Structural Contraction of Zeolitic. Imidazolate Frameworks: Membrane. Application on Porous Metallic Hollow

Transcription

1 Structural Contraction of Zeolitic Imidazolate Frameworks: Membrane Application on Porous Metallic Hollow Fibers for Gas Separation Fernando Cacho-Bailo, a Miren Etxeberría-Benavides, b Oana David, b Carlos Téllez, a Joaquín Coronas a,* a Chemical and Environmental Engineering Department and Instituto de Nanociencia de Aragón (INA), Universidad de Zaragoza, Zaragoza, Spain b Tecnalia Research and Innovation, Energy and Environmental Division, Donostia-San Sebastián, Spain * Corresponding author. coronas@unizar.es Phone: S1

2 Supporting Information Table S1. Linear thermal expansion coefficients (TEC) of materials suitable for use in the fabrication of membranes. TEC 10-6 [K - 1 ] Nickel 13.3 Stainless steel 17.3 Alumina 7.5 Polyamide 110 Polysulfone 56.0 Polyetherimide 50.0 a sod-zn(im) Ag(mIm) MOF ,4 HKUST [Ag(en)]NO Mn 3 [Co(CN) 6 ] Si-CHA HZSM Si-FAU a Theoretical prediction S2

3 Table S2. Fabrication parameters for Ni green compact hollow fibers. Condition Value Bore composition H 2 O/NMP 35/65 Spinneret OD 1.3 mm Spinneret ID 0.7 mm Spinneret temperature 20 ºC Dope flow rate 90 ml h -1 Bore flow rate 30 ml h -1 Air gap height 3 cm Take up rate 4.84 m min -1 Room temperature 17 ºC Room humidity 66.2 Quench bath temperature 25 ºC, water Sequential washing procedure Water bath 48 h Methanol bath 3 30 min Hexane bath 3 30 min Drying at ambient conditions 1 1 sin = sin h + + 2h cos Equation S1. = sin Equation S2. = ( ) ; =,, Equation S3. = ( ) Equation S4. = 3 Equation S5. S3

4 Figure S1. Normalized XRD patterns of ZIF-7 and Co-ZIF-9 powders. The simulated pattern of the ZIF-9-III material is also shown for comparison (CCDC number/code /SOTYIL). 10 S4

5 Figure S2. Normalized XRD patterns of ZIF-9-III as a function of temperature in the ºC range. No phase transition but a clear shift in the diffraction peaks was observed (see also Figure 6a), related with a structure expansion/contraction phenomenon. Patterns at 20 ºC after the XRD acquisition is also shown, thus demonstrating the ZIF-9-III stability. Table S3. ZIF-9-III unit cell parameters and volume resulting from the experimental XRD pattern adjustment. T [ºC] a [Å] b [Å] c [Å] β a [º] V [Å 3 ] % b 1.87% -2.13% -3.64% % 0.61% -1.22% -2.73% % -0.37% 1.27% 1.87% % -3.47% 2.54% 1.89% a Monoclinic crystalline system and C 1 2/c 1 (15) space group were maintained. b Variation with respect to the unit cell features at 20 ºC. S5

6 Figure S3. Normalized XRD patterns of ZIF-7-III as a function of temperature in the ºC range (a). No phase transition but a clear shift in the diffraction peaks was observed, related with a structure expansion/contraction phenomenon. The Miller indices of the peaks used for structure refinement are indicated. Patterns at 20 ºC after the XRD acquisition is also shown, thus demonstrating the ZIF-7-III stability. S6

7 Table S4. ZIF-7-III unit cell parameters and volume resulting from the experimental XRD pattern adjustment. T [ºC] a [Å] b [Å] c [Å] β a [º] V [Å 3 ] % b 1.71% -1.88% -2.61% % 2.62% -0.45% -0.38% % -0.88% 1.25% 1.76% % -2.54% 2.19% 1.08% a Monoclinic crystalline system and C 1 2/c 1 (15) space group were maintained. b Variation with respect to the unit cell features at 20 ºC. Table S5. Linear thermal expansion coefficients (TEC) obtained for ZIF-7-III. T range α a a α b a α c a -116 ºC T amb (20 ºC) T amb (20 ºC) 250 ºC ºC 250 ºC a Linear thermal expansion coefficients (TEC), see Equations 3 to 5. b Averaged TEC; α = α v /3 (α v = volumetric TEC). α b Figure S4. Rendering of the ZIF-7-III structure at different viewing directions. Hydrogen atoms were hidden for clarity. The material layers along c-direction can be clearly distinguished, as well as the 4-member ring pores in each layer (a-b plane). S7

