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Article
Modulated UiO–66 based Mixed Matrix Membranes for CO2 Separation
M. Waqas Anjum, Frederik Vermoortele, Asim Laeeq Khan,
Bart Bueken, Dirk E. De Vos, and Ivo F. J. Vankelecom
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b08964 • Publication Date (Web): 12 Oct 2015
Downloaded from http://pubs.acs.org on October 16, 2015

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5 Modulated UiO-66 based Mixed Matrix Membranes for CO2 Separation
6 *
7 M. Waqas Anjuma, Frederik Vermoortele a, Asim Laeeq Khanb, Bart Bueken a, Dirk E. De Vos a, Ivo F.J. Vankelecom a
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a
9 Centre for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, KU Leuven, Kasteelpark Arenberg 23, Box
10 2461, 3001 Leuven, Belgium.
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b
12 Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Pakistan.
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14 *Corresponding author. Tel.: +32 16 321594; fax: +32 16 321998.
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16 *E-mail address: ivo.vankelecom@biw.kuleuven.be (I.F.J. Vankelecom).
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20 Abstract:
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23 Mixed matrix membranes (MMMs) composed of polyimide (PI) and metal-organic frameworks
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(MOFs) were synthesized using Matrimid® as polymer and Zr-terephthalate UiO-66 as filler. The
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26 modulation approach, combined with the use of amine-functionalised linkers, was used for the synthesis
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28 of the MOF fillers in order to enhance the intrinsic separation performance of the MOF and improve the
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30 particle-PI compatibility. The presence of amine groups on the MOF outer surface either introduced
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32 through the linker or through the modulator or through both, led to covalent linking between the fillers
33 and the Matrimid®, which resulted in very stable membranes. In addition, the presence of amine groups
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35 inside the pores of the MOFs and the presence of linker vacancies inside the MOFs, positively influenced
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37 CO2 transport. MMMs with 30 wt% loading showed excellent separation performance for CO2/CH4
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39 mixtures. A significant increase in mixed gas selectivity (47.7) and permeability (19.4 Barrer) compared
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to the unfilled Matrimid membrane (i.e. 50% more selective and 540% more permeable) was thus
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42 achieved for the MMM containing the MOF prepared from 2-aminoterephthalic acid and 4-aminobenzoic
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44 acid, respectively used as linker and as modulator.
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Keywords: CO2/CH4 separation, Modulated MOFs, Mixed matrix membranes, UiO-66, Gas separation
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1. Introduction
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5 Biogas and natural gas are major resources for which CO2 removal is mostly required.
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7 Conventionally, CO2 is removed from gas mixtures by cryogenic distillation or amine-based wet
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9 scrubbing. These methods however have serious environmental drawbacks because of their high energy
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demands.1,2 Membrane separation technology has gained great attention over the past years as an
12 alternative to these conventional industrial processes because it offers a simple continuous process with
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14 low cost and energy requirements.3,4
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16 Extensive efforts have focused on enhancing the gas separation properties, i.e. selectivity and
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18 permeability, of polymeric membranes. Besides synthesizing new polymeric materials or the
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development of post-treatment procedures of the membranes via thermal rearrangement or crosslinking,
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21 one of the most promising alternatives are mixed matrix membranes (MMMs), which combine the
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23 mechanical properties and processability of polymeric materials with the selective properties of well
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25 selected fillers.5 A wide variety of inorganic and organic porous materials,6 such as zeolites,7,8 carbon
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molecular sieves,9 silica,10,11 activated carbons and carbon nanotubes12 have been used as fillers in
28 MMMs. Despite the many reports of improved separation and transport properties in MMMs,13 there are
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30 still technical challenges to be met with MMMs, since the fillers usually do not have a good interfacial
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32 compatibility with the polymer matrix, thus leaving non-selective pathways.14,15 Glassy polymers in
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34 particular do not adhere well to the particle surface. This problem becomes more critical at higher filler
35 loadings.16,17 To solve this problem, different approaches have been explored, including variation in
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37 particle shape and size of the fillers and their surface modifications, as for instance commonly applied in
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39 the past for zeolites18,19 and very recently also for MOFs.20
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41 MOFs are synthesized from metals ions and polyfunctional organic linkers, creating a porous
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material which is highly suitable for separation.21 Their modular build-up offers an unprecedented
44 flexibility of structural fine-tuning by varying the inorganic or organic building unit. Moreover, their pore
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46 systems can be rationally tailored for CO2 selective adsorption.22 A lot of MOF structures have been
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48 developed with great performance in gas separations.23–27 Because of their high separation performance,
