and is environmentally friendly; therefore, membranes
have been widely commercialized [11]. Membrane appli-
cations have been found for the separation of O2/N2
CO2/N2, and vapors, air dehydration, and the removal
of volatile organic compounds from waste [12]. Metal
membranes made of platinum or palladium have good
performance, but the high cost of these metals greatly
influences their selection. Inorganic membranes can be
used as alternatives because of their better chemical
stability and lower fabrication costs; however, their use
requires high temperatures of 200 to 900°C. Organic
polymer membranes increasingly dominate the field because
they are economical and their performance is quite com-
petitive [11]. However, the selectivity and permeability
properties of polymer membranes are limited [13]. These
deficiencies have pushed researchers toward the development
of alternative ways of making membranes that are more stable
and economical and have a high separation performance,
namely through combinations of membrane materials known
as mixed matrix membranes (MMMs). The fabrication
technology for MMMs promises to improve mechanical
properties, producing better separation capabilities and
stability than organic polymer membranes [14]. MMMs
are composite membranes consisting of an organic poly-
mer matrix as a continuous phase and filler particles as
a dispersion phase [15]. One polymer matrix that has
potential in the fabrication of MMMs is polyethersulfone
(PES). This polymer is widely used in the manufacture of
membranes because it has good mechanical properties,
good thermal and chemical stability [16], and high glass
transition temperatures (Tg) of up to 225°C [17]. With
addition of ethylenediamine (EDA)-TiO2 of 5%, PES-based
MMMs had the highest selectivity for CO2/CH4 gas separa-
tion at 41.42 and CO2 permeability at 10.11 Barrers (4 bars)
[18]. In addition, PES/Zeolitic Imidazolate Framework-8
(ZIF-8) MMMs have been investigated for H2/CO2 gas
separation, demonstrating a selectivity of 9.3, and H2/N2
gas separation, demonstrating a selectivity of 11.5 [19].
CO2/CH4 gas selectivity increases from 3.57 to 11.15 with
the addition of a 15% carbon molecular sieve in PES mem-
branes [20].
Promising fillers can increase both permeability and
selectivity. So far, the materials that have been most
widely used as fillers are porous materials such as silica,
carbon nanotubes, zeolites, and graphite, as well as used
in the development of metal–organic frameworks (MOFs)
[15]. MOFs have good porosity, large surface areas, and
adjustable pore sizes and topology, making them ideal
selections as fillers in MMMs [21]. Research on MOF-based
MMMs for CO2 gas separation has been performed in
the past, including on loading of 30 wt% [Ti8O8(OH)4-
(C6H3–C2O4–NH2)6] also known as NH2-Material of Insti-
tute Lavoisier (MIL)-125(Ti) on polysulfone (PSf) have
shown an increase of 320% compared with pristine PSf
membrane [22], [Al(OH)(O2C–C6H4–CO2)] also known as
Material of Institute Lavoisier (MIL)-68(Al) modified into
PSf showed only small increases in H2 and CO2 permeabil-
ities in the ranges of 11.1–12.4 and 4.7–5.4 Barrer, respec-
tively [23]. MMMs containing [Zr6O4(OH)4(C8H4O4)6(NH2)6]
also known as UiO-66-NH2 and Matrimid® polymer [24]
exhibited not only enhanced mechanical and thermal
stabilities, but also CO2 permeability was increased by
200% and CO2/N2 ideal selectivity was increased by
25%. In addition, NH2-Cu3(BTC)2 (BTC: benzene 1,3,5-tri-
carboxylate) deposited on Pebax (Pebax/sub-NH2-Cu-BTC)
showed 303% higher CO2 permeability than neat Pebax due
to the fine dispersion and the presence of groups with a
superior CO2-philicity in the framework [25], and incorpora-
tion of MOF-5 (15 wt%) into polyimide (PI) increased the
permeability toward CO2 gas up to 290% [26].
Trivalent metals, for example, Al3+ ions, are promising
candidates for the synthesis of MOFs because of their por-
osity, low density, and high thermal and physicochemical
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)
stability [27]. Al-fumarate-based MOFs have been investi-
gated by Nuhnen et al. as a filler in Matrimid® polymers,
