Process Safety and Environmental Protection 170 (2023) 709–719

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

A new ternary Pebax®1657/maltitol/ZIF-8 mixed matrix membrane for

efficient CO2 separation
Danial Nobakht , Reza Abedini *
Enhanced Oil Recovery (EOR) and Gas Processing Research Lab, Faculty of Chemical Engineering, Babol Noshirvani University of Technology, 4714871167 Babol, Iran

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

Keywords: In this study, a novel high-performance mixed matrix membrane (MMM) based on poly(ether-b-amide) was
Pebax®1657 fabricated in which the synthesized ZIF-8 nanoparticles embedded into a maltitol-modified Pebax®1657. Mal­
Maltitol, ZIF-8 titol (as an inexpensive low molecular weight additive) provides a good CO2 affinity. Moreover, an existence of
Mixed matrix membrane
selective affinity in ZIF-8 nanoparticles toward CO2, enhances the CO2 permeability and its selectivity over other
CO2 separation
penetrants. The synthesized ZIF-8 nanoparticles were added (0–10 wt%) into the Pebax/maltitol (20 wt%) matrix
to prepare the Pebax/maltitol/ZIF-8 MMMs. Field Emission Scanning electron microscopy (FESEM) was applied
to evaluate the MMM morphology, where excellent dispersion was shown. Thermogravimetric analysis (TGA)
was used to determine the thermal properties of prepared membranes. The TGA results indicated that the
decomposition temperature of membranes raised as the ZIF-8 loading increased within the Pebax matrix. Dif­
ferential scanning calorimetry (DSC) implied the disruptive role of MOF on polymer chain mobility which re­
duces the overall crystallinity and increases the glass transition temperature of MMMs. The analysis of gas
permeability at 30 ◦ C and 10 bar revealed that Pebax/maltitol (20 wt%)/ZIF-8 (10 wt%) membrane showed the
highest CO2 permeability of 429.57 Barrer. In addition, the highest selectivity values of 69.31 and 26.59 for CO2/
N2 and CO2/CH4 separation, respectively; obtained by Pebax/maltitol (20 wt%)/ZIF-8 (5 wt%) at 30 ◦ C and 10
bar. Finally, the performance of Pebax/maltitol (20 wt%)/ZIF-8 (5 wt%) membrane was able to surpass the
Robeson upper bound for the CO2/N2 separation and Robeson prior bound for CO2/CH4 one.

1. Introduction replace instead of conventional methods such as amine adsorption and

Natural gas has always been one of the main fuels in the industries
(Mozafari et al., 2020). However, natural gas transportation is associ­
ated with problems such as pipeline corrosion (Fakoori et al., 2021), gas
hydrates formation (Jomekian et al., 2016), pressure drop in the gas
transfer process (Dorosti et al., 2015) and reduction of the gas heat value
(Raouf et al., 2020), which is due to the presence gas impurities such as
CO2. CH4 is the main ingredient, and CO2 is also the main impurity of
natural gas. Therefore, the CO2 removal from natural gas seems inevi­
table. On the other hand, a small increment of CO2 can cause environ­
mental changes, such as global warming, polar ice melting, and air
pollution (Ahmadpour et al., 2014; Mozafari et al., 2018; Li et al., 2018;
Shahrezaei et al., 2019; Khoshhal Salestan et al., 2021a). Membrane
technology is an effective way for gas separation with prespecified
purposes (Abedini et al., 2018). In the last decade, plenty of studies have
been done on membrane gas separation and many efforts have been
made to improve the membrane performance in gas separation to
cryogenic distillation which consume a lot of energy (Abedini et al.,
2014; Jamshidi et al., 2017). Recently, membrane separation technol­
ogy is better than other technologies due to their simplicity, low energy
consumption (Zhang et al., 2021; Khoshhal Salestan et al., 2021b), easy
scalability (Nezhadmoghadam et al., 2018), high efficiency, and envi­
ronmental protection (Babaei et al., 2020). However, they still suffer
from low productivity and low mechanical and thermal stability
(Nematollahi et al., 2016). Polymers are the main materials employed in
developing the membrane gas separation (Estahbanati et al., 2017).
Polymeric membranes are widely used in industries due to their low
fabrication and maintenance cost, ease of fabrication, and process
ability (Dorosti et al., 2014; Ranjbar et al., 2022a). Most commercial
polymers those employed for membrane synthesis are polysulfone,
polystyrene, polyimide, polyethylene glycol, polydimethylsiloxane and
Pebax®1657, have been showing a trade-off between permeability and
selectivity, introduced by Robeson (Robeson, 2008; Nematollahi et al.,
2019; Kheirtalab et al., 2020; Nobakht and Abedini, 2022). Polymers

* Corresponding author.
E-mail address: abedini@nit.ac.ir (R. Abedini).