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50 these materials were more recently used as fillers in MMMs, e.g. Matrimid® was filled with MOF-5,28
51 [Cu3(BTC)2],16,29 Cu-BPY-HFS,30 and MIL-53(Al)16 while Cu-TPA was incorporated in polyvinyl
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53 acetate30 and in 6FDA-ODA-DAM31. A lot of research is currently focused on obtaining better gas
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55 separation results with MOF based MMMs.32
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In this work, MMMs composed of polyimide (PI) and metal-organic frameworks (MOFs) are
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5 investigated, using the well-known Zr-terephthalate MOF UiO-66. UiO-66 [Zr6O4(OH)4(O2C–C6H4–
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7 CO2)6] is composed of Zr6O4(OH)4 clusters, linked to 12 terephthalate ligands. It is built up as a 3D-
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9 network comprising octahedral and tetrahedral cages in a 1:2 ratio, which are interconnected by
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triangular windows with a diameter of 6Å.33 Computational and experimental work has indicated that
12 these materials have a good performance in CO2/CH4 separation34–36, highly depending on the
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14 substituents on the organic linker. However, 6FDA–ODA membranes containing amine-functionalized
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16 UiO-66 (NH2-UiO-66) showed only a 7% increase in selectivity combined with even a 5% decrease in
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18 pure CO2 permeability, among others due to poor polymer-filler interface properties.37 Very recently, it
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was also shown that appropriate choice of the surface organic moiety of a MOF can enhance the chances
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21 of getting defect-free MMMs. UiO-66 was functionalized with phenyl acetyl groups, which interacted
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23 favorably with the imide groups in the polymer (Matrimid®) through hydrogen bonding and π-stacking.
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25 The MMMs showed increased ideal gas (CO2/N2) selectivity (by 25%) and CO2 permeability (by 200%)
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compared to the unfilled Matrimid®.18 In a recent study, the mesoporosity of Mil-101(Cr) was tuned by
28 impregnating it with poyethylenimine (PEI) in order to enhance CO2 transport. These functionalized
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30 fillers, when embedded into sulfonated poly(ether ether ketone) (SPEEK) matrix and measured in
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32 hydrated environment, increased the mixed gas (CO2/CH4) selectivity by 128% and CO2 permeability by
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34 260% compared to unfilled SPEEK membrane at 40 wt % loading and 10 bar operating pressure. This
35 was attributed to the hydrogen bonding between the sulfonic acid groups and the abundantly available
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37 PEI resulting into good filler-polymer interface compatibility, in addition to an increased amount of
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39 facilitated transport interaction sites for CO2.38
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41 In computational studies, an increased adsorption selectivity of NH2-UiO-66 for CO2 over CH4
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has been reported.39,40 Grafting polar functional groups (–Br, –NH2, –NO2, –(CF3)2, –(OH)2, –SO3H, –
44 CO2H) on the organic linkers has in general been considered as one of the best techniques to enhance
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46 CO2 separations from gases using MOFs.34,36
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48 Modulation of MOFs is a rather new technique through which the internal MOF structure, as well
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50 as the crystal size, particle morphology and outer surface functionalities can be controlled by using
51 monodentate ligands during the synthesis of the material.41 The modulators then compete with the
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53 conventional multidentate ligands for coordination to the metal cations.42 The surface of the particles can
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55 then be tuned better for a desired application, as monodispersed particles can thus be obtained which are
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57 capped by the modulator molecules.43
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The modulation approach was here used to increase the affinity of the fillers for the Matrimid®
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5 matrix, thus reducing the chances for leaks along the crystal-membrane interphase in the composite
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7 membrane. Furthermore, the presence of amine groups on the modulators can create a chemical reaction
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9 between the MOF outer surface and the imide group of the PI, resulting in chemically more stable
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11 membranes that suffer less from plasticization.44,45,46 Moreover, the presence of amine groups on the pore
12 walls via the modulator and/or by using amine-functional linkers, is also expected to increase the
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14 interaction with CO2, and thus create more selective fillers for the CO2/CH4 gas separation. Finally, the
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16 less restricted pores and uncoordinated metal sited obtained by modulation due to the formation of linker
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18 vacancies inside the MOF, can further enhance respectively CO2 diffusion and selectivity through the
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MMMs.47 Matrimid® was chosen as PI because it is an excellent polymer for this type of gas separations
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21 with good mechanical properties and easy availability.7,40
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25 2. Experimental
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28 2.1. Materials
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Polyimide (Matrimid® 9725) was kindly provided by Huntsman (Switzerland). Trichloromethane
31 (chloroform) was supplied by Acros. CO2, CH4 and N2 gases were supplied by Air Liquide (Belgium).
