Metal organic Frameworks as Adsorbents for Hydrogen Purification and Pre-Combustion Carbon Dioxide Capture

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1 Supporting Information for: Metal organic Frameworks as Adsorbents for Hydrogen Purification and Pre-Combustion Carbon Dioxide Capture Zoey R. Herm, Joseph A. Swisher, Berend Smit, Rajamani Krishna, Jeffrey R. Long* Department of Chemistry, University of California, Berkeley, CA , Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA , Van t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands * jrlong@berkeley.edu J. Am. Chem. Soc. S-1

2 Experimental Details Dichloromethane was received from Aldrich and dried over activated 4 Å sieves prior to use. Ethanol was heated to reflux for 24 h over Mg turnings and I 2. 1 All other reagents were obtained from commercial vendors and used without further purification. Powder X-ray diffraction patterns were obtained on a Bruker D8 Advance diffractometer with a Cu anode (λ = Å). Infrared spectra were obtained on a Perkin-Elmer Spectrum 100 Optica FTIR spectrometer furnished with an attenuated total reflectance accessory (ATR). Caution! Beryllium compounds can pose a serious health risk through skin contact and inhalation. All manipulations of solid beryllium-containing materials should be performed in a fumehood or glove bag, taking care not to generate airborne dust in the open air under any circumstances. Synthesis of 1,3,5-triphenylbenzene. 1,3,5-triphenylbenzene was prepared according to literature procedure. 2 Synthesis of 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid (H 3 BTB). H 3 BTB was synthesized from 1,3,5-triphenylbenzene and nitric acid according to literature procedure. 3 Synthesis of MOF-177. MOF-177 was prepared according to literature procedure. 4 Synthesis of Be 12 (OH) 12 (1,3,5-benzenetribenzoate) 4 (BeBTB). The same sample characterized in Sumida et al. was used for this study. 5 Synthesis of 1,4-benzenedi(4 -pyrazolyl) (H 2 BDP). H 2 BDP was synthesized according to literature procedure. 6 Synthesis of CoBDP. CoBDP was synthesized according to literature procedure. 6 Synthesis of 1,3,5-tris(triazol-5-yl)benzene (H 3 BTTri). H 3 BTTri was synthesized according to literature procedure. 7 Synthesis of CuBTTri. CuBTTri was synthesized according to literature procedure. 7 Synthesis of Mg 2 (dobdc). Mg 2 (dobdc) was synthesized according to literature procedure. 8 Activation of MOF Activation of the sample was performed by transferring the collected product into a nitrogen-filled glove bag, where the solid was soaked in N,Ndimethylformamide (50 ml) for 24 h. The supernatant was decanted and replenished a further two times over two days. The solid was then soaked in dichloromethane (50 ml) for 24 h. The supernatant was decanted and replenished a further three times over three days, and after the final wash a gentle stream of nitrogen was passed over the sample so as to remove excess solvent. The product is hygroscopic and was therefore stored in a glove box under a dinitrogen S-2

3 atmosphere. The final degassing was performed on a vacuum manifold at 1 mtorr and 100 C for 10 h. Surface area was determined by 77 K N 2 adsorption and confirmed with literature data. 10 Powder pattern was compared to the simulated pattern from the crystal structure. 11 Activation of BeBTB. BeBTB was activated according to literature procedure. 5 Activation of CoBDP. CoBDP was evacuated at ambient temperature at 1000 mtorr for 24 h and then transferred quickly to a Schlenk flask in a glovebag. The sample was then evacuated at 1 mtorr for two days and brought to 170 C at a ramp rate of 5 C per hour. Activation of CuBTTri. CuBTTri was activated according to literature procedure. 7 Activation of Mg 2 (dobdc). Mg 2 (dobdc) was activated using a strategy adapted from the literature procedure. 8 The yellow microcrystalline material was combined and washed repeatedly with DMF and soaked in DMF for 24 h. The DMF was decanted, and freshly distilled methanol was added. The solid was then transferred to a nitrogen-filled glovebox. The methanol was decanted and the solid was soaked in DMF on a hotplate set at 100 C for 18 h. The DMF was decanted and replaced, and the solid was soaked at 100 C for 4 h. The DMF was decanted and replaced by methanol, which was decanted and replenished 6 times with a minimum of 6 hours between washes. Low-Pressure Gas Sorption Measurements and Surface Area Calculations. Lowpressure gas adsorption was used in two contexts in this study: to measure the surface area of the prepared metal organic framework samples and to measure adsorption of CO 2 onto Mg 2 (dobdc) below 1 bar. Mg 2 (dobdc) required this measurement due to the open Mg 2+ sites which interact strongly with CO 2 (see Figure S20). During these measurements, glass sample tubes of a known weight were loaded with approximately 200 mg of sample, and sealed using a TranSeal. Samples were degassed on a Micromeritics ASAP 2020 analyzer until the outgas rate was no more than 1 mtorr/min as described above. The degassed sample and sample tube were weighed precisely and then transferred back to the analyzer (with the TranSeal preventing exposure of the sample to the air after degassing). The outgas rate was again confirmed to be less than 1 mtorr/min. Adsorption isotherms were measured at 77 K in a liquid nitrogen bath for and N 2 and 313 K in an isothermal water bath for CO 2. Langmuir and BET surface areas were calculated using the Micromeritics software and the method of Snurr and coworkers, 12 respectively. Although Langmuir surface areas are inherently inapplicable in microporous metal organic frameworks, due to the ambiguity in BET surface area calculations for flexible materials, we report both. 13 S-3

