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Functional Inorganic Materials and Devices

All-Nanoporous Hybrid Membranes: Incorporating Zeolite Nanoparticles
and Nanosheets with Zeolitic Imidazolate Framework Matrices
Kiwon Eum, Shaowei Yang, Byunghyun Min, Chen Ma, Jeffrey H Drese, Yash Tamhankar, and Sankar Nair
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c06227 • Publication Date (Web): 28 May 2020
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All-Nanoporous Hybrid Membranes: Incorporating Zeolite Nanoparticles and
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9 Nanosheets with Zeolitic Imidazolate Framework Matrices
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13 Kiwon Eum1,‡,§, Shaowei Yang1,‡, Byunghyun Min1,‡, Chen Ma1, Jeffrey H. Drese2, Yash
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Tamhankar2, and Sankar Nair1,*
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19 School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA
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21 30332-0100, USA
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Phillips 66 Research Center, Phillips 66 Company, CPL-02-218, Highway 60 & 123,
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Bartlesville, OK 74003, USA
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30 These authors contributed equally.
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33 Present address: Department of Chemical Engineering, Soongsil University, Seoul, 156-743,
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35 Republic of Korea
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39 *Corresponding author: sankar.nair@chbe.gatech.edu
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45 KEYWORDS MOFs, zeolites, hybrid materials, membranes, separation
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3 ABSTRACT: Metal-organic framework (MOF) membranes have attractive molecular separation
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6 properties but require challenging thin film deposition techniques on expensive/specialty supports
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8 to obtain high performance levels relative to conventional polymer membranes. We demonstrate
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10 and analyze in detail the new concept of All-Nanoporous Hybrid Membranes (ANHMs), which
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combines two or more nanoporous materials of different morphologies into a single membrane
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15 without the use of any polymeric materials. This allows access to a previously accessible region
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17 of very high permeability and selectivity properties, a feature that also allows ANHMs to show
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high performance even when fabricated with simple coating and solvent evaporation methods on
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22 low-cost supports. We synthesize several types of ANHMs that combine the MOF material ZIF-8
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24 with the high-silica zeolite MFI (the latter being employed in both nanoparticle and nanosheet
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26 forms). We show that continuous ANHMs can be obtained with high (~50%) volume fractions of
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29 both MOF and zeolite components. Analysis of the multilayer microstructures of these ANHMs
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31 by multiple techniques allows estimation of the propylene/propane separation properties of
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33 individual ANHM layers, providing initial insight into the dramatically increased permeability and
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selectivity observed in ANHMs in relation to single-phase nanoporous membranes.
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39 INTRODUCTION
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42 Membrane-based processes are of great interest for conducting molecular separations with
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44 lower energy consumption and environmental impact.1 Conventional polymeric membranes are
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46 well known to face a fundamental trade-off between permeability and selectivity characteristics
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referred to as the ‘Robeson upper bound’ (shown schematically in Figure 1). To transcend this
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51 limitation, a number of approaches have emerged to construct hybrid or ‘mixed-matrix’
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53 membranes (MMMs), which incorporate higher-performance nanoporous materials such as metal-
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organic frameworks (MOFs) or zeolites in the polymeric membrane matrix in order to boost the
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3 membrane performance.2-5 However, this approach usually allows only a moderate increase in the
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6 membrane performance over the baseline polymeric membrane, whereas many pure nanoporous
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8 membranes have orders-of-magnitude higher performance characteristics than most polymers and
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10 polymer-nanoporous material MMMs (Figure 1). However, pure nanoporous membranes face a
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different challenge, namely the difficulty of facile and scalable fabrication of a large variety of
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15 membranes for different applications.6-8 Unlike polymeric membranes which can be fabricated in
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17 a rational manner with a vast range of polymer compositions, nanoporous membranes require
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specialized thin film crystallization, growth, or deposition techniques that vary greatly from one
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22 material to another.9–11
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26 In the last few years, the fabrication of membranes from nanoporous zeolitic imidazolate
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29 frameworks (ZIFs) - which are a large subclass of MOFs - have attracted much research attention.
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31 An important aspect of this work is the increasing ability to fabricate molecularly selective and
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33 thin (in many cases, submicron) ZIF membrane coatings. A number of methods have been
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developed recently to exploit the use of liquid, vapor, and solid phases, as well as electrochemical
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38 and electrophoretic techniques, for delivery of precursors (mainly Zn2+ metal ions and imidazolate
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40 linkers) and ZIF seeds to the membrane substrate, resulting ultimately in the formation of
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crystalline ZIF membrane coatings.12-29 The vast majority of the above work has focused on the
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45 material ZIF-8, which has been of particular interest for propylene/propane separations. Recently,
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47 we have introduced the concept of “all-nanoporous hybrid membranes” (abbreviated as AHNM in
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49 this work).30 The key idea of the ANHM concept is to fabricate hybrid or ‘mixed-matrix’
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52 membranes containing two (or more) nanoporous materials – and no polymeric materials – in the
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54 membrane layer. As depicted schematically in Figure 1, such ‘dual-phase’ or even ‘multi-phase’
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3 ANHMs allow us to access an entirely new range of permeability and selectivity characteristics
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6 that are not possible to achieve with single-phase materials (e.g., polymers, nanoporous materials)
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8 or polymer-based mixed-matrix membranes, thus allowing us to surpass previous “upper bounds”
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10 on membrane performance. The judicious selection of materials allows one to target increases in
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permeability, selectivity, or both properties as desired. In our first report of the ANHM concept,
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15 we showed that incorporation of only 13 vol% of zeolite MFI nanoparticles during growth of a
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17 ZIF-8 membrane led to a highly permeable ANHM which surpassed all previous “upper bounds”
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on propylene/propane performance characteristics.30 Furthermore, the expected enhancements in
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22 permeation properties could be estimated using the same kinds of modeling approaches (such as
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24 the Maxwell model and other related formulations) that are currently used for estimating the
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26 characteristics of conventional polymer-based MMMs.31
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31 The focus of the present paper is to further develop the ANHM concept through a more
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33 detailed study of their synthesis processes and their separation properties. The ZIF-8/MFI system
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offers an excellent initial basis for studying ANHMs due to the established procedures for ZIF-8
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38 membrane coatings and the well-established permeation properties of both materials, and is
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40 therefore used in this work. In particular, we generalize the fabrication of ZIF-8/MFI ANHMs to
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include both 3D MFI nanoparticles as well as 2D MFI nanosheets.32 Furthermore, we will focus
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45 on the use of direct evaporation-based conversion of ZIF-8 precursor solutions into ZIF-8
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47 membranes,33,34 since this approach has greater potential to yield thin membranes with minimal
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49 usage of solvents and precursors compared to full solvothermal growth of polycrystalline ZIF
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52 membranes from bulk liquid phases.13,23,25,35 While a number of studies already exist in the
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54 literature for optimizing synthesis techniques to produce ZIF-8 membranes, this work develops in
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3 detail a new way to dramatically enhancing the intrinsic properties of the membrane (permeability
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6 and selectivity) through the ANHM approach. However, this approach is certainly expected to be
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8 compatible with the existing methods for production of pure ZIF membranes, and could be used
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10 to dramatically boost their performance. Secondly, the ANHM approach can also be valuable in
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improving or simplifying the membrane synthesis process itself. The ideal ZIF membrane
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15 production process would involve a simple coating of the ZIF precursor solution and its
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17 evaporation-induced transformation to a membrane layer, on inexpensive and easily mass-
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produced substrate materials (e.g., a ceramic or polymer) whose pore structures or surfaces are not
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22 specially engineered or modified. However, existing approaches to ZIF membrane formation have
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24 often required the use of specialized or engineered substrates, whereas ZIF membranes made by
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26 simple coating processes on inexpensive substrates typically show poor selectivity.36–38 As we will
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29 show in this paper, the ANHM approach can also dramatically improve the quality of ZIF
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31 membranes even with use of a simple, non-engineered substrate material.