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33 ZrCl4 (99.95%) was purchased from ABCR, while N,N-dimethylformamide (DMF) (extra pure),
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35 terephthalic acid (98%), benzoic acid (98%), 2-aminoterephthalic acid (98%) and 4-aminobenzoic acid
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37 (ABA) (99%) were supplied by Sigma-Aldrich and hydrochloric acid (HCl) (37wt% solution in water) by
38 Fischer.
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40 2.2. Preparation of MOFs
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43 In a typical synthesis, 6.4 g of ZrCl4 and 4.6 g of terephthalic acid were dissolved in 300 ml DMF.
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45 HCl was added as crystallizing agent (2.75 ml), and BA or ABA were added as modulators in a 50/1
46 molar ratio relative to the linker. This synthesis mixture was heated at 120 °C for 24 h, during which the
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48 MOF precipitates as a microcrystalline powder. Replacement of terephthalic acid by 2-aminoterephthalic
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50 acid (5 g) in the same synthesis gave highly crystalline NH2-UiO-66. The detailed synthesis procedure is
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52 described elsewhere.47,48 Following these procedures, the MOFs were synthesized as shown in Table 1.
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Table 1: Details of as-synthesized MOFs
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6 MOF Linker Modulator
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8 UiO-66 BDC -
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10 UiO-66-BA BDC BA
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UiO-66-ABA BDC ABA
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15 NH2-UiO-66-BA NH2-BDC BA
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17 NH2-UiO-66-ABA NH2-BDC ABA
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21 2.3. Preparation of unfilled polymeric membrane
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23 Matrimid® was dried at 110 °C overnight in an oven and then dissolved in chloroform and stirred for
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25 24 h to form a 6.3 % (w/w) viscous solution. The solution was cast onto a flat petri dish which was then
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27 covered with an inverted funnel (10.5 cm in diameter and 16 cm in height) fully wrapped with aluminum
28 foil in order to control the evaporation rate of the solvent at room temperature for at least 24 h in a N2
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30 bag. The resulting film was transferred to an oven at 40 °C after which the temperature was raised at a
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32 rate of 20 °C/h to 270 °C which was kept constant for 6 h and then slowly cooled down to room
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34 temperature. At least 3 circular coupons of 2.24 cm2 (with an effective area of 1.54 cm2 during
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permeation) were cut from the prepared membranes and used for gas permeation experiments.
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37 2.4.Preparation of MMMs
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39 All membranes were synthesized in a N2 filled bag to avoid any chance of phase inversion of
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41 Matrimid® due to humidity, which could lead to defects in the membranes.49,50 The MMMs were
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prepared using a priming protocol.13 Matrimid® and the MOFs were dried overnight at 110 °C and 150
44 °C respectively. 30 wt% suspensions of all MOFs were prepared by solution blending with chloroform,
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46 as determined by equation (1).
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48 ( ) [ ] (1)
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52 The required amount of filler was first added in half the amount of total required solvent, and stirred
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54 for a few hours at room temperature to allow uniform dispersion. The required amount of polymer was
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56 added to the rest of the solvent and stirred for at least 6 h at 40 °C to make a homogeneous solution.
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Then, 20% of the total amount of this polymer solution was slowly added to the MOF suspension in a N2
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gas filled bag by using a priming technique. Priming of the MOF particle solution with the polymer
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5 solution before the addition of the bulk polymer reduces the stress at the particle-polymer interface.14 The
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7 solutions (MOF + 20% polymer + solvent) were stirred for 4 h, followed by addition of 30% of the total
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9 polymer into the solution and stirring for another 2 h. This step was repeated until the total amount of
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polymer was added. Before every addition, the solution (MOF + polymer) was sonicated for 20 min.
12 After the final additions, the solutions were stirred for another 24 h. To adequately disperse the MOF
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14 particles in the Matrimid® matrix, the suspensions used for the MMM preparation were stirred and
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16 sonicated for at least 2 min each to achieve homogeneous suspensions. From onward, the preparation
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18 procedure for the MMMs was similar to the pure polymer membrane preparation described above, except
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that the MMMs were annealed at 170 °C due to presence of amine groups in MMM structures.