showing increased permeability for the separation of CO2
and CH4 gases [28]. One type of MOF is the Material of
Institute Lavoisier (MIL). MIL-n types based on Al3+ metal
ions that have been investigated in gas separation pro-
cesses include MIL-53(Al) and NH2-MIL-53(Al) in polyviny-
lidene fluoride [29] and MIL-68(Al) in polysulfone [23].
Another aluminum-based MIL-n is MIL-100(Al). The synth-
esis of an aluminum trimesate-based MIL-100 was first
performed by Volkringer et al. using the hydrothermal
method [30], and MIL-100(Al) has been investigated for
hydrogen storage with a Pd metal carrier [31], as a catalyst
in sulfoxidation reactions [32], and for the loading of doxo-
rubicin hydrochloride on MIL-100(Al) gel as an anticancer
treatment [33]. The use of MIL-100(Al) filler for separation
applications has never been done; therefore, this study
aimed at researching the development of MMMs using
MIL-100(Al) with PES polymers, expecting that this would
improve the CO2 gas separation abilities of MMMs.
2 Materials and methods
2.1 Materials
All chemicals were used in analytical grade without
further purification. Aluminum nitrate nonahydrate (99%)
and benzene-1,3,5 tricarboxylic acid (95%) were commer-
cially provided by Sigma Aldrich, Germany. Ethanol (99%),
N,N′-dimethylformamide (DMF, 99.8%), PES (99%), and
N,N′-dimethylacetamide (99%) were supplied by Merck
EMSURE, Germany. Nitrogen (UHP 99.995%), oxygen (UHP
99.9%), and carbon dioxide (UHP 99.9%) gases were pur-
chased from Samator, Indonesia.
2.2 Methods
2.2.1 Synthesis of MIL-100(Al)
The MIL-100(Al) was synthesized under the solvothermal
conditions according to a procedure modified from the
literature [33]. Al(NO3)3·9H2O (2.851 g, 7.6 mmol) and tri-
mesic acid (H3BTC: benzene 1,3,5-tricarboxylate) (1.051 g,
5 mmol) were dissolved in ethanol (36 mL) and stirred
for 15 min at room temperature. The solution was then
 309
placed in a Teflon linedSS Autoclave and heated at 120°C
for 1 h. The resulting white gel was dried in an oven
at 80°C for 19 h until a yellow solid was obtained, which
was then washed with DMF (1 × 30 mL) and ethanol
(1 × 30 mL) to remove the remaining ligand. The MIL-100(Al)
material was activated at 100°C for 2 h and sonicated for 5 h
to reduce particle size (yield: 87.19%).
2.2.2 Preparation of MMMs based on PES/MIL-100(Al)
The preparation of MMMs was performed with a phase
inversion method modified from the study by Dama et al.
[34]. Filler MIL-100(Al) in different weight percentages of
5, 10, 20, and 30% (w/w) was added to dimethylaceta-
mide. Each mixture was sonicated for 20–30 min so that
the MIL-100(Al) was well dispersed in the solution and
then stirred for 1 h at room temperature to homogenize it.
Afterward, PES (35%) (w/w) was added to each mixture
and stirred for 24 h at room temperature. Each obtained
dope solution was cast on a glass plate (20 × 15 cm). Next,
each membrane on a glass plate was evaporated for about
20 s and then dipped in a water-filled coagulant tub, and
after the membrane was removed from the glass plate, the
membrane was washed with distilled water for 24 h, fol-
lowed by solvent exchange with methanol for 2 h and drying
for 48 h at room temperature to evaporate the solvent.
2.2.3 Gas separation test
The resulting membranes were tested for permeability
and selectivity using a single gas (N2, O2, and CO2) flat
sheet membrane method as reported by Lee et al. [35].
The measurement was performed at a pressure of 1 bar
and room temperature. Each membrane was fabricated
by cutting it in a circle with an effective diameter of
5.7 cm, placing it on a membrane permeation cell, and
then sealing it before connecting it to the gas stream. The
data were collected by measuring the amount of time
taken for the gas to reach a volume of 10 mL, with the
volume of gas measured with a bubble flow meter and the
time was measured with a stopwatch. Data retrieval was
done twice. The scheme of the gas permeation test equip-
ment is shown in Figure 1 [36]. The permeability and
selectivity of each membrane were calculated based on
equations (1) and (2) [37].
V
Pi Q 273.15 t 273.15 (1)
= =
l (A × ΔP ) T (A × ΔP ) T
310  Witri Wahyu Lestari et al.