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RESULTS AND DISCUSSION
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39 ANHM Materials and Membrane Architectures
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41 The overall scheme of ZIF-8/MFI ANHM synthesis in this paper is depicted in Figure 2.
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43 The two nanoporous materials of interest in this work are shown in Figure 2a. The MOF material
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46 ZIF-8 is constructed from Zn2+ ions and 2-methylimidazole (2-MeIM) linkers. It has a 3D pore
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48 network with a nominal crystallographic limiting pore diameter of 0.35 nm. However, the
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50 rotational flexibility of the linkers surrounding the pore leads to a much larger effective pore size
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~0.42 nm.39,40 As a result, ZIF-8 can permeate propylene (C3H6, kinetic diameter 0.42 nm) with
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55 an intrinsic room-temperature permeability of ~300 Barrer (1 Barrer = 3.348×10-16 mol·m-1·s-1·Pa-
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), but greatly retards permeation of propane (C3H8, kinetic diameter 0.43 nm) to ~2 Barrer. For
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6 this reason, ZIF-8 is attractive for propylene/propane separation. On the other hand, the pure-silica
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8 (SiO2) MFI zeolite used in this work has much larger pores (~0.53 nm), with very high propylene
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10 permeability (>8000 Barrer) but nearly no selectivity over propane.30 For this study, MFI materials
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with two different morphologies were prepared: high-aspect-ratio (2D) MFI nanosheets32,41 and
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15 isotropic 3D MFI nanoparticles.42 Transmission electron microscopy (TEM) and High-resolution
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17 transmission electron microscopy (HRTEM) imaging (Figures 2b-2c) confirm the highly
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crystalline and nanoporous structure of both MFI materials. The crystal size distribution of MFI
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22 nanoparticles is obtained as 104±17 nm from the TEM images (Figure S1). Low-magnification
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24 TEM images of the exfoliated 2D MFI nanosheets confirm their thin flake-like morphology with
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26 100-200 nm lateral size. HRTEM imaging and fast Fourier transform (FFT) analysis confirm the
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29 highly ordered MFI nanopores and the high crystallinity. Powder X-ray diffraction (PXRD, Figure
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31 3a-d) also confirms the MFI structure of these materials. As expected, the PXRD patterns of the
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33 as-made 2D MFI material shows only sharp (h0l) reflections because the layered MFIs were grown
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preferentially in the a-c crystallographic plane with the unit-cell thickness in the b-direction.41
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41 In addition to pure ZIF-8 membranes (Figure 2d, Case 0), we prepared three types of ZIF-
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43 8/MFI ANHMs on -alumina supports: ZIF-8 with MFI nanoparticles only (Case 1), ZIF-8 with
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46 MFI nanosheets only (Case 2), and ZIF-8 with MFI nanoparticles and MFI nanosheets (Case 3).
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48 The Supporting Information provides full details of the preparation of these membranes. In Cases
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50 1-3, MFI coatings were first made on the bare alumina support before coating of ZIF-8. Figure 2d
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53 also depicts the three types of MFI coatings. For Case 1, MFI nanoparticles were dispersed in a
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55 dilute polyethyleneimine (PEI) solution as a binder and then dip-coated on the support. For Case
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3 2, an MFI nanosheet suspension was vacuum-filtered on to the support. For Case 3, we sequentially
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6 performed the operations of Case 1 and Case 2 in order to obtain a dual layer that contains an MFI
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8 nanosheet layer on top of an MFI nanoparticle layer. For Cases 0-3, the ZIF-8 coating is made by
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10 the method of solvent evaporation-induced formation of a continuous ZIF-8 layer at elevated
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temperature.33 The highly concentrated ZIF-8 precursor solution infiltrates into the MFI inter-
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15 particle/inter-sheet spaces, and solvent evaporation induces supersaturation and ZIF-8
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17 crystallization.
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20 Synthesis and Characterization of ANHM Layers
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In general, the Case 0-3 membranes display four possible types of layers, which we index
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26 as Layer A (pure ZIF-8 layer), Layer B (ZIF-8/MFI nanoparticle ANHM layer), Layer C (ZIF-
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28 8/MFI nanosheet ANHM layer), and Layer D (ZIF-8 penetrated into the bulk alumina support).