https://doi.org/10.1016/j.psep.2022.12.058
Received 7 August 2022; Received in revised form 19 December 2022; Accepted 19 December 2022
Available online 21 December 2022
0957-5820/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
D. Nobakht and R. Abedini
containing ether, carboxylate, amine or acetate groups are more
appropriate candidates for developing membranes for CO2 separation,
because such functional groups show affinity to CO2 and improve CO2
permeability and its selectivity to other gases (Ranjbar et al., 2022b;
Kheirtalab et al., 2020; Rabiee et al., 2014).
However, low permeability and selectivity, lack of stability in in­
dustrial conditions, and weak durability have limited the widespread
use of polymeric membranes in gas separation tasks. Different methods
(like blending, grafting, cross-linking, etc.) have been used to overcome
this limitation (Sanaeepur et al., 2019a). Moreover, developing mixed
matrix membranes (MMMs) is one such effort to improve the perfor­
mance of polymeric membranes for gas separations. In MMMs, perme­
ability and selectivity can be balanced by incorporating mineral fillers
through an organic polymer network (Jamshidi et al., 2017).
As an alternative to conventional polymer membranes, MMMs, have
the special feature of molecular sieve minerals combined with the cost-
effectiveness of organic polymer materials (Hosseinzadeh Beiragh et al.,
2016; Ravanchi et al., 2009). The minerals with high degree of chemical
and mechanical strength are used as a dispersed phase to fabricate
MMM. MMMs accent the advantages of both polymers and inorganic
additives including easy processability and high selectivity (Aroon et al.,
2010; Bastani et al., 2013; Nematollahi et al., 2022). However, fabri­
cation of mixed matrix membranes (MMMs) is associated with problems
such as poor interaction among the incorporated particles and the
polymer matrix, as well as poor particle dispersion within the polymer
matrix. One of the essential factors in MMMs is the morphology of
polymer-filler interface, which can significantly affect membrane per­
formance (Raouf et al., 2020; Sadeghi et al., 2016).
Thus, the type of filler is a key factor that must be carefully selected,
as it must provide the required adhesion to the polymer matrix and not
show defects at the polymer-filler interface. Thus, an appropriate filler
can provide significant permeability and selectivity to the mixed matrix
membrane. In addition, plasticization due to the presence of CO2 within
a polymer matrix may deteriorate the membrane selectivity for gas
mixture separation, which can be eliminated by crosslinking the poly­
mer or adding fillers to the matrix (Meshkat et al., 2020). Mixed matrix
membranes with rubbery polymers usually show higher permeability
and lower selectivity than glassy ones. The higher permeability of
rubbery polymers is due to the high chain mobility and large free frac­
tional volume (FFV). On the other hand, glassy polymers with restricted
chain movement and lower FFV suggest higher selectivity due to their
molecular sieve property.
However, rubbery polymers have less mechanical stability, which
limits their use in industry (Hosseinkhani et al., 2014; Rabiee et al.,
2015). Polyether-based polymers improve the solubility of CO2 due to
their polar ether groups and have attracted more attention recently.
However, if polyethylene oxide is used alone in the membrane, it is
associated with problems such as crystallization and low mechanical
strength (Liu et al., 2016). Among the most popular polymers, which
include polyether, the polyether block amide (PEBA) copolymer is a
combination of a polyether rubbery polymer (which interacts with CO2)
and a polyamide glassy polymer (which provides the required me­
chanical strength) (Wang et al., 2012). One class of polyether block
amide as a trading name of Pebax copolymer has been used in numerous
membrane researches (Meshkat et al., 2018). Pebax®1657 with 60 wt%
of polyether (rubbery content) and 40 wt% of polyamide (glassy con­
tent) has been shown a suitable CO2 permeability. Therefore, it seems
that more efforts should be made to increase the CO2 selectivity over
other gases. For this purpose, several research has been done to blend
Pebax with low molecular weight liquid polymers (such as polyethylene
glycol, polypropylene glycol), polyols (such as polyvinyl alcohol, glyc­
erol, sorbitol, and maltitol), and ionic liquids (such as [emim] [BF4],
[bmim] [BF4]) (Nobakht and Abedini, 2022; Hassanzadeh et al., 2022;
Sanaeepur et al., 2019a). The hydroxyl and carbonyl groups of these
polymers can interact with CO2 molecules by the Lewis acid-base
mechanism. These interactions occur between the positive charge of
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Process Safety and Environmental Protection 170 (2023) 709–719
the carbon atom in the CO2 molecule and the negative charge of the
oxygen atom in the hydroxyl group, and improve the permeability of
CO2 compared to other gases (Kheirtalab et al., 2020; Nobakht and
Abedini, 2022). Kheirtalab et al. (2020) improved the separation prop­
erties of pure Pebax®1657 membrane by adding PVA. They showed that
CO2 permeability and CO2/CH4 selectivity in Pebax/PVA (10 wt%)
membrane increased by 2.3% and 32.6%, respectively. But CO2/N2
selectivity in Pebax/PVA (15 wt%) reaches its maximum value, where it
is increased by 101.3% compared to pure Pebax®1657. Rahman et al.
(2013) prepared Pebax/PEG-POSS blend membrane for CO2 separation.
In this study, they examined two grades of Pebax (1657 and 2533). By
adding 30 wt% PEG-POSS in the Pebax polymer network, CO2 perme­