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22 3. Characterization
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25 The glass transition temperature (Tg) of the membranes pre-dried at 120 °C was measured using a TA
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27 instrument DSCQ1000 at a heating rate of 10 °C/min under a flow of N2 gas. The membrane morphology
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29 was analyzed using scanning electron microscopy (SEM Philips XL30 FEG) in order to examine the
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31 particle morphologies and the dispersion of the filler particles in the PI matrix. Membrane cross-sections
32 were obtained by breaking dry membranes frozen in liquid nitrogen. Prior to analysis, a gold film was
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34 sputtered onto the samples. The mechanical strength of the membranes was studied using a dynamic
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36 mechanical analyzer (DMAQ800) at room temperature. Slabs of the selected membranes (length = 10.5
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38 mm, width = 5 mm, thickness = 70 to 100 µm) were measured. Elemental analysis was conducted by
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using Vario Max CN of Elementar (measurements based on Dumas method). An ALPHA Bruker ATR-
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41 FTIR spectrometer was used to investigate the crosslinking of NH2-bearing MOFs with Matrimid®. The
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43 nitrogen sorption isotherms were measured with a Coulter 100 Gas Sorption analyzer (US) in order to
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45 determine the BET surface areas. Prior to the measurements, the samples were outgassed at 100 °C under
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vacuum for 10 h. The nitrogen sorption data were recorded at 77 K. The Brunauer-Emmet-Teller (BET)
48 method was used to obtain surface areas from the isotherms. Powder X-ray diffraction (XRD) patterns
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50 were recorded on a STOE STADI P COMBI diffractometer with an image plate position sensitive
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52 detector (IP PSD) in the 2θ region from 5° to 60°, with internal resolution of 0.03° and counting time of
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54 1200 s. The measurements were performed in transmission mode at room temperature using CuKα1
55 radiation with λ = 1.54056 Å selected by means of a Ge (111) monochromator.
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3.1. Gas permeability
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6 The gas permeation experiments were carried out by using a high-throughput gas separation (HTGS)
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8 membrane system (HTML, Belgium) set-up, described elsewhere.51 Pure CO2 and mixed gas selectivity
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10 and permeability values were measured. The equipment can simultaneously measure gas permeance and
11 selectivity of 16 membrane coupons using variable feed compositions, pressures and temperatures. The
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13 composition of the permeates was analyzed by a compact gas chromatograph (CGC, Interscience) and
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15 subsequently the sample loop was swept by a vacuum pump (Pfeiffer Dua 2.5).
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17 Prior to the measurements, the module was evacuated by a vacuum pump for almost 3 h to
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remove residual gases. The gas mixture was then fed into the module at a rate of 1 l/min, controlled by
20 mass flow controllers (MFC, Bronkhorst). The permeate was allowed to enter into the CGC by opening
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22 the 16 way-valve to determine the selectivity. The gas permeance was measured using a constant volume
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24 auxiliary cylinder (maximum measurement limit of 10 mbar) connected to a MKS Baratron® pressure
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26 transducer. The upstream pressure was adjusted by a back-pressure regulator mounted on the purge line.
27 For gas permeability determinations, the valve between the auxiliary cylinder and the vacuum
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29 pump was closed and the permeate was sent to an auxiliary cylinder for expansion by opening a three-
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31 way valve to measure the rate of increase in pressure with respect to time (dP/dt) until it reached steady-
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33 state. The mixed gas permeability was calculated by using the constant volume method described above
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and is given by the equation (2).
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37 ( ) ( )
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where V is the downstream volume (cm3) and A the membrane permeation area (cm2), P1 is the pressure
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43 the steady rate of pressure increase in the downstream side in torr/sec. Mole fractions of component i in
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45 the downstream and upstream are designated by yi and xi respectively. The mixed-gas selectivity was
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47 calculated by the ratio of the mole fraction of the two gases downstream (y) and upstream (x) using
48 following equation (3):
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50 α i/j = (Y i / Y j) / (X i / X j) (3)
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52 where xi and xj are the mole fractions of components i and j in the upstream respectively, while yi and yj
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54 are the mole fractions of components i and j in the downstream, respectively.