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30 Figure S2 depicts these layers schematically using Case 3 membrane as an example, since it
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33 contains all the four layers A-D. Table 1 contains the detailed thickness estimates of each layer
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35 in the Case 0-3 membranes. Figure 4a shows a top-view SEM image of the alumina support, which
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37 has an effective macropore size of 87 nm and a coarse surface texture with RMS roughness
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40 (measured with AFM) of ~140 nm (Figures S3-S4).43 After dip-coating with a ~1.5 m layer of
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42 ~104 nm closely packed MFI nanoparticles (Figure 4c, upper panels), the surface roughness
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44 decreases to ~40 nm.42 Upon depositing the ZIF-8 film on the bare alumina support to obtain the
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47 Case 0 membrane (Figure 4b), we find a ~400 nm ZIF-8 surface layer A and also severe
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49 penetration of the ZIF-8 (~7 m) into the bulk of the support (layer D). On the other hand, the
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51 same ZIF-8 deposition conditions on the MFI nanoparticle-coated support led to a multilayered
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54 Case 1 membrane (Figure 4c, bottom panel) consisting of a thin (~ 500 nm) ZIF-8 top layer A, a
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56 ZIF-8/MFI ANHM layer B (~1.5 m), and a much lower extent of penetration (~3 m) of ZIF-8
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3 into the bulk alumina support (layer D). In the ANHM layer, the ZIF-8 and MFI nanoparticles
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6 showed excellent adhesion into a single composite material, as shown in Figure 4c as well as in
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8 the high-magnification SEM image of Figure S5. EDX elemental mapping analysis further reveals
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10 the dual-phase nature of the intermediate ZIF-8/MFI layer B in the Case 1 membrane (Figure S6),
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and the XRD pattern (Figure 3e-f) shows both the ZIF-8 and MFI diffraction peaks. The existence
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15 of the MFI nanoparticle layer reduces the penetration of the ZIF-8 in the alumina support (i.e. the
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17 layer D thickness), and the overall membrane thickness dramatically reduces from Case 0 (7.3 m)
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20 to Case 1 (4.8 m). Case 1 also shows a much more uniform thickness than Case 0 as shown by
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22 the higher-magnification SEM images of Figure S7, with a smaller standard deviation (Table 1).
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27 Although the ZIF-8/MFI nanoparticle layer B forms a highly permeable dual-phase ANHM
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29 layer and also retards the penetration of the ZIF-8 precursors into the bulk alumina support, the
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31 packing of sphere-like nanoparticles is not the ideal physical barrier to precursor infiltration.
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Instead, the use of the 2D MFI nanosheet layer C is hypothesized to have a larger barrier effect
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36 due to the high aspect ratio (~100) of the nanosheets. As shown in Figure 4d, the initial 2D MFI
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38 nanosheet layer coating is about 200 nm in thickness. After the ZIF-8 deposition step, the resulting
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Case 2 membrane indeed shows a large further reduction of the overall thickness (to 1.9 m) from
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43 Case 1, mainly due to the further reduction of the ZIF-8 infiltration into the alumina support (layer
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45 D, Table 1). The higher-magnification SEM cross-section image (Figure S8) shows a compact
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ZIF-8 (layer A) as well as clear infiltration of ZIF-8 between the MFI nanosheets to form a ZIF-
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50 8/MFI nanosheet ANHM (layer C). EDX elemental mapping of this membrane clearly reveals the
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52 presence of co-existence of 2D MFI nanosheets and ZIF-8 in the layer C (Figure 4e). The XRD
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patterns confirm the formation of ZIF-8 (Figure 3g-h). It is also noted that the transport paths
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3 available to molecules in the ANHM layers can be manipulated by switching from Case 1 (layer
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6 B) to Case 2 (layer C). In layer B, spherically-shaped MFI nanoparticles of larger pore size (> 0.5
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8 nm) are embedded in the ZIF-8 matrix of smaller pore size (~0.4 nm), whereas in layer C the 2D
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10 MFI nanosheets of larger pore size (> 0.5 nm) are sandwiched between ZIF-8 regions of smaller
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pore size (~0.4 nm) in a manner that approximates a series-resistance type transport of molecules.
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15 The Case 3 membrane (Figures 3i-j and 4f) combines all the four types of layers in the order A-
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17 C-B-D from top to bottom. While the presence of both types of MFI-containing layers B and C is
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expected to cause a further suppression of the layer D thickness, an additional advantage of this
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22 configuration over Case 2 is that the MFI nanoparticle layer smoothens out the roughness of the
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24 underlying alumina support (as seen earlier in Figure S3) and provides a highly permeable and
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26 smooth underlayer for the coating of the 2D MFI nanosheets. As seen in Figure 4f and Table 1,
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29 the Case 3 membrane has the lowest overall thickness and the lowest layer D thickness. Moving
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31 from Case 0 to Case 3 leads to the drastic reduction of the layer D (ZIF-8 infiltration into alumina)
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33 contribution to the overall membrane thickness, from 94% to 40%.