ability was doubled in both grades. Although the selectivity of CO2/N2
and CO2/CH4 has doubled in Pebax®2533, it has not changed signifi­
cantly in Pebax®1657. Sanaeepur et al. (2019a) were able to improve
CO2/N2 selectivity by adding glycerol to Pebax. The results demon­
strated that adding 15 wt% of glycerol to Pebax increased CO2/N2
selectivity by 172%. Sanaeepur et al. (2019b) also investigated the effect
of Pe/CA membrane on CO2 separation. They indicated that the
permeability and selectivity of CO2 in the CA/Pe (8 wt%) membrane
improved by 25% and 59%, respectively, compared to pure CA
membrane.
The presence of different nanoparticles in the Pebax-based mixed
matrix membrane is a suitable method to improve the separation per­
formance and physicochemical properties (Jazebizadeh and Khazraei,
2017). Many materials such as metal-organic frameworks (MOFs)
(Jusoh et al., 2016), carbon nanotubes (CNTs) (Li et al., 2015), graphene
and graphene oxide (GO) (Dong et al., 2016), covalent organic frame­
works (COFs) (Meshkat et al., 2020), nano-silica (Barooah and Mandal,
2018), ceramics, and zeolites are used to prepare highly permeable and
selective mixed matrix membranes (Barooah and Mandal, 2019). MOFs
are highly regular crystalline tiny porous materials composed of
self-assembling cation metals and organic bonding agents. MOFs are
considered as an ideal choice for fillers due to their adjustable pore size,
high porosity and specific surface area, high CO2 adsorption capacity,
and relatively good thermal and chemical stability (Erucar and Keskin,
2013; Doosti and Abedini, 2022). For example, UiO-66 is one of the MOF
particles used expensively in MMM synthesis for CO2 separation. Wang
et al. (2020) incorporated the UiO-66 and UiO-66-NH2 metal organic
frameworks (MOFs) nanoparticles into a Tröger’s base polymer, dime­
thylbiphenyl Tröger’s base polymer (DMBPTB). The CO2 permeability of
the UiO-66/DMBPTB membranes increased significantly, but selectivity
decreased slightly. Moreover, the composite membranes with
amine-functionalized UiO-66 nanoparticles displayed higher perme­
ability and selectivity to the CO2/CH4 gas pair. The best gas separation
performance was obtained for the UiO-66-NH2 (30 wt%)/DMBPTB
composite membrane, where the CO2/CH4 selectivity was 18.0, and the
CO2 permeability was 744 Barrer. Moreover, Zeolitic imidazolate
frameworks (ZIFs) also are another type of MOF structure. They are
porous crystals with a three-dimensional structure that are formed by
combining metal ions (zinc, cobalt, etc.) and quadrilateral imidazole
(Zhang et al., 2021). Their most important feature is the large-diameter
cages and narrow holes in the CO2 kinetic diameter range (Koros and
Zhang, 2017). The addition of MOF in polymers to produce mixed ma­
trix membranes is currently an active research field in gas separation
membranes. ZIF-8 is the most widely studied ZIF in the field of gas
separation membranes. It has a zinc(II) centered metal framework with
nitrogen atoms in positions 1 and 3 of the five members of the imidazole
rings in the form of sodalite (Meshkat et al., 2020). Kheirtalab et al.
(2020) made the Pebax®1657/PVA/GO ternary mixed matrix mem­
brane. They were able to increase CO2 permeability to 236.48 barrer and
CO2/CH4 selectivity to 33.63 by adding 10 wt% of polyvinyl alcohol and
6 wt% of graphene oxide to the Pebax polymer network. They also
examined CO2/N2 separation, with the best values being Pebax/PVA
(15 wt%)/GO (6 wt%), Where CO2 permeability was 228.34, and
CO2/N2 selectivity was 124.09. Shahrezaei et al. (2019) improved the
D. Nobakht and R. Abedini
performance of Pebax®1657/Glycerol by adding copper nanoparticles
to the blend membrane. Pebax/Glycerol (15 wt%)/Cu (1.5 wt%) mixed
matrix membrane with 63.6 barrer permeability and 200 for CO2/N2
selectivity exhibited the best performance. Jomekian et al. (2016)
improved the membrane gas separation performance by adding ZIF-8
particles to Pebax®1657 membrane. Thus, Pebax/ZIF-8 (8 wt%)
Showed CO2 permeability of 752 barrer and CO2/CH4 selectivity of 16.1.
Zhang et al. (2021) added ZIF-8 and CNT to the Pebax®1657 polymer
network for CO2 separation. The 5 wt% ZIF-8 @CNT membrane had the
best CO2 separation performance, with CO2 permeability reaching 225.5
barrer and CO2/N2 selectivity reaching 48.9. Meshkat et al. (2020)
investigated the effect of ZIF-8 and ZIF-67 on the Pebax polymer
network in CO2 separation. The results showed that CO2 permeability in
Pebax/ZIF-67 increased by 130% and in Pebax/ZIF-8 by 85% compared
to pure Pebax. The selectivity of CO2/CH4 and CO2/N2 in ZIF-67 is
higher than ZIF-8 due to the smaller pore size of ZIF-67.
In this study, the polar grade Pebax (i.e., Pebax®1657) was used as a
based polymer phase of membrane. As mentioned earlier, the existence
of a polar group such as hydroxyl within the membrane matrix can
intensify the interaction among CO2 and membrane. Thus, maltitol (as a
polyalcoholic compound) given its nine hydroxyl groups in the structure
used as an excellent candidate for blending with Pebax to improve the
membrane separation performance. Fig. 1 demonstrates the possible
Lewis acid-base interactions between the hydroxyl (OH) groups of
maltitol and CO2 molecules, which ultimately increase CO2 perme­
ability. Synthesized ZIF-8 (as a filler) also is applied to incorporate with
Pebax/maltitol blend to develop a mixed matrix membrane. Addition of
ZIF-8 is also expected to increase the CO2/N2 and CO2/CH4 selectivities
because the pore size of ZIF-8 is in the kinetic diameter range of CO2 and
