Supporting Information. Tuning the Interplay between Selectivity and Permeability of ZIF-7 Mixed Matrix Membranes

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1 Supporting Information Tuning the Interplay between Selectivity and Permeability of ZIF-7 Mixed Matrix Membranes Bassem A. Al-Maythalony,,* Ahmed M. Alloush, Muhammed Faizan, Hatim Dafallah, Mohammed A. A. Elgzoly, Adam A. A. Seliman, Amir Al-Ahmed, Zain H. Yamani, Mohamed A. M. Habib, Kyle E. Cordova,, and Omar M. Yaghi,,,* King Abdulaziz City for Science and Technology Technology Innovation Center on Carbon Capture and Sequestration (KACST-TIC on CCS) at King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia Center for Research Excellence in Nanotechnology (CENT), King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia Department of Chemistry, University of California-Berkeley; Materials Sciences Division, Lawrence Berkeley National Laboratory; Kavli Energy NanoSciences Institute at Berkeley; and Berkeley Global Science Institute, Berkeley, California 94720, United States *Correspondence should be addressed to: S-1

2 Table of Contents Section S1 Structural characterization of nzif-7 and PSM-nZIF-7 S3-S15 Section S2 Characterization of pure PEI membrane and the corresponding mixed matrix membranes (MMM) S16-S24 Section S3 Gas permeation analysis S25-S35 Section S4 Thermodynamic gas adsorption measurements S36-S39 Section S5 References S40-S41 S-2

3 Section S1: Structural characterization of nzif-7 and PSM-nZIF-7 Figure S1. Powder X-ray diffraction analysis (PXRD) of nzif-7 (red) in comparison to the diffraction pattern simulated from single crystal structure of ZIF-7 (black). S-3

4 Figure S2. Scanning electron microscopy images (SEM) of the as-synthesized nzif-7 displaying the uniform morphology and narrow size dispersity (500 nm scale bar). S-4

5 Figure S3. PXRD analysis of PSM-nZIF-7 (blue) and nzif-7 (red) in comparison to the diffraction pattern simulated from single crystal structure of ZIF-7 (black). S-5

6 Figure S4. Fourier transform infrared (FTIR) spectrum of nzif-7. S-6

7 Figure S5. 1 H NMR spectrum of the digested sample of nzif-7. S-7

8 Figure S6. 13 C NMR spectrum of the digested sample of nzif-7. S-8

9 Figure S7. 1 H NMR spectrum of the digested sample of PSM-nZIF-7 after 3 d. S-9

10 Figure S8. 13 C NMR spectrum of the digested sample of PSM-nZIF-7 after 3 d. S-10

11 Figure S9. SEM of the PSM-nZIF-7 displaying the uniform morphology and narrow size dispersity (500 nm scale bar). S-11

12 Figure S10. FTIR spectrum of PSM-nZIF-7. S-12

13 Figure S11. N 2 adsorption isotherms of nzif-7 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. S-13

14 Figure S12. N 2 adsorption isotherms of PSM-nZIF-7 at 77 K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. S-14

15 Figure S13. Thermogravimetric analysis (TGA) of nzif-7 and PSM-nZIF-7, at a heating rate of 5 C min -1 under airflow. S-15

16 Section S2. Characterization of pure PEI membrane and the corresponding mixed matrix membranes (MMM) Figure S14. SEM images of the cross sections of the PSM-nZIF-7/PEI MMM (50 µm scale bar). The inset depicts the sponge-like features of the PSM-nZIF/PEI MMM (10 µm scale bar). S-16

17 Figure S15. SEM and energy dispersive X-ray spectroscopy (EDX) analysis of the cross section of the pure PEI membrane. S-17