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39 Separation Properties of ANHM Layers
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42 The equimolar C3H6/C3H8 binary mixture separation properties of the Case 0-3 membranes
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44 were measured with a steady-state Wicke-Kallenbach technique at 298 K. The observed
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permeances and mixture selectivities (Figure 5) show a number of interesting and significant
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49 features, which can be understood with the help of the microstructural characteristics shown in
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51 Table 1 and Figure 3. The numerical values of the C3H6 and C3H8 permeances and selectivities
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53 are listed in Table S1. The Case 0 (pure ZIF-8) membrane shows low permeance of ~10 GPU as
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3 of 50-150). The low permeance is clearly a result of the deep infiltration of ZIF-8 into the support
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6 (Layer D, see Table 1). The low selectivity indicates that the infiltrated layer is also of defective
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8 quality and may have void/low-density regions or incompletely crystallized regions. This behavior
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10 highlights the practical limitations associated with fabricating ZIF-8 membranes by simple
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coatings on readily available support materials. The Case 1 membranes (containing ZIF-8 and MFI
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15 nanoparticles) show significant improvement over Case 0, with doubling of permeance (~20 GPU)
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17 as well as increase in selectivity (~30). Qualitatively, the permeance increase is understood in
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terms of the large reduction of the infiltrated layer (Table 1), while the selectivity increase is
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22 understood in terms of the increased influence of the other two layers – Layer B (ZIF-8/MFI
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24 nanoparticle ANHM) and Layer A (pure ZIF-8 top layer) – relative to the infiltrated Layer D. With
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26 Case 2 membranes (containing ZIF-8 and MFI nanosheets), a further increase in permeance (~45
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29 GPU) is observed with the same selectivity as in Case 1. The permeance increase can again be
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31 understood in terms of the continuing reduction of overall membrane thickness, mainly due to the
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33 reduction of Layer D (infiltration) but also due to the replacement of Layer B by the much thinner
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Layer C (ZIF-8/MFI nanosheet ANHM). However, the Case 3 membranes (containing all four
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38 Layers A-D) show the most dramatic effects: a large increase in both the C3H6 permeance (~65
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40 GPU) and in the selectivity (~70). Referring to Table 1, the further increase in permeance over
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Case 2 cannot be simply explained by overall thickness reduction since this is not significantly
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45 lower than Case 2. Rather, the key factor is the greatly increased contribution of the two highly
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47 permeable ANHM layers (Layers B and C) to the overall membrane thickness relative to the
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49 infiltrated Layer D. The same factor seems to be also responsible for the drastic increase in the
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52 selectivity of Case 3 membranes. While the Case 1 and 2 membranes do show increased selectivity
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54 over Case 0 due to the higher quality of the ANHM layers (Layer B and Layer C), a large influence
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3 of the defective infiltrated Layer D is still present. With the much lower influence of Layer D in
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6 Case 3 membranes, the high-quality ANHM layers are able to increase the membrane performance
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8 substantially.
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Analysis with Simple Series Resistance Model
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16 To obtain initial semi-quantitative insight on the properties of the ZIF-8/MFI ANHMs, in
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18 particular the properties of the two ANHM layers (Layer B and Layer C) in the Case 1-3
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20 membranes, we have analyzed the permeance data of Table S1 using a simple series-resistance
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23 model of permeation in a multi-layered membrane (Eqn. S1-S4, Supporting Information). A basic
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25 assumption for this analysis is that the fundamental permeability and selectivity characteristics of
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27 any particular layer are approximately the same wherever encountered in the four types of
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membranes (Case 0-3), e.g., the permeability and selectivity characteristics of Layer B (ZIF-8/MFI
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32 nanoparticle layer) remain the same across Case 1 and Case 3 membranes even though the Layer
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34 B thicknesses may differ across these membranes as obtained from Table 1. This assumption is
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36 quite reasonable since all the Case 0-3 membranes are synthesized under very similar conditions.
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39 We also assume that the permeance of the underlying bare -alumina support can be neglected
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41 from the analysis, since it is much higher (~7000 GPU for C3H6) than the permeances of the Case
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0-3 membranes. The thicknesses of each layer in the Case 0-3 membranes are taken from the
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46 experimental data of Table 1, and the total measured permeances are taken from the experimental
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48 data of Table S1. By applying Eqn. S1 sequentially to Case 0-3 membranes, we estimate the C3H6
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50 and C3H8 permeabilities and C3H6/C3H8 selectivities of all the four layers (A-D). Additionally, we
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53 have conducted error propagation calculations (see Supporting Information) to quantify the
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55 uncertainties in the obtained permeabilities and selectivities based upon the known error bars on
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3 the measured input quantities. Furthermore, model fitting was carried out with a number of
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6 different starting guesses in order to minimize physically unrealistic values. Nevertheless, given
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8 the simplicity of the model, the obtained fitting results should be used only for semi-quantitative
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10 inferences and relative comparisons between the different Case 0-3 membranes.
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15 The results of this analysis are shown in Table S2. The listed numerical values of the layer
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17 permeabilities and selectivities must be considered only as approximate/suggestive due to the
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model assumptions listed above and the error propagation. However, the results clearly allow two
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22 important inferences. Firstly, both Layer A (ZIF-8 top layer) and Layer D (infiltrated ZIF-8 layer)
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24 are defective and have low selectivities. Attempts to develop simple methods of coating ZIF-8
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26 membranes directly on inexpensive, non-tailored supports (Case 0 in this work) often result in
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29 defective membranes that would require substantial effort in optimizing the synthesis conditions
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31 to improve their properties. As also seen experimentally in Table 1, infiltration into the support is
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33 the main contributor to low membrane permeance in Case 0 membranes. Secondly, the ANHM
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Layers B and C are of high quality in terms of both permeability and selectivity and allow a large
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38 boost in the membrane performance. In terms of permeability, the use of 2D MFI nanosheets with
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40 out-of-plane oriented channels leads to the largest increase in permeability seen in Layer C.