8 Figure S5. SEM images of the cross section (a) and wall detail (b) of a green Ni HF. Figure S6. Hg porosimetry of the sintered 25-µm Ni HF support. S8

9 Figure S7. SEM images, at different magnifications, of the ZIF-9 (a,b) and ZIF-7 (c,d) powdered materials collected during the HF membrane microfluidic fabrication and in-batch synthesized, respectively. S9

10 Figure S8. Weight loss curves of ZIF-9 and ZIF-7 powders (top), together with that of the HF membrane (down) obtained by TG analyses in air atmosphere. ZIF-7 showed a 180 ºC-higher thermal stability than ZIF-9. A MOF content of 4.1 wt% in the fabricated membrane was calculated. No weight loss was observed in the powdered material before 300 ºC, thus indicating they were activated. Figure S9. Gas permeances obtained with the as-synthesized ZIF-9@Ni HF membrane at 35 ºC in the studied H 2 /CO 2 and He/CH 4 mixtures with respect to the molecular kinetic diameter and the inversed square root of S10

11 the molecular weight. A combination of molecular sieving and Knudsen-driven gas transport mechanisms can be deduced. Figure S10. ZIF-9@Ni HF membrane activation data during the H 2 /CO 2 separation testing. A gas permeance increase can be observed through the successive heating cycles, the H 2 /CO 2 selectivity remaining constant. Figure S11. Weight loss and weight loss rate curves of the PEG400 in oxidative (air) and inert (N 2 ) atmospheres. PEG400 evaporation at temperatures from 200 ºC was possibly related to the gas permeance increase observed in the ZIF-9@Ni HF membrane. S11

12 Figure S12. Weight variation of the Ni HF support when submitted to a 250 ºC temperature program in a reductive 50/50 v/v H 2 /CO 2 atmosphere for 24 h. No NiO reduction in the bulk support could be deduced. Ni HF after TG Ni HF before TG Ni powder Simulated NiO theta / ºFigure S13. Normalized XRD patterns of Ni powder and Ni HF before and after 250 ºC temperature program in a reductive 50/50 v/v H 2 /CO 2 atmosphere for 24 h (see previous Figure S12). NiO intensities cannot be seen in the sample treated at high temperature. S12

13 Table S6. Averaged superficial elemental composition by EDX. O [wt%] Ni [wt%] Total [wt%] Ni HF support before TGA a 4.5 c Ni HF support after TGA b 1.3 c a Green as-synthesized Ni HF support. b Ni HF support sample after the 24 h 250 ºC program in a reductive atmosphere for 24 h. c A local NiO reduction to Ni can be deduced in the external surface of the support, thus contributing to the observed increase in the gas permeance of the resulting membrane. Table S7. Permeation data dependence on temperature of the activated ZIF-9@Ni HF membrane in the H 2 /CO 2 mixture separation. T [ºC] H 2 permeance CO 2 permeance [mol m -2 s -1 Pa -1 ] [GPU] [mol m -2 s -1 Pa -1 ] [GPU] α H2/CO2 ln(p H2 ) ln(p CO2 ) S13

14 Figure S14. Gas permeance data fit to the Arrhenius equation. A 3-fold higher apparent activation energy was calculated for CO 2 than for H 2. S14

15 Table S8. H 2 /CO 2 separation performance with MOF-supported HF (or tubular) membranes. INORGANIC A B C D - E F G H I J Ref. MOF Support OD [µm] ID [µm] a α H2/CO2 P H2 [GPU] 11 ZIF-8 Al 2 O 3 /ZnO ZIF-8 YSZ ZIF-8 Al 2 O ZIF-8 C ZIF-8 Al 2 O 3 +APTES * ZIF-8 Al 2 O ZIF-8 Al 2 O ZIF-8 Al 2 O ZIF-8 Al 2 O ZIF-8 Al 2 O ZIF-8 Al 2 O 3 /ZnO POLYMERIC K This work ZIF-9-III Ni L M N O P Q R 22 ZIF-7 PVDF * ZIF-8 PVDF * HKUST-1 PVDF ZIF-8 PVDF ZIF-7 PVDF NH 2 -MIL-53 PVDF ZIF-9/ZIF-8 P ZIF-9/ZIF-67 P HKUST-1 PAN a Asterisks note ideal selectivities. S15