18 Figure S16. SEM and EDX analysis of nzif-7/pei MMM s surface showing the presence of zinc. S-18

19 Figure S17. SEM and EDX analysis of PSM-nZIF-7/PEI MMM s surface showing the presence of zinc. S-19

20 Figure S18. SEM and EDX analysis of nzif-7/pei MMM s cross sections showing the presence of zinc. S-20

21 Figure S19. SEM and EDX analysis of PSM-nZIF-7/PEI (right) MMM s cross sections showing the presence of zinc. S-21

22 Figure S20. EDX-derived elemental mapping of zinc on the surface (A,B) and cross section (C,D) of nzif-7/pei MMM. S-22

23 Figure S21. EDX-derived elemental mapping of zinc on the surface (A,B) and cross section (C,D) of PSM-nZIF-7/PEI MMM. S-23

24 Figure S22. TGA of the pure PEI membrane (black), nzif-7/pei MMM (red) and PSMnZIF-7/PEI MMM (blue), at a heating rate of 5 C min -1 under air flow. S-24

25 Section S3. Gas permeation analysis Scheme S1. Custom built constant-volume/variable-pressure (CV/VP) gas permeation setup. S-25

26 Figure S23. General expression of time lag and steady state criteria found through CV/VP measurements. Permeability of the pure gas calculated from the equation: P SS LR dp dp d d Vdl dt dt ( pup pd ) ART = (1) Where P is the permeability coefficient in Barrer (10-10 cm 3 (STP) cm/(cm 2 s cmhg)), dp d /dt SS is the downstream pressure rise (cmhg/s) at the steady state, dp d /dt LR is the downstream leak rate (cmhg/s), V d is the downstream volume (cm 3 ), l is the membrane thickness (cm), p up is the upstream pressure (cmhg), A is the membrane area (cm 2 ), R is the gas constant [0.278 cm 3 cmhg/(cm 3 (STP) K)], and T is the temperature at measurement (K). S-26

27 The apparent diffusion coefficient calculated from the time lag θ (s) using the equation (2) S solubility coefficient (cm 3 (STP)/(cm 3 permeation occurs via the solution-diffusion mechanism cmhg)) calculated from the equation, assuming (3) Selectivity for a gas pair, i and j, is calculated by (4) Figure S24: Single gas permeation vs. time for pure PEI membrane at 35 ºC and 1520 Torr. S-27

28 Figure S25: Single gas permeation vs. time for nzif-7/pei MMM at 35 ºC and 1520 Torr. S-28

29 Figure S26: Single gas permeation vs. time for PSM-nZIF-7/PEI MMM at 35 ºC and 1520 Torr. S-29

30 Table S1: Gas permeation results for PEI membrane. Gas Lennard Jones Diameter d LJ [Å] Normal boiling Point [K] Permeability [barrer] Permeance [mol/(s m 2 Pa)] Diffusivity Coefficient (D) [cm 2 /s] Solubility Coefficient (S) [cm 3 (gas)/(cm 3 (MOF)cmHg)] H E E E Timelag (θ) [sec] N E E E O E E E CH E E E CO E E E C 2H E E E C 3H E E E Table S2: Gas permeation results for nzif-7/pei MMM. Gas Lennard Jones Diameter d LJ [Å] Normal boiling Point [K] Permeability [barrer] Permeance [mol/(s m 2 Pa)] Diffusivity Coefficient (D) [cm 2 /s] Solubility Coefficient (S) [cm 3 (gas)/(cm 3 (MOF)cmHg)] H E E E Timelag (θ) [sec] N E E E O E E E CH E E E CO E E E C 2H E E E C 3H E E E Table S3: Gas permeation results for PSM-nZIF-7/PEI MMM. Gas Lennard Jones Diameter d LJ [Å] Normal boiling Point [K] Permeability [barrer] Permeance [mol/(s m 2 Pa)] Diffusivity Coefficient (D) [cm 2 /s] Solubility Coefficient (S) [cm 3 (gas)/(cm 3 (MOF)cmHg)] H E E E N E E E O E E E Timelag (θ) [sec] CH E E E CO E E E C 2H E E E C 3H E E E S-30