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45 Although it is clear that Layers B and C have favorable separation characteristics, the
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47 uncertainty values of the selectivities are large and their values must be taken only in a qualitative
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49 sense. However, from the fitted estimates in Table S2 and the overall experimentally obtained
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52 properties of the ANHMs, an intriguing question arises whether the properties of the ZIF-8-like
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54 material in Layer B and Layer C could be fundamentally different from those of “bulk” ZIF-8. In
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3 our recent work, we used a “one-step” interfacial processing method to synthesize a ZIF-8/MFI
4
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6 nanoparticle ANHM with a dispersed MFI volume fraction of ~13%, which allowed a significant
7
8 increase in permeability and maintained high selectivity.30 We also showed these results to be well
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10 consistent with predictions of conventional models of permeation in hybrid membranes (such as
11
12
13
the Maxwell model). In the present Layers B and C, we encounter a very different membrane
14
15 morphology. The MFI volume fractions are clearly very high (most likely 50% or more), given
16
17 the closely packed MFI nanoparticles or stacked MFI nanosheets (Figure 4). The estimated
18
19
selectivities of these two layers in Table S2 are equivalent or even higher than what is expected in
20
21
22 a “defect-free” pure bulk ZIF-8 membrane. This is surprising since the MFI nanoparticles and
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24 nanosheets by themselves are expected to have a low C3H6/C3H8 intrinsic selectivity (< 3)30 on
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26 account of their larger pore size than ZIF-8. At the same time, the estimated permeabilities of
27
28
29 Layers B and C (while higher than pure ZIF-8) are still much lower than what would be expected
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31 from a composite containing ~50 vol% MFI zeolite (which has a C3H6 permeability > 8000
32
33 barrer).30 This simultaneous increase in selectivity and decrease in permeability (relative to
34
35
36
expected ranges based on bulk properties of ZIF-8 and MFI) hints significantly towards a likely
37
38 change in the properties of the ZIF-8-like material in these layers, rather than simply an data-fitting
39
40 artifact introduced by the model. In other words, the crystallization of the ZIF-8 matrix in the
41
42
confined microscopic spaces between the densely-packed MFI nanoparticles/nanosheets may lead
43
44
45 to the formation of crystalline – or even partially amorphous – regions with considerably smaller
46
47 effective ZIF-8 pore size than that of bulk ZIF-8 (perhaps as a consequence of greater rigidity of
48
49 the confined ZIF-8 lattice). In fact, such effects in ZIF-8 have recently been shown to be induced
50
51
52 with surprising ease by factors such as the application of electric fields, leading to remarkably high
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54 selectivities but low permeabilities.19,44 Additionally, the structure of the nanoscopic interfaces
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3 between the ZIF-8 and MFI regions is unknown, and these interfaces may have significantly
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6 different selectivity than bulk ZIF-8. While a detailed examination of the structure of ZIF-8 within
7
8 the Layer B and Layer C microstructures is clearly outside the scope of this paper, the remarkable
9
10 permeation properties of ANHMs shown in this work create a strong motivation for the future
11
12
13
detailed study of MOF-zeolite heterostructures and their interfaces. The foregoing hypotheses
14
15 could be tested, for example, by a combination of detailed diffusion and high-resolution
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17 crystallographic measurements in composite particles along with molecular simulation studies, to
18
19
probe bulk and interfacial structural changes.
20
21
22
23
24 At the moment we restrict ourselves to comparing the estimated Layer B and Layer C
25
26 properties from Table S2 with literature data on single-phase nanoporous membranes and
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29 polymer-based membranes. Figure S9 shows a Robeson-type plot of membrane permeability
30
31 versus selectivity for C3H6/C3H8 separation.7-8,11,13-20,22-26,30,47-51 Only materials with C3H6
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33 permeability > 1 Barrer (= 3.348×10-16 mol·m-1·s-1·Pa-1) are shown for technological significance.
34
35
36
As is well known, polymeric materials have difficulty in overcoming the permeability-selectivity
37
38 ‘upper bound’, whereas polymer-nanoporous material MMMs are able to access a limited region
39
40 above it. Among pure nanoporous membranes, zeolite membranes have shown high permeabilities
41
42
but rather low selectivity, whereas ZIF-8 and ZIF-67 membranes show excellent selectivities but
43
44
45 lower permeabilities due to their smaller pore sizes. Although the error propagation uncertainty
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47 ranges for ANHM Layer B and Layer C properties (depicted as rectangles) are significantly high,
48
49 they– along with the early ZIF-8/MFI nanoparticle ANHM demonstrated recently by us30 – show
50
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52 the ability to move into the extreme right region of the Robeson plot.
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3 CONCLUSIONS
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The All-Nanoporous Hybrid Membranes (ANHM) approach to multiphase membranes has
7
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9 been studied in detail, in the particular context of nanoporous membranes for propylene/propane
10
11 separation. The combination of a ZIF-8 matrix with high volume fractions of zeolite MFI
12
13 nanoparticles or high-aspect-ratio nanosheets can be used to fabricate a variety of multilayer
14
15
16 ANHM structures. In addition to formation of ANHM layers, the presence of MFI nanoparticle
17
18 and nanosheet coatings prior to ZIF-8 crystallization is very effective in preventing infiltration of
19
20 the ZIF-8 precursor solution into the support. This leads to a substantial increase in propylene
21
22
23 permeances, while the ANHM layers impart high propylene/propane selectivity. Detailed
24
25 investigation of microstructure-permeation property relationships reveals a synergistic
26
27 performance enhancement effect in the ANHM layers. The present ANHM processing
28
29
30
methodology, based upon precursor/nanoparticle coatings and subsequent evaporative
31
32 crystallization of membranes, should also be transferable to flexible supports. While our previous
33
34 report30 on ZIF-8/MFI (13 vol%) ANHMs on polymeric hollow fibers is an encouraging
35
36 indication, further work is certainly needed to demonstrate the use of flexible supports for ANHMs
37
38
39 with higher zeolite volume fractions such as those demonstrated in the present work. It can also be
40
41 expected that the fabrication of ANHMs with different MOF/zeolite or MOF/MOF combinations
42
43 can lead to a large new class of membranes with unprecedented separation properties.
44
45
46
47
48
49
50
EXPERIMENTAL SECTION
51
52
53 Materials. For alumina disk preparation, -Al2O3 (A16-SG, average size of ~500 nm) was
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55 supplied by Almatis. For ZIF-8 membrane fabrication, Zinc Acetate dihydrate (ZnAc·2H2O) and
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3 2-Methylimidazole (2-MeIM) was obtained from Sigma Aldrich. Dimethylacetamide (DMAc)
4
5
6 was purchased from Acros Organics and homemade DI-water was used. (Thermo Scientific 7128)
7
8 Methanol (MeOH) was purchased from VWR and used as received. For synthesis of long alkyl
9
10 chain structure directing agent (C22-6-6), N,N,Nʹ,Nʹ-tetramethyl-1,6-diaminohexane and 1-
11
12
13
bromohexane were obtained from Sigma Aldrich. 1-bromodocosane was purchased from TCI. For
14
15 MFI zeolite synthesis, tetraethyl orthosilicate (TEOS), 1M tetrapropylammonium hydroxide
16
17 solution (1M TPAOH), sodium hydroxide (NaOH) and sulfuric acid (H2SO4) was purchased from
18
19
Sigma Aldrich.
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22 Alumina disk support preparation. Disk substrates were prepared by procedures similar to work
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24 of Gu et al.43 The alumina powder was pressed at 130-bar pressure in a module with diameter of
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26 25 mm. The grain disk was then sintered at 1423 K for 6h to consolidate the disk with ramping
27
28
29 rate of 5 K/min. The resulting disk had diameter of ~24 mm. The disk was polished with 600 mesh
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31 silicon carbide sandpaper carefully before usage. The disk was ~2 mm thick and had average pore
32
33 size around 100 nm.