also ZIF-8 particles have a tendency to adsorb CO2 molecule (see Fig. 1).
Finally, the obtained mixed matrix membranes are examined by FTIR,
FESEM, TGA, DSC, and BET analyses, and the gas separation mem­
branes’ performance is also investigated through gas permeation tests.
2. Experimental
2.1. Materials
Pebax® MH 1657 as a base polymer (Merk, Germany), maltitol as a
modifier (Merk, Germany), ethanol (99%) as a solvent (Merk, Germany),
and deionized (DI) water as a solvent (BEHAZMA, Iran) were used. The
materials employed for the synthesis of ZIF-8 nanoparticles include zinc
nitrate hexahydrate [Zn (NO3)20.6 H2O], 2-methylimidazole (Hmim)
[C4H6N2], and methanol (99%) were all of them provided by Merk
Fig. 1. Schematic representation of intermolecular interaction between the constituents of Pebax/maltitol/ZIF-8 membranes with CO2.
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Process Safety and Environmental Protection 170 (2023) 709–719
(Germany) and used without further purification.
2.2. Synthesis of ZIF-8
The ZIF-8 synthesis has followed the procedure explained by Bar­
ooah and Mandal (2019), in which 2-methyl imidazole (6.48 g) and zinc
nitrate (2.933 g) are dissolved separately in 200 ml of methanol. The
2-methyl imidazole solution is then slowly added into the zinc nitrate
solution. The final solution is stirred vigorously at room temperature for
1 h and then rested for 24 h. After settling, the excess solvent is dec­
anted, and the remaining material is centrifuged for 15 min at 5000 rpm
for three times. The obtained ZIF-8 powders are then dried in an oven at
50 ◦ C for 12 h.
2.3. Membrane preparation
To prepare Pebax/maltitol, certain amount of Pebax was added to
the ethanol/DI water (70/30 wt%) solvent and stirred for 24 h at 80 ◦ C
under reflux condition to obtain an uniform and semi-transparent so­
lution. Specific amounts of maltitol were solved with DI water and then
added to the Pebax solution dropwise. The resulting solution then stirred
for 24 h, and transferred to a Teflon petri dish and allowed to rest over
night for solvent evaporation. It is then placed in an oven at 60 ◦ C for
12 h for further evaporation of any remaining solvent.
To prepare mixed matrix membranes: first, a certain amount of ZIF-8
powder is dispersed in ethanol/water solution (70/30) using an ultra­
sonic bath for 1 h. Next, Pebax granules are added to the ZIF-8/solvent
suspension and stirred at 70 ◦ C for 4 h. After that, a specified maltitol
powder is added to the solution and vigorously stirred for 4 h to achieve
a homogeneous solution. The final solution is sonicated again for 1 h for
better ZIF-8 dispersion within the Pebax solution and then poured in a
petri dish and dried in an oven at 60 ◦ C for 12 h.
2.4. Membrane characterization
2.4.1. Fourier transform infrared spectroscopy – attenuated total
reflectance (FTIR–ATR)
Fourier transform infrared spectroscopy – attenuated total reflec­
tance (FTIR–ATR) was performed by means of spectrophotometer
(JASCO 6300 Model, Japan) over the wavenumber range of 400 –
4500 cm− 1 and resolution of 4 cm− 1.
2.4.2. Field emission scanning electron microscopy (FESEM)
Field emission scanning electron microscopy (FESEM) were applied
D. Nobakht and R. Abedini
to study the morphology of membranes. First, the membrane samples
were submerged in liquid nitrogen to fractured for a clean cut and then
coated with gold. Finally, the cross-sectional morphology of the samples
was examined by using a microscope (Leo 1430 VP Model, incorporated
by Germany and England).
2.4.3. Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) was conducted using a STA1500
from Rheometric Scientific to test the thermal stability of the Pebax/
maltitol/ZIF-8 MMMs. The samples were dried in a vacuum oven for
24 h at 60 ◦ C for moisture removal, then were heated from 25◦ to 800◦ C
at a heating rate of 10 ◦ C/min under the nitrogen atmosphere.
2.4.4. Differential scanning calorimetry (DSC)
Thermal behavior of membranes was studied by double-scanned
differential scanning calorimetry (DSC, F200 Model, Netzsch, Ger­
many). For this purpose, the samples were heated from − 100 to 250 ◦ C
at a rate of 10 ◦ C/min under nitrogen atmosphere. Melting temperature
(Tm), glass transition temperature (Tg), crystallization temperature,
crystallization percentage, and heat of fusion (ΔHm) of membranes were
measured.
Fig. 2. ZIF-8 analysis, (a) FTIR-ATR spectra, (b) FESEM image, and (c) BET analysis.
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Process Safety and Environmental Protection 170 (2023) 709–719
2.4.5. Nitrogen adsorption-desorption isotherm and BET analysis
A BELSORP (mini 2 Model, Japan) instrument was used to obtain the
BET specific surface area of ZIF-8 at 77 K nitrogen adsorption-
desorption isotherm. Prior to analysis, the samples were degassed at
140 ◦ C for 24 h. The internal surface area was determined by Bruner
Emmett-Teller (BET) method and the micropore volume by the t plot
method.
2.5. Gas permeation measurements
The permeability of pure gases (CO2, CH4, and N2) was determined
by the constant volume/variable pressure method. A feed gas was
introduced to the membrane cell at a temperature of 30 ◦ C and feed
pressure of 2, 6, and 10 bar. The accumulated permeate gas in the
downstream chamber was analyzed by calibrated gas pressure sensors.
The pure gas permeability and ideal selectivity were calculated ac­
cording to Eqs. (1) and (2), respectively:
273.15 × 1010 VL dp
P= [ 0 ×76] ( ) (1)
760AT p14.7 dt
PA
αA/B = (2)
PB
D. Nobakht and R. Abedini Process Safety and Environmental Protection 170 (2023) 709–719