16 Figure S15. Performance comparison of the MOF-supported membranes with a tubular or HF conformation in the H 2 /CO 2 separation, both with inorganic (black) and polymeric (red) supports. Only the membranes reporting mixture selectivities are shown. The X-axis displays the membrane permeance normalized by the outer diameter (OD) of the corresponding support, as a measure of the membrane efficiency. HF-OD sizes, in the 10 mm-300 µm range, are shown in Table S8. The Ni HF (610 µm) used in this work displays the highest efficiency (in terms of area to volume ratio) among the inorganic-supported HF membranes considered. Supporting Information References (1) Bouëssel du Bourg, L.; Ortiz, A. U.; Boutin, A.; Coudert, F.X. Thermal and Mechanical Stability of Zeolitic Imidazolate Frameworks Polymorphs. APL Materials 2014, 2 (12), (2) Ogborn, J. M.; Collings, I. E.; Moggach, S. A.; Thompson, A. L.; Goodwin, A. L. Supramolecular Mechanics in a Metal-Organic Framework. Chem. Sci. 2012, 3 (10), (3) Zhou, W.; Wu, H.; Yildirim, T.; Simpson, J. R.; Walker, A. R. H. Origin of the Exceptional Negative Thermal Expansion in Metal-Organic Framework-5 Zn 4 O(1,4-benzenedicarboxylate) 3. Phys. Rev. B 2008, 78 (5), (4) Schneemann, A.; Bon, V.; Schwedler, I.; Senkovska, I.; Kaskel, S.; Fischer, R. A. Flexible Metal-Organic Frameworks. Chem. Soc. Rev. 2014, 43 (16), (5) Cai, W.; Katrusiak, A. Giant Negative Linear Compression Positively Coupled to Massive Thermal Expansion in a Metal Organic Framework. Nat. Commun. 2014, 5, S16

17 (6) Adak, S.; Daemen, L. L.; Hartl, M.; Williams, D.; Summerhill, J.; Nakotte, H. Thermal Expansion in 3D-Metal Prussian Blue Analogs a Survey Study. J. Solid State Chem. 2011, 184 (11), (7) Woodcock, D. A.; Lightfoot, P.; Villaescusa, L. A.; Díaz-Cabañas, M.J.; Camblor, M. A.; Engberg, D. Negative Thermal Expansion in the Siliceous Zeolites Chabazite and ITQ-4: A Neutron Powder Diffraction Study. Chem. Mater. 1999, 11 (9), (8) Marinkovic, B. A.; Jardim, P. M.; Saavedra, A.; Lau, L. Y.; Baehtz, C.; de Avillez, R. R.; Rizzo, F. Negative Thermal Expansion in Hydrated HZSM-5 Orthorhombic Zeolite. Microporous Mesoporous Mater. 2004, 71 (1 3), (9) P. Attfield, M. Strong Negative Thermal Expansion in Siliceous Faujasite. Chem. Commun. 1998, (5), (10) Zhao, P.; Lampronti, G. I.; Lloyd, G. O.; Wharmby, M. T.; Facq, S.; Cheetham, A. K.; Redfern, S. A. T. Phase Transitions in Zeolitic Imidazolate Framework 7: the Importance of Framework Flexibility and Guest-Induced Instability. Chem. Mater. 2014, 26 (5), (11) Wang, X.; Sun, M.; Meng, B.; Tan, X.; Liu, J.; Wang, S.; Liu, S. Formation of Continuous and Highly Permeable ZIF-8 Membranes on Porous Alumina and Zinc Oxide Hollow Fibers. Chem. Commun. 2016, 52 (92), (12) Pan, Y.; Wang, B.; Lai, Z. Synthesis of Ceramic Hollow Fiber Supported Zeolitic Imidazolate Framework-8 (ZIF-8) Membranes with High Hydrogen Permeability. J. Membr. Sci. 2012, (0), (13) Tao, K.; Kong, C.; Chen, L. High Performance ZIF-8 Molecular Sieve Membrane on Hollow Ceramic Fiber Via Crystallizing-Rubbing Seed Deposition. Chem. Eng. J. 2013, 220 (0), 1-5. (14) Kong, L.; Zhang, X.; Liu, H.; Wang, T.; Qiu, J. Preparation of ZIF-8 Membranes Supported on Macroporous Carbon Tubes Via a Dipcoating Rubbing Method. J. Phys. Chem. Solids 2015, 77 (0), (15) Xie, Z.; Yang, J.; Wang, J.; Bai, J.; Yin, H.; Yuan, B.; Lu, J.; Zhang, Y.; Zhou, L.; Duan, C. Deposition of Chemically Modified α-al 2 O 3 Particles for High Performance ZIF-8 Membrane on a Macroporous Tube. Chem. Commun. 2012, 48 (48), (16) Huang, K.; Dong, Z.; Li, Q.; Jin, W. Growth of a ZIF-8 Membrane on the Inner-Surface of a Ceramic Hollow Fiber Via Cycling Precursors. Chem. Commun. 2013, 49 (87), (17) Tao, K.; Cao, L.; Lin, Y.; Kong, C.; Chen, L. A Hollow Ceramic Fiber Supported ZIF-8 Membrane with Enhanced Gas Separation Performance Prepared by Hot Dip-Coating Seeding. J. Mater. Chem. A 2013, 1 (42), (18) Xu, G.; Yao, J.; Wang, K.; He, L.; Webley, P. A.; Chen, C.; Wang, H. Preparation of ZIF-8 Membranes Supported on Ceramic Hollow Fibers from a Concentrated Synthesis Gel. J. Membr. Sci. 2011, (0), S17

