Matrimid®/Cu3(BTC)2 mixed matrix membrane for gas separation

Introduction
1. Polymeric membrane is used in many gas separations due to its low capital cost, ability to
fabricate easily into commercially viable hollow fibers or flat sheets that can be processed into
modules, stability at high pressures, low energy consumption compared to alternative unit
operations and easy scalability
2. Trade-off between permeability and selectivity is observed in Robeson plot
3. Many improvements had done by using inorganic particles (e.g. zeolites), carbon molecular sieves,
inorganic oxides, organic fillers, fullerene and carbon nanotubes were used to prepare mixed matrix
membrane, which is also called as hybrid membrane. It takes the advantages of superior transport
properties of inorganic materials with the ease of separation from polymeric membrane to surpass
Robeson plot
4. There are many issues that is required to be addressed for large scale production of mixed matrix
membrane, which are generation of non-selective voids (incompatibility between fillers and polymer
at the interface), which cause the gas molecules to diffuse easily and thus reduce the overall
separation efficiency of the membrane. Thus, some other interactive functional groups are chosen,
such as silane-coupling agent or highly permeable silicon rubber.
5. Cu3(BTC)2 is one of the most studied for gas adsorption and storage, which it possess the structure
as shown:
a) Main channel pore size: 0.9 nm diameter
b) Tetrahedral pockets: 0.5 nm diameter
c) Angular window: 0.35 nm diameter

6. Some studies in MOF-based MMM:

a) Addition of MOF (Cu-BPY-HFS, Cu-4,4’-bipyridine-hexafluorosilicate) into densed MMM increase
the gas permeability but decreases CO2/CH4 and H2/CO2 selectivities, which is possibly due to the
formation of non-selective voids
b) Addition of MOF (Cu3(BTC)2) into polydimethylsiloxane (PDMS, (C2H6OSi)n) and polysulphone (PSf)
shows high adsorption affinity for CO2 and H2, Mn(HCOO)2 showed high adsorption affinity for H2
only.
c) Higher loading reduced the gas solubility but increases the permeability, which indicates defective
membrane with interfacial voids.
d) 30 wt% MOF-5 (ZnO4-based) loaded Matrimid MMM showed 55% increase in CO2 permeability
with 6% increased in CO2/CH4 selectivity.
e) CuTPA (Cu and terephthalic acid, C6H4(COOH)2) with PVAc (poly(vinyl acetate)) membrane shows
an improvement over unfilled one for gas transport)

Reagents
1. PI Matrimid 9725 and PSf Ultrason S 6010 Natural
2. PDMS monomer (A) and crosslinker (B)
3. Non-woven polypropylene/polyethylene fabric Novatexx 2471
4. *N-methylpyrrolidinone (NMP)
5. *Isopropanol
6. *Cyclohexane
7. *1,3-dioxolane
8. CO2, CH4, N2
* done without further treatment

MOF and membrane synthesis

(A) Cu3(BTC)2
1. Materials to be added into the beaker are: Cu(NO3)2.3H2O = 1.22 g; H3(BTC) = 0.58 g; bi-distilled
water = 0.58 g *(water that had distilled twice); Ethanol = 13.135 g
2. The materials are stirred in beaker for 30 minutes and heating in a Teflon line steel autoclave
(Thermal Reactor) at 110 oC or 15 hr.
3. Crystal were washed with ethanol and water (1:1) before drying at 60 oC overnight and next at 110
o
C for a day

** Grafting of amine:
1. 0.5 g Cu3(BTC)2 was activated at 393 K and outgassed to 10-1 Pa to obtain porous matrix evacuated
with free cavities available for adsorption of other molecules of interest
2. Cu3(BTC)2 was added with toluene (30 mL), and amine is added (with the best is 1:1 Cu : amine
ratio)
3. Resulting suspension was refluxed under N2 for 12 hr (temperature ?) to optimize the extent of
amine grafting
4. The solid product was washed copiously with hexane to ensure complete removal of non-
appended substituent