where P is the pure gas permeability, Barrer (1 Barrer = 10− 10 cm3 (STP) 3297 cm− 1 in pure Pebax membrane to wavenumber of 3296 cm− 1 in
cm/ (cm2 cmHg s)); V is the constant volume of the downstream Pebax/maltitol (20 wt%) blend membrane. In the case of Pebax/maltitol
chamber of the membrane holder (cm3); L is the thickness of membrane (20 wt%) MMMs containing 3, 5, and 10 wt% of ZIF-8, the band position
(cm); A is the effective membrane area (cm2); T is the absolute tem­ of N–H did not change significantly and showed the same number.
perature (K); p0 is the pressure of feed flow (atm), and dp/dt is the rate of
pressure increase at the steady-state condition in the downstream (atm/ 3.2.2. FESEM analysis
s). PA and PB are the permeabilities of the gases A and B, respectively. The gas permeability performance of membranes is strongly affected
by membrane morphology (Nobakht and Abedini, 2022). The thickness,
the surface, and cross-sectional FESEM images of MMMs with different
3. Results and discussion
loading of ZIF-8 are depicted in Fig. 5. As can be seen in Fig. 5, a uniform
cross-section of the neat Pebax membrane without any defects. As can be
3.1. Characterization of ZIF-8
seen in Fig. 5, the roughness rises by adding 20 wt% maltitol in the
Pebax matrix. The dispersed ZIF-8 powder can be observed clearly in
The FTIR-ATR spectra of the synthesized ZIF-8 filler was represented
MMMs (Fig. 5). By increasing ZIF-8 loading, the roughness increased
in Fig. 2(a). The spectra demonstrated the adsorption bands of the
with a higher effective area which can entrap the gas molecules and so
imidazole functional group. The absorption bands at 3133 cm− 1 and
facilitates molecular transport (Zhang et al., 2021). The cross-sectional
2926 cm− 1 were assigned to the imidazole aromatic and aliphatic C− H
images of the synthesized Pebax/maltitol (20 wt%)/ZIF-8 (3, 5, and
stretch, respectively. The band observed at 1576 cm− 1 is attributed to
10 wt%) MMMs reveal the uniform dispersion of ZIF-8 nanoparticles in
the C–– N stretching vibrations. The wavenumber region of 1500 –
the blend matrix at low loading (3 and 5 wt%), while their agglomera­
900 cm− 1 and below 800 cm− 1 corresponds to the in-plane and out-of-
tion improved at a high loading of 10 wt%. The significant difference
plane bending of the imidazole rings, respectively (Barooah and Man­
between surface energies of nanoparticles and polymers may be the
dal, 2019; Meshkat et al., 2020). The morphologies of ZIF-8 products
primary cause of the accumulation of nanoparticles in the polymer
and the statistical particle size distributions were investigated by FESEM
matrix (Meshkat et al., 2020).
images. As seen in Fig. 2(b), ZIF-8 has a sodalite topology with a particle
size of approximately 60 nm, which has good uniformity. The N2
3.2.3. TGA analysis
adsorption-desorption isotherm of synthesized ZIF-8 is presented in
The TGA curves of ZIF-8 nanoparticle, Pebax/maltitol blend mem­
Fig. 2(c). As shown in Table 1, this analysis demonstrates BET surface
brane, and Pe/mal/ZIF-8 MMM are demonstrated in Fig. 6. As shown in
area, Langmuir surface area, volume, and pore size distribution. The
the Fig. 6, the weight loss diagram of samples exhibited three weight loss
analysis indicates the high specific area of synthesized ZIF-8, about
stages. For ZIF-8 particles, there is no significant weight loss to 400 ◦ C
1003.2 m2/g, and as can be seen in Fig. 2(c), the maximum gas
(about 5 wt%), which may be referred to the physically absorbed
adsorption capacity is about 230.5 cm3/g.
moisture evaporation. The weight drops at 400–500 ◦ C (about 40 wt%)
can be assigned to loss of solvent moisture entrapped in the ZIF-8
3.2. Characterization of membrane
nanocrystal. From 500 to 800 ◦ C, the weight loss (about 20 wt%) was
due to the decomposition of ZIF-8 (Barooah and Mandal, 2019; Zheng
3.2.1. FTIR-ATR analysis
et al., 2019). The TGA curves of MMMs also display three main zones.
The FTIR-ATR spectra of pure Pebax®1657, maltitol, Pebax/maltitol
The first zone corresponds to the moisture and solvent evaporation. The
(20 wt%) blend membrane, and mixed matrix membranes containing 3,
second one with the highest weight loss of any MMM is polymer chain
5, and 10 wt% of ZIF-8 were analyzed in the wavenumber range of 650 –
degradation. The final weight loss is ascribed to the chain carbonization
3950 cm− 1, and the obtained results were depicted in Fig. 3. In pure
(Kheirtalab et al., 2020; Nobakht and Abedini, 2022). As can be seen in
Pebax membrane spectrum, the adsorption bands at 848, 1096, 1732,
Fig. 6, the decomposition temperature (Td) of pure Pebax and maltitol is
and 2938 cm− 1 are related to the tensile vibration of –O–H, C–O–C,
about 370 and 209 ◦ C, respectively. Due to the lower thermal stability of
C–– O, and –CH3 groups, respectively. In addition, the bands at 1637 and
maltitol (as poly alcoholic compounds), the Td of blend membranes is
3297 cm− 1 are contributed to the mobility of the H–N–C– – O and N–H
reduced compared to the pure Pebax. The degradation of ZIF-8 initiates
groups in the hard polyamide (PA) segment of Pebax polymer, respec­
from about 504 ◦ C. The TGA curves indicate that as the loading of ZIF-8
tively (Habib et al., 2020; Kheirtalab et al., 2020; Taheri et al., 2021). In
increases, the decomposition temperature of MMMs increases. The
the spectrum of pure maltitol, the bands at 3337 and 2923 cm− 1 sig­
degradation temperature of the Pebax/maltitol/ZIF-8 (3 wt%) mem­
nifies the hydroxyl group (O–H) and C–H symmetric vibrations (Kheir­
brane is about 320 ◦ C, while for the Pebax/maltitol/ZIF-8 (10 wt%)
talab et al., 2020). The bands at 1433 and 1018 cm− 1 also attributed to
membrane, this number is about 378 ◦ C. This increase in decomposition
the –CH2 bending and C–O stretching, respectively. As can be seen in
temperature is due to the higher thermal stability of ZIF-8 particles.
Fig. 3, the spectrum of the Pebax/maltitol (20 wt%) blend membranes,
the location of characteristic peaks is negligibly varied due to the
3.2.4. DSC analysis
interaction between Pebax with maltitol (Sanaeepur et al., 2019a). Fig. 4
DSC analysis usually provides invaluable information about the
exhibits the probable mechanism of intermolecular interactions in the
thermal behavior of the membrane. It can be applied simultaneously to
Pebax/maltitol blend membranes. These slight shifts can be attituded to
examine parameters such as glass transition temperature (Tg), percent­
diminishing intermolecular hydrogen bonds among PA and PEO seg­
age of crystallization, melting temperature (Tm), and crystallization
ments in pure Pebax and leading to the formation of new intermolecular
temperature. Fig. 7 represents the DSC thermogram of pure Pebax,
hydrogen bonds between Pebax and maltitol. Furthermore, the tensile
Pebax/maltitol (20 wt%), Pebax/maltitol (20 wt%)/ZIF-8 (3 wt%),
vibration of the N–H hydrogen bond encountered a displacement from
Pebax/maltitol (20 wt%)/ZIF-8 (5 wt%), and Pebax/maltitol (20 wt
%)/ZIF-8 (10 wt%) membranes. In the thermogram of Pebax, two sharp
Table 1 peaks were observed at 16.58 and 205.67 ◦ C, which correspond to the
BET results and N2 adsorption-desorption of ZIF-8 particles.
melting points of PEO and PA segments, respectively. The obtained Tg
Mean Total t-method Volume BET Langmuir for neat Pebax is − 52.63 ◦ C, which is in good agreement with what is
Pore Pore micropore Adsorption surface surface reported in the literature (Kheirtalab et al., 2020; Sanaeepur et al.,
diameter Volume Volume (cm3/g) area area (m2/
(nm) (cm3/g) (cm3/g) m2/g) g)
2019a). Since maltitol with Tg of 43.10 ◦ C (Hadjikinova and Marudova,
2016) which higher than the Tg of Pebax, the glass transition tempera­
1.83 0.4607 0.3882 230.5 1003.2 1138
ture of the blend membranes increases by approximately 6 ◦ C. As shown