Figure 1: Single gas permeation rig (adapted from Gunawan et al. [36]).

where, 2.3 Characterization of the materials

Pi = gas permeability (GPU  l i [1 GPU = 1 × 10−6 cm3
P
 
X-ray diffraction (XRD) (X-Pert Pan Analytical) was used
(STP)/cm3 s cm Hg] or Barrer [1 Barrer = 1 × 10−10 cm3
to analyze the phase purity and crystallinity of the pre-
(STP)/cm2 s cm Hg])
pared materials. The functional groups of the compounds
l = membrane density (cm)
were observed using Fourier-transform infrared spectro-
V = measured volume (cm3, STP)
scopy (FTIR) (Shimadzu IR Prestige-21). The thermal stabi-
A = membrane area (cm2)
lity of the materials was measured using TG analysis to a
t = required time for gas to pass through the membrane (s)
temperature of 900°C (Hitachi STA 7000) with a heating
ΔP = gas pressure (cm Hg)
rate of 10°C/min under nitrogen flow. The morphology
T = temperature condition during the measurement (K)
and elemental composition of the materials were observed
Pi by a scanning electron microscope-energy dispersion X-ray
αi / j = (2) (SEM–EDX) (FEI Inspect-S50). A surface area analyzer
Pj
(SAA) (Quadrasorb Evo, Quantachrome) was used to
where, monitor the surface area and porosity of the materials.
αi / j = selectivity of the membrane for gas i and gas j
Pi = permeability of gas i (Barrer) Ethical approval: The conducted research is not related to
Pj = permeability of gas j (Barrer) either human or animal use.
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)  311

3 Results and discussion

3.1 Characterization of the materials

3.1.1 X-ray diffraction (XRD)

The characterization of the prepared materials using XRD

was performed to determine the purity and suitability of
the phase. The XRD analyses demonstrated that the peak
of the synthesized MIL-100(Al) corresponds to the stan-
dard pattern for MIL-100(Al) (CCDC No. 789872) but
has lower crystallinity as shown by the broad peak in
Figure 2. This result is in accordance with the study con-
ducted by Xia et al. [38], which stated that the powder
XRD of MIL-100(Al) synthesized through gel formation
shows low crystallinity.
3.1.2 Fourier transform infrared spectroscopy (FTIR)
The properties of the synthesized MIL-100(Al) can also be
seen in the shift of the absorption peak shown in the FTIR
analysis of this material in comparison with the H3BTC
ligand (Figure 3). These results are in accordance with the
research reported by Xia et al. [38].
The significant shift from 1,721 to 1,673 cm−1 corre-
sponds to the stretching vibration of the carbonyl group
(C]O) caused by the deprotonation of the C]O–H group
by the free ligand that is coordinated with the Al3+ metal
ion in MIL-100(Al). In addition, there is also a shift in the
absorption peak of the OH group from 2,500–3,100 cm−1
Figure 3: FTIR spectra of the synthesized MIL-100(Al) and H3BTC
ligand.
to 2,886–3,650 cm−1, representing the formation of hydrogen
bonding, whereas OH in MIL-100(Al) comes from the
ligand that forms MIL-100(Al) with the formula {Al3O
(OH)(H2O)2[BTC]2 · xH2O}. Al–O bonds are generally
observed at wavenumbers below 700 cm−1. The absorp-
tion peak at 675 cm−1 in the synthesis results shows the
Al–O bond that has been coordinated with the carboxyl
group of the H3BTC ligand. The uptake of the C–O func-
tional groups also matched the literature at wave number
1,246 cm−1 [39] (Table 1).
The success of the membrane preparation can be
seen in a comparison of the FTIR spectra of the neat
PES membrane and that of the PES/MIL-100(Al) mem-
branes (Figure 4). The comparison of the PES FTIR spectra
with those of the PES/MIL-100(Al) with different percen-
tage additions of MIL-100(Al) shows that there were no
changes to the structure of the PES, which is demon-
strated by the similar FTIR spectra. The addition of MIL-
100(Al) to PES causes the character of the MIL-100(Al) to
be more visible. This is marked by a widening of the
absorption peak of the OH functional groups at 3,447 cm−1
due to overlapping OH groups from the –OH ligand and