(B) Prior to making membrane

Polymer (matrimid and PSf) and [Cu3(BTC)2] were dried overnight at 110 oC

(C) Making Mixed Matrix Membrane

1. 10 wt%, 20 wt% and 30 wt% MOF were dispersed in a mixture of NMP and dioxolane (1:2) for 2 hr
with mechanical stirring
𝑤𝑡. 𝑀𝑂𝐹
𝑀𝑂𝐹 𝑙𝑜𝑎𝑑𝑖𝑛𝑔 (𝑤𝑡%) = ( ) × 100
𝑤𝑡. 𝑀𝑂𝐹 + 𝑤𝑡. 𝑝𝑜𝑙𝑦𝑚𝑒𝑟
2. 1/4th of the total amount of polymer was added to the mixture and stirred for 2 hr as pre-coating
procedure
3. The step (2) is repeated until the requisite total polymer amount was added
4. The final mixture was stirred for 3 hr
5. The solution was kept undisturbed at room temperature overnight
6. Membrane was prepared by phase-inversion method:
a) MOF/polymer was cast on non-woven support
b) After 30 s evaporation time, it is solidified by immersion in water bath at room temperature for 30
minutes
c) The membrane was immersed in IPA for 20 minutes
d) The membranes were dried at 70 oC in an oven for 1 day
e) To seal membrane defects, 30 wt% PDMS solution in cyclohexane (A:9, B:1)* was deposited on
each membrane by spin coating at 700 rpm for 40 s
f) The coated membrane were then cured at 90 oC for 24 hr in an oven

* A concentration of 18 wt% polymer/filler mixture was found to be too dilute to keep the fillers in
suspension before casting, while 22 wt% solution was very viscous and difficult to cast, so 20 wt%
solutions were prepared

Characterization Technique
1. Scanning Electron Microscope (SEM)
2. Glass transition temperature of the membrane
3. Mechanical strength with different loadings
4. Thermal stability (TGA)
5. X-ray diffraction (XRD)
6. BET measurement
7. Film density
8. Effective permeability: Maxwell Relation
9. Permeation measurement

Result and Discussion

1. MOF characterization:
a) Type I adsorption isotherm with steep initial N2 uptake with no hysteresis (high level of
microporosity in the structure)
b) High BET surface area, which XRD measurements are in agreement with single crystal data
c) Pore volume is about 0.5 cm3/g
d) Thermal stability of shows two step-decrease in weight loss
= 1st weight loss is about 50 – 120 oC, which is due to desorption of water
= 2nd weight loss is about 300 oC, which is due to disintegration of MOF structure
e) in SEM, distinct cubic crystalline structure and particle size around 10 μm is observed.

2. MMM characterization
a) Highly permeable PDMS is added to seal the non-selective voids on the membrane surface
b) Crystals are shown to be embedded within the polymer matrix immediately below the thin
selective layer, and fillers with 30 wt% loaded membrane are well distributed and embedded in the
polymer matrix
c) Tg values is slightly higher than unfilled PI membrane
d) d-spacing of PI membrane increases from 10 wt% to 30 wt%, which is due to the increased in
polymer interchain distances that lead to an increase in fractional free volume
e) The increased density follows from the higher density of MOF compared to polymer and also
indicate minimal presence of defects

3. Thermal properties of [Cu3(BTC)2]/PI

a) Thermal decomposition (Td) of PI starts around 487 oC and for [Cu3(BTC)2] around 300 oC
b) Increasing [Cu3(BTC)2] content increases Td content up till 30% loading
c) Increase in thermal stability of MMM can be attributed to:
= High thermal stability of [Cu3(BTC)2]
= Interactions between [Cu3(BTC)2] and PI matrix

4. Mechanical properties of [Cu3(BTC)2]/PI

a) Linear increase in increasing Cu3(BTC)2 content
b) Tensile strength and elongation break decrease with increasing Cu3(BTC)2 content, which indicates
more rigid structure for MMM due to presence of Cu3(BTC)2 compared with unfilled PI

5. Effect of CO2 composition on mixed-gas selectivity

a) Increasing CO2/CH4 selectivity in increasing filler loading (testing condition 10 bar and 35 oC)
b) The blend was found to result in a membrane with enhanced stability against CO2 to induce
plasticization (how?)