31 Figure S27. H 2 /CH 4 relationship between permeability (P) and gas pair selectivity (α) in comparison with the Robeson upper bound curve for pure PEI membrane (black square), nzif-7/pei MMM (red triangle) and PSM-nZIF-7/PEI MMM (blue circle). S-31

32 Figure S28. H 2 /CO 2 relationship between permeability (P) and gas pair selectivity (α) in comparison with the Robeson upper bound curve for pure PEI membrane (black square), nzif-7/pei MMM (red triangle) and PSM-nZIF-7/PEI MMM (blue circle). S-32

33 Figure S29. CO 2 /CH 4 relationship between permeability (P) and gas pair selectivity (α) in comparison with the Robeson upper bound curve for pure PEI membrane (black square), nzif-7/pei MMM (red triangle) and PSM-nZIF-7/PEI MMM (blue circle). S-33

34 Figure S30. CO 2 /N 2 relationship between permeability (P) and gas pair selectivity (α) in comparison with the Robeson upper bound curve for pure PEI membrane (black square), nzif-7/pei MMM (red triangle) and PSM-nZIF-7/PEI MMM (blue circle). S-34

35 Table S4. Comparison of the current membrane performance with ZIF-7/polymers, MOF/Ultem and other best performing ZIF/polymer Mixed Matrix Membranes. Material Polymer MOF (wt%) Temp. (ºC) P (atm) α (CO 2/N 2) α (CO 2/CH 4) P CO 2 (barrer) α (H 2/CO 2) P H 2 (barrer) - PEI * nzif-7 PEI * PSM-nZIF-7 PEI * ZIF-7/polymer MMM ZIF-7 PBI 10,25, ZIF-7 Pebax (2.75 CO 2) MOF/Ultem MMMs ZIF-90 Ultem IRMOF-1 Ultem 10, ZIF-8 Ultem 10,13 25, GPU** - - MIL-53 Ultem NH 2-MIL- 53(Al) Ultem (3.0) - - HKUST-1 Ultem Other high performing ZIF/polymers MMMs ZIF-8 PIM ZIF-8 6FDAdurene ZIF-8 Pebax 5-35 RT 2, ZIF-8 ZIF-71 ZIF-90 6FDAdurene 6FDAdurene 6FDA- DAM 3-30 RT 2, ZIF-90 Matrimid Notes: *This work; ** Gas permeation units (GPU) = 10 6 (cm 3 (STP))/(cm 2 s cmhg)); IRMOF = isoreticular metal-organic framework; MIL-53 = Materials Institute Lavoisier-53; HKUST-1 = Hong Kong University of Science and Technology; PBI = polybenzimidazole; Pebax = polyether block amide; Ultem = polyetherimide (PEI); PIM-1 = polymer of intrinsic microposority; 6FDA-durene = (hexafluorodianhydride)-based polyimide; PES = polyethersulfone; 6FDA-DAM = (hexafluorodianhydride)-based polyimide; and Matrimid = thermoplastic polyimide. Ref S-35

36 Section S4. Thermodynamic gas adsorption measurements Figure S31. CO 2 isotherms for nzif-7 at 273 (black squares), 298 (red triangles), and 313 (blue circles) K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. S-36

37 Figure S32. CO 2 isotherms for PSM-nZIF-7 at 273 (black squares), 298 (red triangles), and 313 (blue circles) K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. S-37

38 Figure S33. N 2 (black squares), CH 4 (red triangles) and CO 2 (blue circles) isotherms for nzif-7 at 298 K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. S-38

39 Figure S34. N 2 (black squares), CH 4 (red triangles) and CO 2 (blue circles) isotherms for PSM-nZIF-7 at 298 K. Filled and open symbols represent adsorption and desorption branches, respectively. The connecting curves are guides for the eye. Table S5. Summary of the thermodynamic gas adsorption measurements for nzif-7 and PSM-nZIF-7. A BET m 2 g -1 A Lang m 2 g -1 uptake CO 2 (273 K) CO 2 uptake (298 K) CO 2 uptake (313 K) N 2 uptake (298 K) CH 4 uptake (298 K) nzif PSM-nZIF S-39