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Fig. 3. FTIR-ATR spectra of MMM, a) pure Pebax 1657, b) Pebax/maltitol (20 wt%), c) Pebax/maltitol (20 wt%)/ZIF-8 (3 wt%), d) Pebax/maltitol (20 wt%)/ZIF-8
(5 wt%), e) Pebax/maltitol (20 wt%)/ZIF-8 (10 wt%), f) pure maltitol.

Fig. 4. Schematic representation of intermolecular interaction among Pebax, ZIF-8 and maltitol in MMM.

in the DSC curves, there is no new glass transition change when maltitol calculated using the following equation:
is added to the Pebax matrix, which means that appropriate miscibility
ΔHm
of maltitol with Pebax is achieved (Nobakht and Abedini, 2022). As XCristallinity = ◦ (3)
ΔHm
shown in Fig. 7, by adding ZIF-8 nanoparticles from 0 to 10 wt% to the
Pebax matrix the Tg increases from − 46.22 to − 41.55 ◦ C. The increase
where ΔHm is the heat needed for melting crystals, that’s achieved by
in Tg can be attributed to the restriction in polymer chain mobility due to
integrating the surface area below the melting peaks, and ΔHm⁰ is the
the incorporated ZIF-8 particles within the membrane matrix (Zheng
enthalpy of melting in a 100% crystalline state which is 166.4 (J/g) and
et al., 2019). The crystallization degree of the membrane samples can be
230 (J/g) for PEO and PA (as Pebax segments), respectively (Meshkat

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D. Nobakht and R. Abedini Process Safety and Environmental Protection 170 (2023) 709–719

Fig. 5. The surface and cross-sectional images of (a, a′ ) pure Pebax, (b, b′ ) Pebax/maltitol (20 wt%), (c, c′ ) Pebax/maltitol (20 wt%)/ZIF-8 (3 wt%), (d, d′ ) Pebax/
maltitol (20 wt%)/ZIF-8 (5 wt%), (e, e′ ) Pebax/maltitol (20 wt%)/ZIF-8 (10 wt%).

Fig. 6. The TGA curves of ZIF-8 powder, pure Pebax, maltitol, Pebax/maltitol
blend membrane, and Pebax/maltitol/ZIF-8 MMMs. Fig. 7. DSC thermogram of neat, blend and mixed matrix membranes.