6. Influence of filler
a) CO2/CH4 and CO2/H2 selectivity increases with increasing PI loading, and PI/Psf blended form
perform not as satisfactory as compared to PI

7. CO2 feed content

a) Decreasing selectivity with increasing CO2 content in the feed gas
b) Strong interaction between PI and CO2 disrupts the polymer chain packing and enhances the
intersegmental mobility, thereby increasing the diffusion of better retained molecule (CH4 and N2)
through the membrane more substantially than that of the CO2.

8. MOF contribution
a) Selectivity of MOF can be ascribed to the differences in the electrostatic interaction of the
different gas molecules with the membrane constituents (CO2 has stronger quadrupole moment, N2
is weaker and CH4 do not possess such effect)
b) Increase in permeance due to the increased d-spacing of the membrane

9. CO2 composition on mixed gas permeance

a) CO2 permeance is higher than unfilled PI, and increases with increasing filler loading
b) Asymmetric structure is important method to increase the permeance of the membrane
10. Discussion in overall performance
a) Compared with asymmetric unfilled PI membrane, the new membrane show a lower permeance
but 40% increase in CO2/CH4 selectivity
b) Facilitation ratio increase with increasing filler loading
c) The extra selectivity aspect introduced by the filler could be either due to competitive adsorption
of the two gases or molecular sieving effect

Zn(SiF6)-PEO Mixed Matrix Membrane

Experimental
1. Materials:
Poly(ethylene glycol) diacrylate, PEGDA
Poly(ethylene glycol) methyl ether acrylate, PEGMEA
Azobisisobutylonitrile, AIBN
Zinc hexafluorosilicate, ZnSiF6
Pyrazine
Methanol

Synthesis of Zn(pyrz)2(SiF6) crystal

1. Pyrazine prepared by dissolving 1.3 mmol pyrazine in 2 ml of methanol
2. ZnSiF6 prepared by dissolving 0.6 mmol Zn(SiF6) in 2 ml of methanol
3. Solution 1 and solution 2 are reacted at room temperature without agitation for 3 days
4. After reaction, harvested crystal were washed with copious amount of methanol and dried at 60
o
C in convection oven
5. The crystals were gently ground before the usage in membrane filtration

Synthesis of submicron Zn(pyrz)2(SiF6) crystal

1. Same step for step 1 and 2, with the exception that the solution are poured in vial, which was
sonicated in an ultrasonic bath at room temperature for 2 hour
2. The formation of white solid particles could be visually identified after 2 hours
3. Filtration was conducted to collect the crystal formed using methanol to wash out residual
membrane filtration
4. The crystal were dried at 60 oC in convection oven

Crosslinked polyethylene oxide membrane

1. Monomeric solution was prepared by mixing two PEO monomers, 1.6 g PEGMEA and 0.4 g PEGDA.
2. A small amount of AIBN (0.005 g) was added to initiate polymerization (left for 1 day)
3. Fully activated Zn(pyrz)2(SiF6) crystal were added to PEO monomeric solution (? g), which was
vigorously agitated for at least 1 day to disperse into the solution before membrane fabrication
4. The solution prepared was sandwiched between two glass plates whose gap thickness was
controlled by placing spacers
5. The membrane was solidified by polymerization of PEO monomers at 65 oC for 1 hr

Characterization
1. Gas adsorption of Zn(pyrz)2(SiF6) crystals
2. Size of Zn(pyrz)2(SiF6) crystal were analyzed using dynamic light scattering
3. TGA for the crystal
4. Morphology of crystal and membrane using FESEM
5. Gas permeation test (CO2/N2: 20/80) and CO2/CH4: 50/50)
6. Prediction of membrane performance using Maxwell Model