18 (19) Kong, L.; Zhang, X.; Liu, Y.; Li, S.; Liu, H.; Qiu, J.; Yeung, K. L. In Situ Fabrication of High-Permeance ZIF-8 Tubular Membranes in a Continuous Flow System. Mater. Chem. Phys. 2014, 148 (1 2), (20) Zhang, X.; Liu, Y.; Kong, L.; Liu, H.; Qiu, J.; Han, W.; Weng, L. T.; Yeung, K. L.; Zhu, W. A Simple and Scalable Method for Preparing Low-Defect ZIF-8 Tubular Membranes. J. Mater. Chem. A 2013, 1 (36), (21) Drobek, M.; Bechelany, M.; Vallicari, C.; Abou Chaaya, A.; Charmette, C.; Salvador- Levehang, C.; Miele, P.; Julbe, A. An Innovative Approach for the Preparation of Confined ZIF-8 Membranes by Conversion of ZnO ALD Layers. J. Membr. Sci. 2015, 475 (0), (22) Li, W.; Meng, Q.; Li, X.; Zhang, C.; Fan, Z.; Zhang, G. Non-Activation ZnO Array as a Buffering Layer to Fabricate Strongly Adhesive Metal-Organic Framework/PVDF Hollow Fiber Membranes. Chem. Commun. 2014, 50 (68), (23) Li, W.; Meng, Q.; Zhang, C.; Zhang, G. Metal Organic Framework/PVDF Composite Membranes with High H 2 Permselectivity Synthesized by Ammoniation. Chem. Eur. J. 2015, 21 (19), (24) Li, W.; Su, P.; Zhang, G.; Shen, C.; Meng, Q. Preparation of Continuous NH 2 -MIL-53 Membrane on Ammoniated Polyvinylidene Fluoride Hollow Fiber for Efficient H 2 Purification. J. Membr. Sci. 2015, 495, (25) Cacho-Bailo, F.; Matito-Martos, I.; Perez-Carbajo, J.; Etxeberria-Benavides, M.; Karvan, O.; Sebastian, V.; Calero, S.; Tellez, C.; Coronas, J. On the Molecular Mechanisms for the H 2 /CO 2 Separation Performance of Zeolite Imidazolate Framework Two-Layered Membranes. Chem. Sci. 2017, 8, (26) Li, W.; Yang, Z.; Zhang, G.; Fan, Z.; Meng, Q.; Shen, C.; Gao, C. Stiff Metal-Organic Framework-Polyacrylonitrile Hollow Fiber Composite Membranes with High Gas Permeability. J. Mater. Chem. A 2014, 2 (7), S18