Table 1: Comparison of the absorption spectra of the synthesized

MIL-100(Al) with the H3BTC ligand and MIL-100(Al) in the literature

Absorption Wavenumber (cm−1)

H3BTC [38] Synthesized MIL-100(Al)

MIL-100(Al) literature [38]

O–H 2,500–3,100 2,886–3,650 2,500–3,500

C]O stretch 1,721 1,673 1,670–1,729
Figure 2: Diffractogram of synthesized MIL-100(Al) as compared
C–O 1,276 1,246 1,131–1,221
with the standard patterns of CCDC No. 789872 and the H3BTC
Al–O — 675 680–620
ligand (ICSD No. 30245).
312  Witri Wahyu Lestari et al.

3.1.3 Scanning electron microscopy (SEM)

SEM analysis was used in this study to determine the

morphology and particle size of the MIL-100(Al) and
the effect of the addition of MIL-100(Al) to PES on the
density of the MMMs. The morphology of the synthesized
MIL-100(Al) showed an irregular shape (Figure 5) with an
average particle size of 1.69 ± 0.35 µm (see ESI Figures S1).
The morphological appearance of the MIL-100(Al) is in
accordance with a study conducted by Feng et al. [33].
Differences in synthesis methods can affect morphology
due to different solvents that are used, for example, the
MIL-100(Al) synthesized by Volkringer et al. [30] under
Figure 4: FTIR spectra of MIL-100(Al), PES, and MIL-100(Al)/PES hydrothermal conditions using H2O and HNO3 solvents
MMMs with several different percentage additions of MIL-100(Al)
had an octahedral form.
to PES.
The surface morphologies of the resulting MMMs are
shown in Figure 6. The neat PES membrane is almost
H2O molecules in the MIL-100(Al) (formula {Al3O(OH)
defect-free, representing the dense layer, and the surface
(H2O)2[BTC]2 · xH2O}) and overlapping OH from water during
images of MMM up to 20 wt% MIL-100(Al) loading also
coagulation. The PES uptake band is in accordance with
look like a dense membrane. However, the MIL-100(Al)
the study by Mushtaq et al. [40] and is listed in Table 2,
does not appear to be homogenously distributed in the
showing the uptake at 1,149 and 1,241 cm−1, which corre-
MMMs with 5 and 10% additions of MIL-100(Al). This may
sponds to the absorption peak of the S]O group. CSO2C
be occurred since the amount of MIL-100(Al) incorpo-
absorption is indicated at wavenumber 1,324 cm−1. C–O
rated is very small. In contrast, the MIL-100(Al) is well
uptake at 1,237 and 1,100 cm−1 indicates the presence of
distributed at a 20% addition, but at a 30% addition, the
ether groups. The absorption of C]C aromatic is shown in
agglomeration has occurred that might be due to too large
the area of 1,576–1,487 cm−1. The addition of MIL-100(Al) to
loading of MOFs, affecting membrane performance [13],
PES does not produce a new absorption peak, indicating that
and this is shown in Figure 6e. The effect of the addition of
there is no chemical bond between the PES and MIL-100(Al).
MIL-100(Al) can also be seen from the morphologies of
However, non-covalent interactions might have occurred (but
the cross-sections (Figure 7). Each cross-section mor-
could not be observed in FTIR) such as π–π stacking between
phology appears as an asymmetrical structure with a
the aromatic rings, ion–dipol interaction between metal ion
dense top layer where the filler is located and a lower
part of MOF and sulfon and ether group and also dipol–dipol
layer with a cavity formed like fingers, which accords
interaction; therefore, good composite could be formed and
with a previous study conducted by Qadir et al. [41].
reinforced each other. The decrements in intensity of OH
The distribution of the aluminum from MIL-100(Al) in
band in PES/MIL-100(Al) 5% might be due to lower content
the membrane is demonstrated through EDX analysis as
of water during the coagulation process in MMM casting or
shown in Table 3 and Appendix 2.
during MOF activation.