715
D. Nobakht and R. Abedini Process Safety and Environmental Protection 170 (2023) 709–719

et al., 2018). The degree of total crystallinity is calculated as follow: enhances the dissolution of penetrant gases (as an initial step of gas
transport in the membrane). The dipole-quadrupole interactions be­
Xtotal.cristallinity = 0.6 × XPEO.cristallinity + 0.4 (4)
tween CO2 and membrane were established by the ether oxygen of
Table 2 listed the measured Tg, Tm, and calculated XC for all mem­ Pebax and CO2, as well as the electrostatic interactions between unco­
brane samples. The addition of maltitol into Pebax leads to an increase in ordinated nitrogen on the imidazolate linker and unsaturated metal
Tm (Nobakht and Abedini, 2022; Sanaeepur et al., 2019a). Also, the zones of ZIF-8 with CO2 molecules, leading to more soluble CO2. The
crystallinity degree of the Pebax/maltitol (20 wt%) blend membrane is polar nature of C–– O bonds (as an element of CO2 molecule) favors its
reduced by 4.2% compared to pure Pebax, which is the result of preferential adsorption on polar ZIF-8 walls, which are intrinsically
appropriate interactions between the hydroxyl groups of maltitol and polarized by the uncoordinated nitrogen atoms of the imidazolate
the carbonyl groups of PA (in the Pebax chain). This interaction can linkers. In general, the concentration of CO2 in the matrix is higher than
disrupt the polymeric chain of Pebax and increase the chain mobility CH4 or N2 under similar conditions, due to the higher condensability,
(Nobakht and Abedini, 2022). As can be seen in Table 2, the crystallinity smaller size, and polarizability, as well as intrinsic electrostatic prop­
of the MMM diminishes after loading ZIF-8, which implies a shift to a erties of the ether oxygen in the polymer together with the metal and
rubberier state. In fact, despite the increase in PEO melting point, MMM linker in the ZIF-8 framework (Meshkat et al., 2020).
does not tend to rigidification, thus limiting chain mobility (Meshkat The results revealed that the CO2 permeability improved from
et al., 2020). 189.65 barrer in Pebax/maltitol (20 wt%) to 258.97 barrer in Pebax/
maltitol (20 wt%)/ZIF-8 (5 wt%), which indicates 37% modification.
The best performance for CO2/N2 separation assigns to Pebax/maltitol
3.3. Gas permeability results (20 wt%)/ZIF-8 (5 wt%) MMM. As can be seen in Fig. 10, the CO2/N2
selectivity enhanced from 45.58 to 48.77 as the ZIF-8 content raised
Fig. 8 shows the permeability of CO2, CH4, and N2 gases and the from 0 to 5 wt%, respectively. A similar mechanism as CO2/CH4 sepa­
calculated CO2/CH4 and CO2/N2 selectivity of MMMs with various ZIF-8 ration emerged for CO2/N2. In addition, the permeability of N2 is a
loadings (0–10 wt%) at a temperature of 30 ◦ C. function of its diffusivity, and an increase in membrane free volume
As shown in the Fig. 8, the gas permeability of MMM is increased could enhance its permeability. Since the N2 has the largest kinetic size
with ZIF-8 loading compared to Pebax/maltitol (20 wt%) blend mem­ than CO2, its permeability modification was weaker, and consequently,
brane. This is due to the role of ZIF-8, which reduces crystallinity, and the CO2/N2 separation was 7% improved.
finally enhances the CO2 permeability. By increasing ZIF-8 content
within the MMM, the CO2 permeability improved while the CO2 selec­ 3.3.1. Effect of feed pressure
tivity over CH4 and N2, dropped slightly at the higher loading of ZIF-8 (i. The effect of feed pressure on gas permeability and selectivity was
e., 10 wt%). This small reduction in CO2/CH4 and CO2/N2 selectivities studied for all MMMs, and the results are shown in Fig. 8. Three possible
may be due to the some degree of MOF agglomeration that is possible at mechanisms can affect the gas permeation properties of membranes by
extra loading of ZIF-8 (Zhang et al., 2021; Zheng et al., 2019). Among all increasing pressure. First, rising the feed pressure (i.e., increasing the
the prepared membranes for CO2/CH4 separation, Pebax/maltitol driving force for penetrant diffusion) enhances the gas permeability.
(20 wt%)/ZIF-8 (5 wt%) MMM reveals the best performance. The values Second, the membrane-free volume diminishes as the feed pressure in­
for CO2 permeability and CO2/CH4 selectivity are 397.85 barrer and creases, which influences the gas permeability. Third, the gas concen­
26.59 at 10 bar and 30 ◦ C. However, Pebax/maltitol (20 wt%) mem­ tration in the membrane matrix increases by increasing feed pressure,
brane in all ZIF-8 (3, 5, and 10 wt%) loading implied a better perfor­ which enhances the gas solubility (especially for condensable gas)
mance in CO2/CH4 and CO2/N2 separation compared to neat blend (Kheirtalab et al., 2020; Nobakht and Abedini, 2022). This permeability
membrane. Therefore, the CO2/CH4 selectivity improved from 23.94 at behavior can be illustrated via plasticization and polymer chains
blend membrane to 26.59 at 5 wt% of ZIF-8 within the membrane ma­ arrangement, which increase by higher CO2 feed pressure. On the other
trix (11% enhancement). On the one hand, the contribution of kinetic hand, the gas penetration driving force increases with higher feed
diffusional parameters such as MOF intrinsic porosity (large surface area pressure. Moreover, the sorption of condensable gases at higher pressure
1003 m2 for ZIF-8), kinetic diameter of gases (CO2 = 3.3 Å, N2 = 3.6 Å is enhanced due to a strong interaction between the polar groups of the
and CH4 = 3.8 Å), and the disturbing role of MOF on polymer chain membrane and the gases, which results in polymer plasticization and
structure (decreased crystallinity) should be considered when explain­ finally enhances the gas permeability. CO2 has a smaller molecular ki­
ing the gas permeability results. Moreover, the thermodynamic solubi­ netic diameter than N2 and CH4. Permeability rate increment for larger
lity parameters can’t be ignored in enhancing selective gas transport. gas molecules is lower than for smaller ones. Thus, their diffusion
More accurately, two important thermodynamic factors of CO2 are the increased lower than CO2, and the CO2/CH4 and CO2/N2 selectivity
condensability and the quadrupole moment (Gholami et al., 2017; improved (Dorosti and Alizadehdakhel, 2018; Jomekian et al., 2016).
Robeson et al., 2014). The condensability of CO2 is higher than CH4 and Fig. 8 presents the shifts in gas permeability and selectivity of
N2 (304.2 K vs. 191.5 K and 126.2 K critical temperature), which Pebax/maltitol/ZIF-8 membranes versus ZIF-8 loading at a pressure
range of 2 – 10 bar. CO2 permeability in Pebax/maltitol (20 wt%)/ZIF-8
Table 2 (5 wt%) improved from 258.97 barrer at 2–397.85barrer at 10 bar.
DSC results and crystallinity degree of mixed matrix membranes. CO2/CH4 and CO2/N2 selectivity in Pebax/maltitol (20 wt%)/ZIF-8
Membrane Tg Tm, Tm, PA XC, XC, PA XC,
(5 wt%) also enhanced from 18.34 to 26.59 and 48.77–69.31,
PEO PEO Total
respectively.
Pebax ZIF- (◦ C) ( C)
◦
(◦ C) (%) (%) (%)
8 3.3.2. Membrane performance study
Pebax 0 -52.63 16.58 205.67 16.75 32.76 23.15 The separation performance of neat Pebax, blend, and mixed matrix
Pebax/ 0 -46.64 18.57 206.72 16.11 31.27 22.17 membranes in CO2/CH4 and CO2/N2 separation can be assessed by
20Mal Robeson bound. As shown in Figs. 9 and 10, the membrane performance
Pebax/ 3 -44.72 19.24 207.85 15.87 31.01 21.92
20Mal
leads to approaching the Robeson bound with increasing pressures.
Pebax/ 5 -43.21 19.85 208.34 15.62 30.69 21.64 Higher ZIF-8 loading together with feed pressure improve the selectivity
20Mal of CO2/CH4 and CO2/N2. Higher CO2 condensability, higher ZIF-8 af­
Pebax/ 10 -41.55 20.45 208.66 15.21 30.24 21.22 finity to adsorb CO2, and higher pressure are three reasons to approach
20Mal
the Robeson upper bound (an attractive industrial area), which could be