40 Section S5. References 1. Hou, X.-J.; Li, H.; He, P. Theoretical Investigation for Adsorption of CO 2 and CO on MIL-101 Compounds with Unsaturated Metal Sites. Comp. Theor. Chem. 2015, 1055, Liu, B.; Jiang, Y.-H.; Li, Z.-S.; Hou, L.; Wang, Y.-Y. Selective CO 2 Adsorption in a Microporous Metal-Organic framework with Suitable Pore Sizes and Open Metal Sites. Inorg. Chem. Front. 2015, 2, Bae, T. H.; Lee, J. S.; Qiu, W.; Koros, W. J.; Jones, C. W.; Nair, S. A High Performance Gas Separation Membrane Containing Submicrometer sized Metal Organic Framework Crystals. Angew. Chem., Int. Ed. 2010, 49, Yang, Y.; Lin, R.; Ge, L.; Hou, L.; Bernhardt, P.; Rufford, T. E.; Wang, S.; Rudolph, V.; Wang, Y.; Zhu, Z. Synthesis and Characterization of Three Amino-Functionalized Metal Organic Frameworks Based on the 2-Aminoterephthalic Ligand. Dalton Trans. 2015, 44, Regufe, M. J.; Tamajon, J.; Ribeiro, A. M.; Ferreira, A.; Lee, U.-H.; Hwang, Y. K.; Chang, J.-S.; Serre, C.; Loureiro, J. M.; Rodrigues, A. E. Syngas Purification by Porous Amino-Functionalized Titanium Terephthalate MIL-125. Energy Fuels 2015, 29, Haldar, R.; Reddy, S. K.; Suresh, V. M.; Mohapatra, S.; Balasubramanian, S.; Maji, T. K. Flexible and Rigid Amine Functionalized Microporous Frameworks Based on Different Secondary Building Units: Supramolecular Isomerism, Selective CO 2 Capture, and Catalysis. Chem. Eur. J. 2014, 20, Serra Crespo, P.; Wezendonk, T. A.; Bach Samario, C.; Sundar, N.; Verouden, K.; Zweemer, M.; Gascon, J.; Berg, H. v. d.; Kapteijn, F. Preliminary Design of a Vacuum Pressure Swing Adsorption Process for Natural Gas Upgrading Based on Amino Functionalized MIL 53. Chem. Eng. Tech. 2015, 38, Gao, W.-Y.; Palakurty, S.; Wojtas, L.; Chen, Y.-S.; Ma, S. Open Metal Sites Dangled on Cobalt Trigonal Prismatic Clusters within Porous MOF for CO 2 Capture. Inorg. Chem. Front. 2015, 2, Chen, Y.; Li, Z.; Liu, Q.; Shen, Y.; Wu, X.; Xu, D.; Ma, X.; Wang, L.; Chen, Q.-H.; Zhang, Z. Microporous Metal Organic Framework with Lantern-like Dodecanuclear Metal Coordination Cages as Nodes for Selective Adsorption of C 2 /C 1 Mixtures and Sensing of Nitrobenzene. Cryst. Growth Design 2015, 15, S-40

41 10. Witte, J.; Neaton, J. B.; Head-Gordon, M. Assessing Electronic Structure Approaches for Gas-Ligand Interactions in Metal-Organic Frameworks: The CO 2 -Benzene Complex. J. Chem. Phys. 2014, 140, Gao, W.-Y.; Pham, T.; Forrest, K. A.; Space, B.; Wojtas, L.; Chen, Y.-S.; Ma, S. The Local Electric Field Favours more than Exposed Nitrogen Atoms on CO 2 Capture: A Case Study on the rht-type MOF Platform. Chem. Commun. 2015, 51, Yoon, M. and Moon, D. New Zr(IV) Based Metal-Organic Framework Comprising a Sulfur-Containing Ligand: Enhancement of CO 2 and H 2 Storage Capacity. Microporous Mesoporous Mater. 2015, 215, S-41

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