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4. Results & discussion
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5 4.1. MOF particle characterization
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7 In Table 2, BET surface areas of the prepared MOFs are listed. The measured BET surface areas of UiO-
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9 66 and NH2-UiO-66 are 1080 m2/g and 940 m2/g, respectively, indicating the high porosity of both
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materials. The surface area of the NH2- modified and of the modulated MOFs are, to some extent,
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15 Table 2: Properties of as-synthesized MOF particles
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MOF BET surface area Vmicropore a Elemental analysis of Particles (%)
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19 (m²/g) cm /g
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N C Zr
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22 UiO-66 1080 0.29 - - -
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24 UiO-66-BA 1147 0.55 1 33.11 28.54
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UiO-66-ABA 800 0.27 2.54 34.91 25.43
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27 NH2-UiO-66 940 0.26 2.77 33.92 22.51
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29 NH2-UiO-66-BA 892 0.25 4.32 24.77 26.60
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31 NH2-UiO-66-ABA 873 0.23 5.93 28.98 24.28
32 a
33 calculated by t-plot method
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36 lower in agreement with reported data and ascribed to synthesis precursors that are left behind in the
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MOF structure.37,52 Only UiO-66 modulated with benzoic acid (UiO-66-BA) has a slightly higher surface
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39 area than UiO-66.48 The SEM pictures (Fig 1) show that the crystal size did not change substantially with
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41 modulation. A narrow crystal size distribution can be observed for all synthesized MOF particles ranging
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43 between 100-200 nm. Some limited aggregation of NH2-UiO-66-ABA MOF particles seems present.
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45 XRD analysis was carried out to verify the crystalline structure and phase purity of the synthesized
46 MOFs. NH2-UiO-66 was expected to have a diffraction pattern similar to that of the conventional UiO-66
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48 MOF material. Fig. 2 shows the powder diffraction pattern of the MOFs, which are all similar to XRD
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50 patterns in literature.33
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(e) NH2-UiO-66-BA, (f) NH2-UiO-66-ABA
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4.2.MMM characterization
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24 The average thickness of these membranes was 70-100 µm and the physical appearance of these
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26 membranes is shown in Fig.3. The SEM images of the MMMs in Fig. 4 show the cross-section of the
27 MOF filled MMMs at 30 wt% loading. All membranes show a uniform MOF dispersion in the polymer
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29 matrix. There is no significant void formation visible around the incorporated fillers.
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46 Fig. 2: Powder X-Ray diffractograms of the as-synthesized MOFs
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49 The fillers also show very little agglomeration, confirming the good interaction between filler and
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51 polymer matrix. The concentric cavities in the MMMs are an indication of a strong interfacial interaction
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53 between the modulated fillers and the polymer matrix (Fig. 4).16,53 While preparing the MMMs, it
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became even visually clear that probe sonication of the solution prior to casting the membranes in the
56 petri dish was essential to accomplish such nice distribution. All membranes were also found to be
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14 Fig. 3: View of selected membranes prepared in petri dishes: (left) NH2-UiO-66-ABA, (right) UiO-66-BA
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17 flexible enough for easy handling and use in permeability measurements, even at the relatively high
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19 loading of 30 wt%. This good particle-polymer interaction is attributed to the hybrid nature of the MOFs
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21 and especially to the precise control over the outer surface of the MOF (in this case via benzoate phenyl
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and/or pendant amine groups). The amine groups might even lead to the covalent linking with the PI-
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24 chains.54,55 With windows of around 6Å in the MOF-structure, it is even additionally plausible for the PI
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26 chains to, at least partially, intrude into the MOF-pores and thus further enhance compatibility and
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28 interactions.
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Fig. 4. SEM images of cross-sections of Matrimid® membranes containing 30 % loading of (a) UiO-66, (b) UiO-
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66-BA, (c) UiO-66-ABA, (d) NH2-UiO-66, (e) NH2-UiO-66-BA, (f) NH2-UiO-66-ABA
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56 Table 3 shows the mechanical properties of the dense MOF-filled PI-membranes at 30 wt%
57 loading. It can be observed that the tensile strength of the MMMs is less than that of unfilled PI
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membranes and that the values of all MMMs are quite close to each other. This could be ascribed to the
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5 incorporation of fillers which act as stress concentrators and therefore, reduce the tensile strength with
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7 MOF loading. On the other hand, the Young’s modulus of the MMMs is higher than for the unfilled PI
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9 membrane, which confirms the good dispersion of the MOFs throughout the PI matrix, as well as a good
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interaction between the fillers and the PI matrix. Moreover, the incorporation of fillers in the polymer
12 matrix does not affect the crystalline nature of these fillers (Fig. 5), as confirmed via XRD.
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30 Fig. 5: X-ray diffractograms of the as-synthesized MOF/PI based MMMs with 30 wt% loading.