716
D. Nobakht and R. Abedini
Fig. 8. The effect of ZIF-8 contents and pressure changes on (a) CO2 permeability, (b) CH4 permeability, (c) N2 permeability, (d) CO2/CH4 selectivity, and (e) CO2/N2
selectivity.
Fig. 9. Comparison of CO2/CH4 separation performances of pure Pebax,
Pebax/maltitol, and Pebax/maltitol/ZIF-8 membranes with Robeson prior and
present bound.
supplied by high-performance membranes. Figs. 11 and 12 also repre­
sent the comparison between the modified Pebax®1657 membranes and
similar studies in CO2/CH4 and CO2/N2 separation. As can be seen, the
performance of each membrane in CO2 separation is a great function of
filler type within the Pebax matrix. According to Figs. 11 and 12, among
different MMMs, some ones have a potential to overcome the Robeson
curve and represent an acceptable performance in terms of permeability
and selectivity. Although, Pebax/maltitol/ZIF-8 showed lower CO2
selectivity compared to some MMMs, its permeability is significantly
717
Process Safety and Environmental Protection 170 (2023) 709–719
Fig. 10. Comparison of CO2/N2 separation performances of pure Pebax, Pebax/
maltitol, and Pebax/maltitol/ZIF-8 membranes with Robeson upper bound.
higher than that of highly selective MMMs. Therefore, the prepared
MMMs in this work have great potential to be employed in gas separa­
tion processes.
4. Conclusions
In this work, ZIF-8 nanoparticles were synthesized and added at
different concentrations (0–10 wt%) into the maltitol modified
Pebax®1657 as the matrix to separate CO2 from N2 and CH4. The mixed
matrix membrane was successfully produced by the solution casting/
solvent evaporation method. The membrane performance was analyzed
D. Nobakht and R. Abedini Process Safety and Environmental Protection 170 (2023) 709–719

Fig. 11. The performance of some modified Pebax®1657 based membranes in CO2/CH4 separation.

Fig. 12. The performance of some modified Pebax®1657 based membranes in CO2/N2 separation.

at 30 ◦ C and 2, 6, and 10 bar. Furthermore, FTIR, FESEM, TGA, DSC, and administration, Funding acquisition.
BET analyses were performed to assess the prepared membrane. It was
found that no chemical interaction between ZIF-8 and modified Pebax
Declaration of Competing Interest
was detected by FTIR analyses, while all the MMM demonstrated
excellent thermal stability below 300 ◦ C based on TGA. DSC analyses
The authors declare that they have no known competing financial
showed lower crystallinity, meaning a rubberier state resulting from the
disruptive role of MOF between the ordered polymer chains. FESEM interests or personal relationships that could have appeared to influence
the work reported in this paper.
images of MMM showed higher roughness compared with pure and
modified Pebax membranes. The obtained results reported that CO2
permeability, CO2/N2, and CO2/CH4 selectivity improved with Acknowledgment
increasing pressure. Finally, the gas permeation results indicated that
Pebax/maltitol (20 wt%)/ZIF-8 (5 wt%) MMM has the best performance The authors acknowledge Babol Noshirvani University of Technol­
in terms of selectivity, which presented CO2/CH4, and CO2/N2 selec­ ogy for financial support of this project (Grant No. BNUT/393054/
tivities of 26.59 and 69.31, respectively. 2020).

CRediT authorship contribution statement References

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