Results and Discussion

Crystal Zn(pyrz)2(SiF6)
1. For large crystal (without sonication), the crystal size is about 5.7 μm using DLS
2. Crystal with size smaller than 1 μm is desirable for fabrication of high quality mixed matrix
membrane with ideal morphology such as good filler/polymer adhesion and uniform distribution of
filler crystals in polymer matrix, thus sonochemical method is employed.
3. Due to slow reaction kinetics in conventional method, it takes a relatively long time, ultrasonic
radiation can increase the rate of reaction such that it can be completed within 2 hours
4. Peak broadening in submicron crystal is observed due to their smaller crystallites
5. In TGA, sonochemically synthesized submicron crystals exhibit similar thermal stability with bulk
crystal, which started to decompose at around 150 oC in air. Initial loss below 150 oC is possibly due
to evaporation of solvents in the pores of Zn(pyrz)2(SiF6) crystal
6. Excellent CO2 adsorption capacity at low CO2 partial pressure, which makes it suitable for
fabrication under low pressure range

Fabrication of MMM
1. Sieve-in-a-cage morphology has been frequently observed due to poor compatibility between two
phases for zeolite-polymer composite membrane
2. Good affinity of the organic ligand in the framework to the PEO chain possess a high mobility at
room temperature
3. For bulk crystal, majority of the crystals were located at the bottom of the membrane, which is
due to crystal settled down during the membrane fabrication.
4. For submicron crystal, clusters could be possibly formed in the polymer matrix, and uniform
distribution of crystal in the matrix is observed due to the submicron crystal were overall effectively
stabilized by the surrounding PEO chains in monomeric solution

Gas Permeation Properties in MMM

1. Improvement in gas separation properties of MMM is observed, due to the selective
adsorption/transport of CO2 through the pores of the crystal
2. N2 and CH4 were hindered by the MOF crystal which decreases its permeability

Prediction
1. Using other membranes such as polyimides based 6FDA-type membrane. However, owing to the
crystalline nature of polyimide, the polymer/filler adhesion property should be carefully controlled
to realize such performance.
ZIF Review

A. Introduction
1. Zeolitic Imidazolate Framework
a) Sub-class of MOFs which are typically similar to zeolites
b) Tetrahedrally coordinated transition metal ions (e.g. Fe, Co, Cu, Zn) connected by organic
imidazole linkers (Im = C3N2H3-) via coordination bond by nitrogen atoms in the 1,3-position of the
imidazolate ligands
c) Bond angle of M-Im-M is similar to the Si-O-Si bond angle (145o) in zeolites
d) ZIF is porous, flexible, chemically and thermally stable crystals (up to 400 oC), which are promising
material for gas separation and storage
e) It is also suitable as size- and shape-selective catalysis due to their pore size (< 5 Å)
f) Their surface area is similar to that of very porous MOFs and it is attributed to the full exposition
of imidazolate-based ligand edges and faces
g) ZIFs also show framework flexibility with respect to gas adsorption and stable under harsh
conditions such as refluxing with organic solvents, water and aqueous alkaline solution.

2. Important features in ZIF membrane synthesis:

General properties:
a) Pore continuity (interconnectivity)
b) Defect-free structure
c) Good adherence to the substrate surface

Effect of substrate
a) Synthesis of ZIF membrane with ceramic support is the most commonly used type of substrate
b) Ceramic support (α-alumina, titania, YSC, ZnO, SiO2) exhibit excellent mechanical and thermal
stability, which permit their use in processes that are carried out at high temperature
c) Titania: promote heterogeneous nucleation but it is too expensive and brittle (easily broken in real
gas separation); α-alumina: excellent mechanical stability, which is the most preferred type of
substrate. Some studies have conducted for support that combines the mechanical stability of α-
alumina and the smooth layer of titania.
d) Surface modification: α-alumina is modified with ZIF organic ligands, polymer or ZnO layer which
function as the source of the metal cation. ZIF have also been grown on the polymeric support such
as porous nylon, porous polyethersulfone and Trolon because the interaction between the
polymeric support and organic ligand can be enhanced