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32 The glass transition temperatures (Tg) of the MMMs are presented in Table 3. The increase in Tg
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34 of the MMMs upon incorporation of fillers further confirms an increased polymer chain rigidity upon
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36 MOF addition, thus again proving the good interactions between polymer matrix and filler.56
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Table 3: Mechanical properties and DSC (Tg) analysis of PI-based MMMs filled with MOF particles at
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40 30 wt% loading
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42 MOF filled MMM Tg Young’s modulus Tensile strength
43 (°C) (GPa) (MPa)
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45 Unfilled PI 302 2.31 93.5
46 UiO-66 319 2.94 65.7
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48 UiO-66-BA 323 2.91 61.5
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50 UiO-66-ABA 313 2.95 58.4
51 NH2-UiO-66 315 3.07 59.3
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53 NH2-UiO-66-BA 320 2.88 68.3
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NH2-UiO-66-ABA 321 3.06 56.1
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Chemical csross-linking is a common way to covalently link polymer chains. It reduces the
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5 plasticization of PI in the presence of highly soluble gases like CO2.57 In this regard, most research has
6
7 been done on PI using diamines as cross-linker.58,59 In this work, using MOFs that contain amino groups
8
9 as part of the linker or as modulator creates a chance for reaction with the imide groups of the polymer by
10
11
converting these into amides. ATR-FTIR spectra of MMMs are presented in Fig. 6. The bands at 1789
12 and 1713 cm−1 are assigned to the symmetric and asymmetric stretching of the C=O groups of the
13
14
polymer imide. The 1361 cm−1 absorption band is attributed to the C–N stretching of the imide 5-
15
16 membered ring of Matrimid®. The possible cross-linking can be confirmed via appearance of the amide
17
18 signals at 1534 (stretch of C–N and/or strong bend of N–H) and 1648 cm−1 (C=O stretch).45 However,
19
20 these peaks were not well pronounced in MMMs with 30 wt% loading. This might be due to the
21
22 relatively low concentration of formed amide groups between the MOF particles and the polymer matrix,
23
24 since only the amino groups at the outer surface of the MOFs can participate in these cross-linking
25
reactions. Keeping this in view, membranes with 50 wt% loading were fabricated to perform additional
26
27 ATR-FTIR spectra. The characteristic bands of the amide group (see grey area at 1538 cm-1 in Fig. 6) (see
28
29 dark grey area), thus confirming the link of the amino groups present on the surface of the MOF particles
30
31 with the Matrimid® matrix.59
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54 Fig. 6: Comparison of ATR-FTIR spectra between 3600 and 1100 cm−1 of the unfilled PI membrane and MMMs
55 containing 50 wt% MOF.
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4.3.Gas separation
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5
6 The mixed gas permeabilities and selectivities for all membranes are shown in table 4. At least 3
7
8 membranes were tested per composition and at least 3 coupons from each membrane were prepared to
9
10 provide reliable data. The selectivity and permeability values of the unfilled polymer membrane (table 4,
11 entry 1) are in agreement with already reported results.10,57,60 The incorporation of all fillers resulted in
12
13 both better permeation rates and separation factors (table 4, entry 1 vs 2-7). Such increase in permeability
14
15 accompanied by an increase in selectivity using binary gas feeds proves that the membranes are defect-
16
17 free and that the filler-polymer combination was well chosen. All CO2 permeabilities at least double
18
19
compared to the unfilled reference membrane, indicating that UiO-66 incorporation thus generally leads
20 to a faster diffusion of the gas molecules due to the introduction of large permanent pores in the
21
22 membranes, providing easy passage for the penetrant gases. The presence of the linker –NH2 group
23
24 increases the selectivity of the MMMs, as attributed to the dipole-quadrupole interaction with CO2, but
25
26 not with CH4. As recently reported, 37 the use of an NH2-functionalised linker instead of the conventional
27 terephthalic acid during MOF-synthesis (table 4, entry 2 vs 5) indeed increases the MMM selectivity and
28
29 permeability, even though the impact does not surpass the statistical error for this data set.