Table 2: Comparison of the absorption peaks of the PES from the

research results with that of the PES from the literature

Absorption Wavenumber (cm−1)

PES MIL-100(Al) PES/

literature [40] MIL-100(Al)

S]O 1,150 and 1,307 — 1,149 and 1,241

CSO2C 1,322 — 1,324
C–O 1,244, 1246 1,237 and 1,100
1,260–1,000
Ar C]C 1,587–1,489 1,372–1,481 1,576–1,487
O–H — 2,886–3,650 3,447
Figure 5: Depiction of the synthesized MIL-100(Al).
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)  313

Figure 6: Surface morphology of (a) PES, (b) PES/MIL-100(Al) 5%, (c) PES/MIL-100(Al) 10%, (d) PES/MIL-100(Al) 20%, and (e) PES/MIL-
100(Al) 30%.
314  Witri Wahyu Lestari et al.
Figure 7: Cross-section of morphological appearance of (a) PES, (b) PES/MIL-100(Al) 5%, (c) PES/MIL-100(Al) 10%, (d) PES/MIL-100(Al)
20%, and (e) PES/MIL-100(Al) 30%.
The addition of MIL-100(Al) to PES can increase the
thickness of the dense layer as shown in Figure 8 and
determine the nature of gas permeation. As shown in
Figure 8, the dense layer thickness increases at higher
MIL-100(Al) loading. It can be attributed since the exchange
rate between the coagulant at the outer layer and the solvent
is slower due to the high concentrated area of the polymer.
It results in the delayed demixing, affecting the formation
of the thicker dense layer.
3.1.4 Thermogravimetric analysis (TGA)
The thermal stability of the synthesized MIL-100(Al) was
determined from TGA analysis. Figure 9 shows that there
are two instances of mass reduction, occurring at tem-
peratures below 200°C and at 500–550°C, which is in
agreement with a previous study by Xia et al. [38]. The
first mass reduction indicates loss of water molecules of
approximately 11.09% at temperatures from 26 to 157°C,
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)  315

Table 3: Results of the EDX analyses of the PES/MIL-100(Al) MMMs

Membrane %w/w C %w/w O %w/w Al

PES/MIL-100(Al) 5% 50.62 49.24 0.13

PES/MIL-100(Al) 10% 50.55 49.03 0.42
PES/MIL-100(Al) 20% 50.39 48.10 1.51
PES/MIL-100(Al) 30% 49.56 49.25 1.19

Figure 10: Thermogram of different percentage additions of MIL-

100(Al) to PES.

MMMs by 40°C as compared with neat PES membrane

(Figure 10), which had thermal stability of up to 500°C.
This is because the thermal stability of MIL-100(Al) (600°C)
is higher than that of PES [32]. The presence of filler inside
the PES membrane can act as a barrier, obstructing the
transport of degradation product.
Figure 8: The thickness of PES/MIL-100(Al) MMMs dense layer with
different percentage additions of MIL-100(Al).
3.1.5 Surface area analyzer (SAA)

SAA analysis was used to determine the surface area and

pore chrematistics of the MIL-100(Al) material, including
pore volume, pore radius, and pore size distribution.
The results of the SAA analysis are shown through the
adsorption–desorption isotherm graph in Figure 11.
The adsorption–desorption isotherm graph for MIL-
100(Al), based on the International Union of Pure and

Figure 9: Thermogram of the synthesized MIL-100(Al).

which is possible due to the loss of 6 water molecules.