Effect of surface modification

a) Heterogenous nucleation is usually difficult, thus surface modification is required
b) Example: 3-aminopropyltriethoxylsilane (APTES) is used to modify ceramic substrates to act as the
binder between membrane layer and support for ZIF-22.
c) Ethoxy group of APTES react with the surface hydroxyl groups of the Al2O3 support, which it can
acts as a covalent linkers
d) ZnO was deposited on a tubular surface to act as an Zn2+ source so as to provide a smooth support
layer to promote homogeneous nucleation
Effect of deprotonators
a) Base are included into the membrane to increase solution pH and thus leads to complete
deprotonation of imidazole-based ligands. This permits the growth of ZIF membrane in all directions
b) Sodium formate (HCOONa) as deprotonator: Sodium formate and zinc salt formed a ZnO layer on
α-alumina substrate that acts as heterogeneous nucleation sites for ZIF-8 crystallization and an
additional Zn source. After heterogeneous nucleation, sodium formate serves as a deprotonator to
obtain well-grown ZIF-8 membrane
c) Ammonium hydroxide is used to promote deprotonation of 2-methylimidazole and promote
nucleation in ZIF-8 membrane
d) Polyethyleneimine (PEI) promotes linkage between the seeds and the support as well as to
deprotonate the organic ligand, as PEI has amino groups in its structure

Effect of solvents
a) Synthesis of ZIF membrane is mainly from dimethylformamide (DMF), methanol and water
b) Use of cost-effective and benign solvents such as water is preferred for health and economical
reason, but only ZIF-8 can be synthesized successfully with water
c) Smaller solvent molecule corresponds to easier activation and more ZIF structural integrity can be
preserved
d) Water helps to promote the deprotonation of organic ligand, for example in ZIF-8 synthesis, 2-
methylimidazole exhibit higher degree of deprotonation in water than in organic solvent

Effect of activation
a) Removal of occluded solvent molecules from ZIF structure, which is usually done with solvent
exchange with a solvent of smaller molecular size (e.g. methanol)
b) However, if pure methanol is used straight away as the solvent exchange unit, the concentration
gradient will be too high where it will cause the damage in ZIF structure and poor gas separation
performance
c) Thus, there is a need to introduce a mixture (e.g. ZMF-methanol solutions at different
compositions) for the activation of the membrane to decrease the diffusion rate of DMF. The
composition of methanol in the activation solution can be increased successively until pure
methanol is used at the end of the activation process. Drying is conducted after solvent exchange,
which it is much easier with more volatile solvent
d) Method to reduce the amount of occluded solvent is constantly sought after as it will lead to
easier activation and preserve high quality of ZIF membrane

Chemical and thermal stability

a) ZIF-69 was stable under boiling methanol, benzene and supercritical CO2 but not stable in boiling
water
b) ZIF-90 and APTES-functionalized ZIF-90 shows an excellent thermal and hydrothermal stability
with outstanding separation performance
c) ZIF-95 also shows high hydrothermal stability
d) Identification of extreme temperature conditions in which the membranes can operate is
important as most of the exhaust or flue gases to be treated, separated or enriched from industrial
processes are present at high temperatures. This ensures reliability and reproducibility in the
separation performance of ZIF membrane
Effect of functionalization
a) Membrane with rigid structures are preferred for the membrane synthesis so that the pore size
can be remained unchanged
b) Post-synthetic modification and functionalization can be done via imine and APTES
functionalization

Configuration
a) ZIF membranes have been successfully synthesized on ceramic and polymeric support.
b) However, tubular configurations are necessary for industrial applications because of their
robustness, high mechanical strength, high flux rates, extended shelf life and ability to be easily
backwashed.
c) ZIF membranes on tubular support is expected to become a more frequently researched topic in
laboratories and pilot plant settings prior to their actual deployment in industrial applications