30
31
32
33
34
Table 4: CO2/CH4 mixed gas separation data for synthesized MOFs-based MMMs with 30 wt% loading
35
36 b c
Entry Membrane αCO2:CH4 P * PCO2
37
38 1 Unfilled PI 31.2 ± 1.1 3.5 ± 0.7 5.9 ± 1.5
39
40 2 PI + UiO-66 35.8 ± 1.5 8.1 ± 0.7 15.7 ± 1.6
41 3 PI + UiO-66-BA 42.9 ± 1.3 9.1 ± 0.8 17.8 ± 1.7
42
43 4 PI + UiO-66-ABA 45.1 ± 1.5 7.0 ± 1.2 13.6 ± 2.3
44 5 PI + NH2-UiO-66 37.3 ± 1.3 9.2 ± 0.9 17.8 ± 1.8
45
46 6 PI + NH2-UiO-66-BA 39.3 ± 1.4 8.9 ± 1.2 17.4 ± 2.3
47 7 PI + NH2-UiO-66-ABA 47.7 ± 1.3 19.4 ± 1.0 38.0 ± 2.2
48 a
49 Standard experimental conditions: upstream pressure = 9 bar, downstream= vacuum, operating temperature = 308 K, as feed= CO2/CH4 (50/50) vol %
b
50 Mixed gas permeability expressed in Barrer
c
51 Obtained by multiplying the mixed gas permeability (in Barrer) with the factor (yCO2/xCO2), where “x” is the mole fraction of CO2 in feed and “y” is the mole
52 fraction of CO2 gas in permeate61
53
54 With respect to modulation, MMM(UiO-66-BA) showed a 20% higher selectivity than
55 MMM(UiO-66) (table 4, entry 3 vs 2 ), due to an improved adhesion of the polymer phase to the filler.
56
57 Also, a relatively more crystalline structure of the MOF is generally obtained via a better controlled
58
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nucleation rate.41 The same effect of BA-modulation (15% more selective) can also be observed by
4
5 comparing MMM(NH2-UiO-66-BA) with MMM(NH2-UiO-66), both containing amino groups on their
6
7 linkers (table 4, entry 6 vs 5). Modulated MOF based MMMs thus generally show an increased CO2
8
9 selectivity over CH4, while they have comparable or higher permeability values than non-modulated
10
11
MOFs in MMMs. The increase in permeability might be attributed to the excess free space in the MOFs
12 created by the modulation, as linker are only fixed to one metal ion. In addition, the better performance of
13
14 MMMs with modulated MOFs can be due to the missing metal coordination inside the MOF structure62
15
16 which could lead to increased CO2-metal interactions.63,64
17
18
19
Finally, the combination of an amine-functionalised modulator and an amine-functionalised
20 linker, by far results in the best performance of all MMMs (over 50% more selective and 540% more
21
22 permeable than the reference Matrimid® membrane and respectively 30% and 140% more selective and
23
24 permeable than the MMM based on the reference UiO-66). The modulation by amino benzoic acid
25
26 groups thus gives the best performance, attributed to the formation of defect-free membranes due to
27 strong -NH2 interactions with the polymer matrix, along with a higher gas permeability attributed to the
28
29 excess free space in the MOFs created by the modulation. In addition, the presence of amine groups
30
31 inside the pores of the MOFs (thanks to both the modulation and the use of amine-functionalised linkers)
32
33 and the presence of linker vacancies inside the MOFs, positively influenced CO2 transport through
34
35
MOFs. Even though the performance of MMMs depends strongly on the operating conditions, reported
36 values represent the best mixed gas separation performances under comparable conditions for CO2/CH4
37
38 achieved by UiO-66 based MMMs so far.
39
40 A broader comparison with literature on CO2/CH4 separations using MOF-based MMMs is given
41
42 in Table 5. Extremely high permeability and selectivity values were achieved when MIL-101 filled with
43 PEI was embedded into SPEEK and measured with hydrated mixed gas feeds.38 Although Matrimid®
44
45 based MMMs filled with ZIF-8 materials showed a very high as selectivity of 124 at 50 wt% loading, the
46
47 reported 40% standard deviation on this number show a significant lack in reliability.7 In addition, the
48
49 selectivity value is based in single gas permeations, which always overestimate real mixed gas
50
selectivities. The MMM containing MOF-5 reduced the ideal CO2/CH4 gas selectivity by 24 % due to a
51
52 poor dispersion of the fillers in the polymer matrix.28 Incorporation of Cu-BPY-HFS in Matrimid® led to
53
54 a remarkable decrease in mixed gas selectivity indicating defects in these MMMs.65 Higher permeability
55
56 values with slightly increased CO2/CH4 selectivities were observed using MIL-53 with Matrimid®, as
57
58
ascribed to the large pores in this MOF.66 Seoane et al. used MIL-53(Al) and MIL-101(Al) functionalized
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with amino groups in MMMs dispersed in fluorinated sulfone-containing copolyimides. In this
4
5 copolymer, the 6FDA-dianhydride part with the CF3 groups was substituted by 3,3´,4,4´-
6
7 diphenylsulfonetetracarboxylic dianydride. The NH2-MIL-101(Al) filled MMM showed a 20% increase
8
9 in ideal gas selectivity with reduced CO2 permeability, while the NH2-MIL-53 based MMM showed a
10
11
slight increase in selectivity at the expense of permeability.67 Nik et al. used amino functionalized MOFs
12 (NH2-MOF-199 and NH2-UiO-66) as fillers in 6FDA/ODA. The NH2-UiO-66 based MMM showed a 5%
13
14 increase in mixed gas selectivity at the expense of a 7% decrease in gas permeability compared to an
15
16 unfilled polymer membrane, attributed to the creation of a rigidified polymer at the filler/polymer
17
18 interface.37 From these results, it is clear that a good polymer-filler interaction and the correct tuning of
19
the MOF inner and outer structure has always been a major challenge for MMMs. The results presented
20
21 in this paper are clearly among the best selectivity/permeability combinations, especially when
22
23 considering the mixed gas data and use of readily available, cheap polymers.