34
35
36
MFI nanoparticle synthesis. MFI nanoparticles were prepared by a procedure similar to the work
37
38 of Tang et al.42 The precursor solution used for synthesis had a molar ratio of 0.33 SiO2 : 0.1
39
40 TPAOH : 0.035 NaOH : 5.56 H2O. It was prepared by first dissolving NaOH pellets in 1 M
41
42
TPAOH solution, followed by fumed silica at 353 K. The precursor was aged at room temperature
43
44
45 for 4 h before receiving hydrothermal treatment. Hydrothermal treatment was conducted at 393 K
46
47 for 12 h. The particles were thoroughly rinsed with DI water before used for substrate coating.
48
49 2D MFI nanosheet suspension preparation. Layered 2D MFI materials were synthesized via a
50
51
52 hydrothermal reaction using C22H45-N(CH3)2-C6H12-N(CH3)2-C6H13]Br2 (C22-6-6) as the structure
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54 directing agent (SDA) as described by Choi et al.41 Firstly, as-synthesized C22-6-6 was dissolved in
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3 deionized water at room temperature, followed by addition of sodium hydroxide. After complete
4
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6 dissolution, TEOS was added dropwise under vigorous stirring. Appropriate amount of sulfuric
7
8 acid was added into the solution to adjust the pH condition. The final gel composition is 30 Na2O:
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10 100 SiO2 : 18 H2SO4 : 8000 H2O. After vigorous stirring at room temperature for 24 h to form a
11
12
13
homogeneous gel, the resulting gel was transferred to a teflon-lined autoclave and heated at 423 K
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15 for 5 days under rotation (40 rpm). The solid product was recovered by centrifugation and washed
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17 with deionized water and dried at 333 K. As-prepared layered MFIs were exfoliated by melt
18
19
compounding as reported by Varoon et al.32 Next, 2.4 g of melt compounded MFI-polystyrene
20
21
22 nanocomposites (4 % zeolite (w/w)) were dispersed in 192 mL of toluene and centrifuged at 8500
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24 rpm for 30 min. The sediments were dispersed and centrifuged again to eliminate the polystyrene.
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26 Purification step by density gradient centrifugation is employed to obtain 2D MFI nanosheets
27
28
29 coating suspension without unexfoliated particles.45 In the process, the sediments after removing
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31 the polystyrene were redispersed in 120 mL of octanol. A nonlinear density gradient was formed
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33 by sequentially placing 5 mL chloroform, 5 mL dichloromethane, 10 mL chlorobenzene, and 20
34
35
36
mL 2D MFI nanosheets suspension in octanol in a 50 mL centrifuge tube. After centrifugation at
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38 8500 rpm for 30 min, top 20 mL of the solution was collected and used as a 2D MFI coating
39
40 suspension.
41
42
ZIF-8/MFI ANHM fabrication. There are three types of steps (a-c) described below, that are used
43
44
45 to prepare membranes for Cases 0-3. Case 0 involves only step c, Case 1 involves step a followed
46
47 by step c, Case 2 involves step b followed by step c, and Case 3 involves step a followed by step
48
49 b followed by step c.
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51
52
53
a. Coating of alumina supports with 3D MFI nanoparticles: An aqueous solution containing 0.4%
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55 (wt) MFI nanoparticles and 1% (wt) polyethyleneimine (PEI) was used for disk substrate
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3 coating. Dip-coating was conducted for 5 s. The coated disks were dried at 333 K oven
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6 overnight and then calcined at 823 K for 6 h with ramping rate of 2 K/min before usage.
7
8 b. Coating of alumina supports with 2D MFI nanosheets: The 2D MFI nanosheet coatings were
9
10 performed by a vacuum-assisted filtration method. The sonicated 45 mL of the coating
11
12
13
suspension was poured over the alumina disk which is held inside the homemade filtration
14
15 module and vacuum was applied. After complete filtration, the disk was dried at 383 K
16
17 overnight and calcined at 823 K for 6 h with a ramping rate of 2 K/min to remove the organic
18
19
structure directing agent from a MFI framework.
20
21
22 c. Coating with ZIF-8: We first prepare a solution containing 1.32 g of zinc acetate dihydrate
23
24 dissolved in a 15 ml of 2:1 (vol/vol) dimethylacetamide/DI-water solvent (Solution 1). Solution
25
26 1 shows a cloudy texture upon mixing. Then, 1 g of 2-methylimidazole dissolved in another
27
28
29 batch of 15 ml of 2:1 (vol/vol) ratio dimethylacetamide/DI-water solvent (Solution 2). Then,
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31 Solution 1 was dissolved in Solution 2 dropwise while stirring, thereby obtaining a
32
33 clear/transparent solution. This solution was stirred for 15 min upon which cloudiness is again
34
35
36
observed. Then, the α-alumina supports (either bare or already coated with various MFI
37
38 materials as described above) were dip-coated in this solution for 10 s, transferred to an oven
39
40 preheated to 473 K and cured for 15 min, cooled at ambient conditions, solvent-exchanged
41
42
with methanol for 12 h, and dried under ambient conditions. Degassing of each membrane was
43
44
45 performed at 393 K for 8 h under 10 SCCM argon sweep condition before gas permeation
46
47 measurements.
48
49 Characterization. XRD patterns were measured on a PANalytical X’Pert Pro diffractometer at
50
51
52 room temperature using Cu Kα radiation and a scanning range of 5−40° 2θ. Surface and cross-
53
54 section SEM images of the membranes were collected with a Hitachi SU 8010 scanning electron
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3 microscope. TEM images were collected by a FEI Tecnai 30 at an acceleration voltage of 300 kV.