Reproducibility
a) Producing ZIF membranes with consistent performance and predictable characteristics is still
challenging
b) Reproducibility is achievable for ZIF membranes but a methodology that guarantees consistently
high performance is still being researched

3. Classification of ZIF membrane synthesis

In-situ growth method
a) Growth of ZIF membrane on porous support that does not contain any crystals attached (seeded)
to its surface
b) After sufficient time is given at elevated temperature, nucleation begins to proceed where ZIF
starts to grow on the support and the membrane is eventually formed.
c) Nucleation, growth and intergrowth of crystals are not decoupled, occurring instead during the
same step for an extended period of time

In-situ growth on unmodified support

a) Challenging because nucleation is hard to achieve and ZIF membrane and support interaction is
usually poor
b) Microwave heating is used to facilitate nucleation and reduce the synthesis time to 4 h or less
(example: ZIF-8 membrane on titania support using methanol as solvent)
c) ZIF-69 on α-alumina substrates for CO2/CO separation are stable under boiling methanol, benzene
and supercritical CO2 but not stable under boiling water
d) Sodium formate in ZIF-8 membrane act as an enhancer of heterogeneous nucleation and
deprotonation
e) In situ synthesis of ZIF-8 membranes on α-alumina by contra-diffusion, which is achieved by
immersing the substrates in a zinc metal solution followed by immersion in a solution containing the
ligand (2-methylimidazolate) and sodium formate

In-situ growth on modified support

a) Surface modification to increase heterogeneous nucleation between ZIF crystal and substrate
b) Modification with an organic ligand prior to ZIF membrane synthesis (e.g. methanolic solution of
an organic linker on the α-alumina disk substrate enhance ZIF crystal intergrowth with the substrate
after heating at 200 oC for 2 hr
c) In-situ synthesis of ZIF-22 membranes on APTES modified TiO2 disk substrate results in molecular
sieving characteristics with pore aperture size of 0.30 nm, relatively high hydrogen permeability and
favourable selectivity
d) APTES is shown to work as a linker between substrate and ZIF crystal, which promote the
nucleation growth of ZIF, which it becomes hydrothermally stable and exhibited excellent separation
performance (e.g. H2/CH4 gas mixtures)
e) Substrate modification can be achieved as well on tubular support

Secondary Growth
a) ZIF membranes on supports that contain attached seeding crystals (which the seeding crystals is
attached by means of physical or chemical treatment.
b) Crystal nucleation, growth and intergrowth do not occur simultaneously in secondary growth
(independent of substrate)
c) ZIF membrane synthesis using secondary growth with prior seeding is accomplished via rubbing,
dip-coating, slip-coating, electrospinning and microwave radiation

Secondary Growth with physically attached seeds

a) Crystals are attached by manual rubbing (by repeatedly applying pressure onto the substrate
surface so as to obtain a smooth surface) or electro-spinning (using high-voltage electric charge to
draw a seed from a syringe containing the seed solution to induce surface charge)
b) Electrospinning has been used to produce ZIF_8 from polyvinylpyrrolidone containing seed
crystals followed by secondary growth under solvothermal conditions

Secondary Growth with chemically attached seeds

a) Seeding techniques are conducted such as dip-coating, slip-coating, thermal seeding, reactive
seeding and microwave-induced thermal deposition (MITD)

Innovative Techniques
Innovations that are related to the preparation of ZIF membrane

Post-synthetic modification
a) Control of pore aperture size of ZIF structures to increase gas separation performance
(constricting the pore aperture size or by reducing defects) or to create active catalytic sites.
However, such action may reduce the pore aperture size and decrease permeability of gases.
b) This modification reduce intercrystalline defects (gate-opening effect can be prevented) as well as
improve in thermal and hydrothermal stability
c) Examples: imine-functionalization of ZIF-90 and APTES-ZIF-90 shows an increased in gas
separation performance

Rapid Thermal Deposition (RTD)

a)