24
25
26 Table 5: CO2/CH4 mixed gas separation data for MOF-based MMMs from literature (T = 35°C).
27
28 MOF Loading Polymer Upstream PCO2 Selectivity Ref.
29 (wt %) pressure (Barrer) CO2/CH4
30 (bar)
38
31 PEI-MIL-101 40 SPEEK 10 1800 HF 57.5HF
32 ZIF-8 50 Matrimid® 5218 3 13.0 124.9SG 7

33 MOF-5 30 ®
Matrimid 5218 2 20.2 44.7SG 28

34 68
Cu-BPY-HFS 30 Matrimid® 5218 4 10.4 25.5SG
35 ® SG 66
36 MIL-53 38 Matrimid 5218 2 51.0 47.0
69
37 NH2-MIL-53 (Al) 25 PSF Udel 1 6.2 46.0*
67
38 NH2-MIL-101 30 6FDA based PI 3 70.9 41.6SG
39 37
MOF-199 25 6FDA-ODA 10 21.8 50.7*
40 UiO-66 25 6FDA-ODA 10 50.4 42.3* 37

41 37
NH2-UiO-66 25 6FDA-ODA 10 13.7 44.7*
42 ®
NH2-UiO-66-ABA 30 Matrimid 9725 9 37.9 47.7* This
43 work
44 HF
Hydrated (saturated) feed gas mixture (30:70 mole%)
45 * Gas feed mixture (50:50 mol %)
46 SG
Single gas
47
48
49
5. Conclusions
50
51
52
MMMs with modulated MOFs were synthesized with 30 wt% loading and their performance for
53 CO2/CH4 separation was verified. Due to the combined effect of a modulated MOF synthesis and the use
54
55 of amine-functional linkers, high-performance MMMs were obtained with Matrimid® as base polymer
56
57 for CO2/CH4 mixed gas separations.
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All MMMs showed an increase in performance relative to the unfilled PI membrane. A significant
4
5 increase in mixed gas selectivity and permeability of the membrane with modulated NH2-UiO-66-ABA
6
7 as filler proved this filler to be a very good candidate for CO2/CH4 separations. The results show that
8
9 modulation is a very practical technique for the synthesis of MOF particles that have the capability to
10
11
increase the separation performance of MMMs by enhancing the surface interaction between filler and
12 the polymer matrix, as well as by increasing selectivities and diffusivities inside the filler.
13
14
15 Acknowledgements
16
17 We thank the financial support from the Flemish government (Methusalem - CASAS, Long term
18
19 structural funding), the Federal government IAP-PAI grant, IAP 7/05 FS2), the OT (11/061) and the
20 IDO-Research fund of the KU Leuven. B.B. would like to acknowledge the FWO Flanders for funding
21
22 (aspirant grant).
23
24
25
26 List of Abbreviations
27
28
29
6FDA 4,4′- (hexafluoroiso-propylidene) diphthalic anhydride
30 BDC Benzene-1,4-dicarboxylate
31 CGS compact gas chromatograph
32
Cu3(BTC)2 (BTC=benzene-1,3,5-tricarboxylate)
33
34 Cu-BPY-HFS Cu–4,4′-bipyridine–hexafluorosilicate
35 Cu-TPA Copper terephthalic acid
36 DAM 1,3,5-trimethyl-2,6-phenylenediamine
37
38 HTGS High throughput gas separation
39 MFC Mass flow controller
40 MIL Matériaux de l'Institut Lavoisier
41
42
MMM Mixed matrix membranes
43 MOF Metal organic framework
44 ODA oxidianiline
45 PEI Polyethylenimine
46
47 PI Polyimide
48 XRD X-ray diffraction
49 ZIF Zeolitic Imidazolate Framework
50
51
52
53
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