Two DMF molecules (ca. 21.12%) that were used during
the purification were probably released at temperature
range 162 to 277°C [30,38]. The third mass reduction was
49.99% at temperatures from 276 to 616°C due to the loss of
two BTC ligand molecules. The total final product residue
of 17.80% Al2O3 was obtained at 520°C [30]. The calculation
of the mass reduction is given in ESI Appendix 3.
The addition of MIL-100(Al) to the MMMs to form
PES/MIL-100(Al) increases the thermal stability of the Figure 11: Nitrogen sorption isotherm analysis of MIL-100(Al).
316  Witri Wahyu Lestari et al.

6.00E-04 material (type I) with a BET surface area of 920 m2/g and
a pore volume of 0.535 cm3/g [33]. Figure 12 shows the
5.00E-04
results for the MIL-100(Al) pore size distribution using
the Barrett, Joyner, and Halenda (BJH) method with a pore
dV(r) (cm3/Ȃ/g)

4.00E-04
volume and radius of 0.026 cc/g and 18.437 Å, respectively.
3.00E-04

2.00E-04

1.00E-04 3.2 Gas separation performance of the PES/

0.00E+00
0 50 100
Pore radius (Å)
Figure 12: Graph of MIL-100(Al) pore distribution.
Applied Chemistry classifications, shows type II, which
indicates a nonporous or macropore material character [42].
Based on an analysis using the Brunauer–Emmett–Teller
(BET) method, a surface area of 1.844 m2/g was obtained.
The synthesized MIL-100(Al) does not have the same char-
acter as that shown in the study by Feng et al., where the
MIL-100(Al) from a gel formation included microporous
Figure 13: Gas permeability graph of CO2, O2, and N2 for different
percentage additions of MIL-100 (Al) to PES.
MIL-100(Al) MMMs
150 200
The gas separation performance by the MMMs can be
known from a gas permeability test using a single gas
(CO2, O2, and N2). A gas permeability test was used to
determine the nature of the gas transport and the effect
of different additions of MIL-100(Al) on the permeability
and selectivity of the membranes. The results for the
gas permeability tests for different additions of MIL-
100(Al) to PES are shown in Figure 13, Table 4, and
Appendix 4.
Figure 13 shows that CO2 gas permeation was higher
than that of N2 or O2. This is because the kinetic diameter
of CO2 (3.20 Å) is smaller than that of O2 (3.46 Å) and N2
(3.64 Å) [42], which can affect gas flow. O2 gas has a
smaller kinetic diameter than N2, but O2 (32) has a greater
molecular weight than N2 (28), and thus molecular weight
can also affect gas flow [44]. The addition of MIL-100(Al)
to PES can increase permeability with a similar pattern of
increase for each gas. Increasing the maximum perme-
ability of the CO2, O2, and N2 gases with the addition of
30% MIL-100(Al) causes the permeability of the CO2 gas to
increase 16 times (1,609%) from 570.03 ± 6.37 Barrer
to 9741.99 ± 1519.91 Barrer, O2 gas to increase 26 times
from 213.89 ± 6.81 Barrer to 5743.87 ± 27.61 Barrer, and N2
gas to increase 14 times from 564.52 ± 5.54 Barrers to
8536.14 ± 744.06 Barrers. The increase in CO2 gas perme-
ability in these PES/MIL-100(Al) MMMs is greater than
that of Matrimid®-based MMMs and UiO-66-NH2 type
MOFs (∼200%) [24].