4
5
6 Atomic force microscopy (AFM) images of inner surfaces of the hollow fibers were obtained with
7
8 an ICON Dimension® scanning probe microscope (Bruker). The AFM was operated under tapping
9
10 mode with Mikromasch NSC14 silicon cantilevers (8 nm tip radius, 5 N/m force constant, and 160
11
12
13
kHz typical resonance frequency). Mixed gas permeation measurements were carried out with the
14
15 Wicke-Kallenbach technique at 298 K. Argon is used as a sweep gas at the permeate side, whose
16
17 pressure will be maintained at 1 bar during permeation measurements. An online gas
18
19
chromatography unit (GC2014, Shimadzu) was used to determine the permeate composition. The
20
21
22 mixture selectivity (α) is calculated as the permeance ratio of the two components.
23
24
25
26 Permeance Equation for Multi-Layer Membranes. Consider the general Case 3 membrane
27
28
29 assembly with four layers: Layer A: pure ZIF-8, Layer B: ZIF-8/MFI nanoparticle ANHM, Layer
30
31 C: ZIF-8/MFI nanosheet ANHM, and Layer D: ZIF-8 penetrated into the bulk alumina support.
32
33 For any permeating species, the permeance (in units of GPU) of the overall membrane assembly
34
35
36
can be easily derived assuming the resistance-in-series model:
37
38
1
39 𝑃̅𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = 𝐿𝐴 𝐿 𝐿 𝐿 (1)
40 + 𝐵 + 𝐶+ 𝐷
𝑃𝐴 𝑃𝐵 𝑃𝐶 𝜀.𝑃𝐷
41
42
43
44 Here, Li denotes the thickness of the layer i = A, B, C, D (in units of m) and Pi denotes the
45
46 permeability (in units of Barrer) of the layer. For Layer D which is infiltrated into the porous
47
48
49
alumina support, the additional factor  (porosity of the support) is present, and PD represents the
50
51 intrinsic permeability of the ZIF-8 material infiltrated in the pores of the support. Here, we use 
52
53 = 0.37 as obtained from mercury porosimetry on the alumina support. Equation 1 can be applied
54
55
56 to the other Cases 0, 1, and 2 by simply eliminating the terms on the right-hand side for layers that
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3 are not present in the membrane. Thus, for any permeating species, a set of four nonlinear
4
5
6 equations can be written corresponding to the Cases 0-3 (see Supporting Information, Equations
7
8 S1-S4). Given the experimental overall permeances (Table S1) and individual layer thicknesses
9
10 (Table 1) for each membrane, the four equations are solved simultaneously to obtain the four
11
12
13
permeabilities PA, PB, PC and PD for the same permeating species. The above procedure is carried
14
15 out for both propylene and propane permeants, and the results are summarized in Table S2. The
16
17 error propagation analysis for this model is also summarized in the Supporting Information
18
19
(Equations S5-S8).
20
21
22
23 ASSOCIATED CONTENT
24
25
26 Supporting Information
27
28
29 Series-resistance model of permeation in a multi-layered membrane and error propagation analysis,
30
31
32
numerical data corresponding to figures, crystal size distribution (CSD), Powder X-ray diffraction
33
34 patterns, AFM, SEM, and pore size distribution analysis data. representative summary of
35
36 C3H6/C3H8 separation performance of reported membranes.
37
38
39 AUTHOR INFORMATION
40
41
42 Corresponding Author
43
44
45 Sankar Nair, School of Chemical & Biomolecular Engineering, Georgia Institute of Technology,
46
47 Atlanta GA 30332-0100, USA
48
49 *E-mail: sankar.nair@chbe.gatech.edu
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51
52
53 Notes
54
55 Conflict of interest: The authors declare no competing financial interests.
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3 ACKNOWLEDGMENT
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5
6 We acknowledge financial support of this work by ARPA-E (#DE-AR-0000751).
7
8
9 REFERENCES
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11 (1) Park, H. B.; Kamcev, J.; Robeson, L. M.; Elimelech, M.; Freeman, B. D. Maximizing the Right
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39 (29) Eum, K.; Ma, C.; Rownaghi, A.; Jones, C. W.; Nair, S. ZIF-8 Membranes via Interfacial
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41 Microfluidic Processing in Polymeric Hollow Fibers: Efficient Propylene Separation at Elevated
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43 Pressures. ACS Appl. Mater. Interfaces 2016, 8 (38), 25337–25342.
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5 Properties of Metal Organic Frameworks/ Polyetherimide Mixed Matrix Membranes. J. Appl.
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15 Tsapatsis, M. Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective
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17 Membrane. Science. 2011, 334 (6052), 72–75.
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20 (33) Shah, M. N.; Gonzalez, M. A.; McCarthy, M. C.; Jeong, H. K. An Unconventional Rapid Synthesis
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22 of High Performance Metal-Organic Framework Membranes. Langmuir 2013, 29 (25), 7896–7902.
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25 (34) Li, W.; Su, P.; Li, Z.; Xu, Z.; Wang, F.; Ou, H.; Zhang, J.; Zhang, G.; Zeng, E. Ultrathin Metal-
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34 Zeolitic-Imidazolate Framework ZIF-8 Membranes for Propylene/Propane Separation.
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36 Microporous Mesoporous Mater. 2018, 259 (15), 155–162.
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39 (36) Jang, E.; Kim, E.; Kim, H.; Lee, T.; Yeom, H. J.; Kim, Y. W.; Choi, J. Formation of ZIF-8
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41 Membranes inside Porous Supports for Improving Both Their H2/CO2 Separation Performance and
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43 Thermal/Mechanical Stability. J. Memb. Sci. 2017, 540, 430–439.
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48 Deposition of Chemically Modified α-Al2O3 Particles for High Performance ZIF-8 Membrane on
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Type Zeolite Membranes. Ind. Eng. Chem. Res. 2005, 44 (1), 226–230.
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18 Boiling Hydrocarbon Mixtures by MFI and FAU Membranes Made by Secondary Growth.
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20 Microporous Mesoporous Mater. 2001, 48 (1–3), 219–228.
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23 (49) Zhang, C.; Dai, Y.; Johnson, J. R.; Karvan, O.; Koros, W. J. High Performance ZIF-8/6FDA-DAM
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25 Mixed Matrix Membrane for Propylene/Propane Separations. J. Memb. Sci. 2012, 389, 34–42.
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28 (50) Yang, F.; Mu, H.; Wang, C.; Xiang, L.; Yao, K. X.; Liu, L.; Yang, Y.; Han, Y.; Li, Y.; Pan, Y.