Table 4: Gas Permeability of the PES/MIL-100(Al) MMMs

Membrane Permeability (Barrer)

N2 O2 CO2

PES neat 564.52 ± 5.54 213.89 ± 6.81 570.03 ± 6.37

PES/MIL-100(Al) 5% 1149.91 ± 63.09 862.13 ± 157.42 1799.51 ± 23.09
PES/MIL-100(Al) 10% 824.62 ± 128.68 448.06 ± 26.78 1749.68 ± 99.05
PES/MIL-100(Al) 20% 1194.20 ± 139.31 492.21 ± 4.99 2210.77 ± 308.46
PES/MIL-100(Al) 30% 8536.14 ± 744.06 5743.87 ± 27.61 9741.99 ± 1519.91
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)
Figure 14: Gas selectivity graph of CO2/O2, CO2/N2, and O2/N2 for
different percentage additions of MIL-100(Al) to PES.
The addition of MIL-100(Al) fillers to PES/MIL-100(Al)
MMMs can increase CO2/O2 gas selectivity as shown in
Figure 14, Table 5, and Appendix 6. An addition of MIL-
100(Al) of 20% can increase the selectivity for CO2/O2 gas
separation from 2.67 ± 0.04 to 4.49 ± 0.67 (68.5%), which
then decreases with an addition of MIL-100(Al) of 30%.
This phenomenon is due to the presence of the filler
agglomeration as shown in Figure 6e and permeability
that is too high. The existence of agglomeration that is
too large will reduce the performance of membrane separa-
tion [13]. CO2/N2 gas selectivity was increased by 110.1% to
2.16 ± 0.46 as compared to a neat PES membrane (1.01 ±
0.00) with an addition of MIL-100(Al) of 10%. The increase
in the CO2 gas separation performance is influenced by
polarity and high CO2 quadrupole moments as compared
with N2 [45], causing the CO2 to be more easily adsorbed,
and so the selectivity for CO2 increases. The increased
selectivity for CO2/N2 from the obtained MMMs is higher
than that of Matrimid®/UiO-66-NH2 MMMs (∼25%) [24].
The gas transport in the membrane is controlled by
the solution–diffusion mechanism of PES matrix with a
Table 5: The selectivity of the PES/MIL-100(Al) MMMs
Membrane
O2/N2
PES neat 0.38 ± 0.01
PES/MIL-100(Al) 5% 0.75 ± 0.18
PES/MIL-100(Al) 10% 0.55 ± 0.12
PES/MIL-100(Al) 20% 0.42 ± 0.05
PES/MIL-100(Al) 30% 0.68 ± 0.06
Knudsen selectivity [47] 0.94
 317
portion of the filler particles. The MIL-100(Al) particles
have pores of about 1.8 nm, which is microporous and
below the region of Knudsen diffusion. Also, the Knudsen
selectivity values are not in agreement with calculated
selectivity values (Table 5), indicating that the gas trans-
port is not controlled by the Knudsen mechanism. The
pore of MIL-100(Al) is bigger than the gas molecular
diameter, leading to the conclusion that the transport
mechanism is not controlled by molecular sieving. The
transport mechanism can be explained by surface diffu-
sion, with a mechanism of more favorable surface diffu-
sion of fast, lower kinetic diameter gas (CO2), relative to
slow, larger kinetic diameter gas (O2 and N2), followed
by gas diffusion in the MIL pores. CO2 gas has higher
polarizability and quadrupole moments (29.11 × 1025/cm3
and 4.30 × 1026/esu cm2, respectively) as compared with
N2 (17.403 × 1025/cm3; 1.52 × 1026/esu cm2) or O2 gas
(15.812 × 1025/cm3; 0.39 × 1026/esu cm2) [45]. This shows
that CO2 gas can be adsorbed more selectively than N2 or
O2 gas due to the greater presence of CO2 quadrupole
moments that can affect the gas separation selectivity
[45]. In addition, after the activation process, the metal
ions in MIL-100(Al) do not have coordinatively saturated
bonds, allowing the CO2 gas to be easily adsorbed. The
interaction with the absorbed gas shows a strong activity
to adsorb in the pore walls, thus gas separation occurs
based on surface diffusion [46].
The separation of O2/N2 gas with an addition of 30%
MIL-100(Al) increased selectivity by 97.9% to 0.75 ± 0.18
as compared with neat PES (0.38 ± 0.01). However,
the O2/N2 performance has lower selectivity than CO2/O2
or CO2/N2. This is because gas permeation is influenced
by the molecular weight of O2 (32), which is greater
than that of N2 (28) [44]. As a result, gas permeation
based on Knudsen diffusion, as shown by produced
O2/N2 selectivity, is close to Knudsen selectivity (0.94).
Knudsen selectivity is calculated based on equation (3)
[47].
Selectivity
CO2/N2 CO2/O2
1.01 ± 0.00 2.67 ± 0.04
1.57 ± 0.11 2.12 ± 0.36
2.16 ± 0.46 3.91 ± 0.01
1.85 ± 0.04 4.49 ± 0.67
1.15 ± 0.28 1.70 ± 0.26
0.80 0.85
318  Witri Wahyu Lestari et al.

Figure 15: Comparison of the O2/N2 gas separation performance as compared with the literature [48,49].

Mj The successful preparation of the MMMs can be eval-

αi , j = (3)
Mi uated by comparing them with the Robeson upper bound
as a dividing boundary between organic and inorganic
where, αi, j is the selectivity of the membrane in gases i
polymer membranes. The for O2/N2 (Figure 15) and CO2/
and j, Mi is the molecular weight of gas i, and Mj is the
N2 gas separation performance (Figure 16) of the pro-
molecular weight of gas j.
duced MMMs has not been able to reach the upper bound

Figure 16: Comparison of CO2/N2 gas separation performance as compared with the literature [49].
 CO2 gas separation using MMMs based on polyethersulfone/MIL-100(Al)
due to low selectivity, but different additions of MIL-
100(Al) can push gas permeation performance toward
the upper bound as compared with neat PES membranes,
so the preparation of the PES/MIL-100(Al) MMMs can be
categorized as successful.
4 Conclusion
The addition of MIL-100(Al) to PES can affect the char-
acteristics of the produced MMMs, including an increase
in thermal stability of 40°C and in the thickness of the
dense membrane layer of up to 3.70 μm. Moreover, the
addition of MIL-100(Al) to PES can improve membrane
performance for the permeability of CO2, O2, and N2 gases
by 16, 26, and 14 times, respectively, as compared with
neat PES membranes. Furthermore, an addition of 20%
MIL-100(Al) can increase the selectivity for CO2/O2 gas
separation from 2.67 to 4.49. CO2/N2 gas selectivity can
be increased from 1.01 to 2.12 with an addition of 10%
MIL-100(Al) as filler. Another strategy for increasing mem-
brane performance is to modify the membrane surface with
the use of a coating material such as polydimethylsiloxane.
Acknowledgments: The authors acknowledge Dr. rer. nat.
Ubed Sonai Fahruddin Arrozzi from the State University
of Malang for the nitrogen sorption isotherm measurement
and Dr. Grandprix T. M. Kadja from Bandung Institute of
Technology for the thermogravimetry measurement. More-
over, we thank the Ministry of Research, Technology and
Higher Education of the Republic of Indonesia through the
University Leading Fundamental Research Grant (PDUPT)
2021 for funding.
Funding information: The funding of this research was sup-
ported by the Ministry of Research, Technology and Higher
Education of the Republic of Indonesia through the University
Leading Fundamental Research Grant (PDUPT) 2021.
Authors’ contributions: W. W. L. – conceptualization;
W. W. L., N. W., D. S. H. – data curation; R. A. A., R. W. –
formal analysis: W. W. L. – funding acquisition; R. A. A.,
M. A. K. – investigation; R. A. A., M. A. K., R. W. –
methodology; W. W. L. – project administration; W. W. L.,
N. W. – resources; R. A. A., M. A. K. – software; W. W. L, N.
W. – supervision; W. W. L, N. W. – validation; R. A. A., M.
A. K., R. W. – visualization; R. A. A., W. W. L. – writing –
original draft; W. W. L., D. S. H., N. W., R. W. – writing –
review & editing.
 319
Conflict of interest: Authors state no conflict of interest.
Data availability statement: All data generated or ana-
lyzed during this study are included in this published
article [and its supplementary information files].
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