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30 Morphological Map of ZIF-8 Crystals with Five Distinctive Shapes: Feature of Filler in Mixed-
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32 Matrix Membranes on C3H6/C3H8 Separation. Chem. Mater. 2018, 30 (10), 3467–3473.
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35 (51) Burns, R. L.; Koros, W. J. Defining the Challenges for C3H6/C3H8 Separation Using Polymeric
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37 Membranes. J. Memb. Sci. 2003, 211 (2), 299–309.
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29 Figure 1: Schematic depiction of the “all-nanoporous hybrid membrane” (ANHM) concept.
30 Single-phase nanoporous materials (MOFs, zeolites) provide higher performance than polymers
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and mixed-matrix membranes, but may not have sufficient performance or processability.
33 Different (color-coded) combinations of nanoporous materials (e.g., MOF+zeolite) can move the
34 ANHM properties to higher permeances (brown arrow), higher selectivities (green arrow), or both
35 (purple arrow), relative to the respective base (matrix) nanoporous material. The enhancements
36 occur in a much higher permeability-selectivity region of the plot than polymer-based mixed-
37 matrix membranes. The combination of properties is non-linear, i.e., tradeoffs can be overcome;
38 and the graph scale is logarithmic, hence large absolute changes in permeability & selectivity occur
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in top right region.
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Figure 2. Overall scheme of ANHM materials and membrane architectures: (a) Pore
28 structures of ZIF-8 (exhibiting framework flexibility with effective pore size ~0.42 nm)39 and MFI
29 (channel size ~0.55 nm along the b-direction as shown, and sinusoidal channel size ~0.53 nm along
30 the a-direction which is not shown). Kinetic dimeters and van der Waals volumes (gray colored
31 volumes) of C3H6 and C3H8 are also shown. (b-c) TEM images, and (inset) HRTEM images, of
32 3D MFI nanoparticles and 2D MFI nanosheets respectively. (d) Schematic of four different types
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of membranes supported on -alumina. Case 0: ZIF-8 only; Case 1: ZIF-8 with MFI nanoparticles,
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35 Case 2: ZIF-8 with MFI nanosheets, and Case 3: ZIF-8 with MFI nanoparticles and MFI
36 nanosheets. The MFI coatings used in Cases 1-3 are also shown in detail: bare alumina support
37 (gray-white), MFI nanoparticle coating (blue), 2D MFI nanosheet coating (red), and 2D MFI
38 nanosheet layer on top of MFI nanoparticle layer (red + blue).
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34 Figure 3. X-ray diffraction patterns: (a) simulated ZIF-8, (b) simulated MFI, (c) MFI
35 nanoparticles, (d) 2D layered MFI nanosheets. The PXRD pattern of 2D layered MFI is from the
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lamellar MFI nanosheet assemblies before the exfoliation step. (e)-(f) Case 1, (g)-(h) Case 2 and
38 (i)-(j) Case 3 membranes after coating of MFI materials only (black) and after coating of ZIF-8
39 (red). MFI peaks are denoted by asterisks (*) and ZIF-8 peaks are denoted by the circles (○). In
40 Case 1 and Case 3, the signals from MFI nanoparticles are seen throughout. In Case 2 and Case 3,
41 there is no XRD signal from the MFI nanosheets, as expected since they have been exfoliated
42 before deposition on the alumina support.
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43 Figure 4. Morphologies of membranes in Cases 0-3. The four types of layers (Figure S3) are A:
44 pure ZIF-8, B: ZIF-8/MFI nanoparticle ANHM, C: ZIF-8/MFI nanosheet ANHM, and D: ZIF-8
45 penetrated into the bulk alumina support. Layer thickness values marked in this figure are from
46 Table 1. (a) SEM top view of bare alumina support, (b) Cross-section SEM image of Case 0 (ZIF-
47 8) membrane showing severe penetration of ZIF-8 into the support, (c) Case 1: MFI nanoparticle
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coating followed by ZIF-8 coating, (d) Case 2: MFI nanoparticle coating followed by ZIF-8
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50 coating, (e) For the Case 2 membrane, EDX elemental maps of zinc (blue), silicon (green) and
51 alumina (red). The dashed line is only a visual guide to demarcate the layers A, C, and D. The
52 intermediate layer C is seen to contain both ZIF-8 (Zn signal) and MFI (Si signal), and (f) Case 3:
53 Sequential MFI nanoparticle and MFI nanosheet coatings followed by ZIF-8 coating.
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membranes at 298 K. The C3H6 permeance and the C3H6/C3H8 mixture selectivities (ratios of the
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31 measured component permeances in the mixture permeation experiments) are shown. The error
32 bars were estimated from three independently prepared membrane samples for each case. The
33 permeance unit of 1 GPU = 3.348×10-10 mol·m-2·s-1·Pa-1.
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7 Table 1. Estimated thicknesses of each layer in Case 0-3 membranes as obtained from SEM image
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measurements. Each value is measured from at least three cross-sections obtained at different
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10 locations of an individual sample, and averaged with three independently fabricated samples. The
11 four types of layers are listed as defined in Figure S3, viz. Layer A: pure ZIF-8, Layer B: ZIF-
12 8/MFI nanoparticle ANHM, Layer C: ZIF-8/MFI nanosheet ANHM, and Layer D: ZIF-8
13 penetrated into the bulk alumina support.
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19 Case 0 Case 1 Case 2 Case 3
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21 Index Thickness % of Thickness % of Thickness % of Thickness % of
22 total total total total
23 [µm] thickness [µm] thickness [µm] thickness [µm] thickness
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A 0.42 ± 0.11 6 0.48 ± 0.21 10 0.34 ± 0.08 19 0.24 ± 0.06 12
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26 B - - 1.51 ± 0.26 31 - - 0.72 ± 0.12 37
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28 C - - - - 0.16 ± 0.04 8 0.16 ± 0.06 8
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30 D 6.86 ± 2.98 94 2.81 ± 0.56 59 1.37 ± 0.45 73 0.79 ± 0.07 40
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32 Total 7.28 ± 2.99 100 4.80 ± 0.59 100 1.87± 0.49 100 1.95 ± 0.15 100
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