4 High-Pressure Gas Sorption Measurements. In a typical measurement, at least 200 mg of sample was loaded in a sample holder in a glove box under an argon atmosphere. Hydrogen and carbon dioxide excess adsorption measurements were performed on an automated Sieverts apparatus (PCTPro-2000 from Hy-Energy Scientific Instruments LLC) over a pressure range of 0-50 bar. UHP-grade hydrogen, carbon dioxide and helium (99.999% purity) were used for all measurements. Total adsorption was calculated using NIST Thermochemical Properties of Fluid Systems: CO 2 and H 2 densities between 0 and 50 bar were fit using a sixth-order polynomial, then multiplied by the pore volume of each material. 14 Interpolation of 313 K Adsorption Data for Zeolite 13X. Belmabkhout et al. 15 reported excess adsorption of CO 2 and H 2 on zeolite 13X at 303 K and 323 K. These were converted to total adsorption using a pore volume of 0.34 cm 3 /g. Carbon dioxide uptake values and hydrogen uptake values were fit to dual- and single-site Langmuir Freundlich fits, respectively. The averages of these curves were taken at intervals of 0.1 bar from 0 to 14 bar, and then these averaged values were again fit to dual- and single-site Langmuir Freundlich fits for the interpolated CO 2 and H 2 data sets, respectively. See Figure S13 for the raw and interpolated data. Ideal Adsorbed Solution Theory Calculations. The ideal adsorbed solution theory (IAST) of Prausnitz and Myers was used to estimate the composition of the adsorbed phase from pure component isotherm data. 16,17 Experimental absolute isotherm data were fit to the dual-site Langmuir-Freundlich isotherm for CO 2 adsorption and the single-site Langmuir-Freundlich model for H 2. H 2 saturation capacities were allowed to refine between two and three times the saturation capacity for CO 2, which was confirmed visually. The integrals were computed numerically and the adsorbed phase composition that minimized the difference between the integrals of the two spreading pressures was found using Mathematica. 18 A sample calculation for determining the mole fraction of CO 2 adsorbed in an 80:20 H 2 :CO 2 mixture in Mg 2 (dobdc) is included below. Selectivities were then calculated according to equation 1, where x i is the mole fraction of component i in the adsorbed phase and y i is the mole fraction of component i in the bulk. Working capacities were calculated according to equation 2 where n t is the total number of adsorbed moles of gas per unit mass of adsorbent and n o i is the number of moles of component i in the adsorbed phase per unit mass of adsorbent. S-4

5 S = x i y j x j y i (1) 1 n t = x i n i o + x j n j o (2) Literature data for zeolites and activated carbons that were reported for comparison to metal organic frameworks were taken from references as mentioned in the text. Zeolite 13X, zeolite 5A, and BPL activated carbon were converted to absolute adsorption because the authors confirmed the data reported were excess or no mention was made of conversion to absolute adsorption in the text. Ideal Adsorbed Solution Theory Validation for CO 2 /H 2 Mixtures in Metal organic Frameworks. The accuracy of the IAST for estimation of component loadings for adsorption of a wide variety of binary mixtures in zeolites has been established with the aid of Configurational-Bias Monte Carlo (CBMC) simulations. 19 As illustration of the validity of the use of the IAST for estimation of CO 2 /H 2 adsorption equilibrium in MOFs we present CBMC results for adsorption of CO 2 /H 2 mixtures in MOF-177 at 313 K, the temperature used in the experimental work. The CBMC simulation methodology is similar to that described in published work. 20 The symbols in Figure S11 represent the pure component adsorption isotherms for CO 2 and H 2 in MOF-177 obtained from CBMC. The continuous solid lines in Figure S11 are the dual-site Langmuir Freundlich fits of the isotherms. The component loadings in an 80:20 H 2 :CO 2 mixture at 313 K, determined using CBMC simulations, are presented Figure S12 as filled symbols. The continuous solid lines are the IAST estimations using the dual-site Langmuir Freundlich fits of the pure component isotherms. It is to be noted that there is excellent agreement between the IAST predictions and the CBMC S-5

6 simulated component loadings in the mixture. This agreement is typical for adsorption of CO 2 :H 2 mixtures in MOFs. S-6

7 S-7

8 Table S1. Adsorption data for MOF-177 at 313 K (pore volume = 1.59 ml/g). 11 CO 2 H 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-8

9 Table S2. Adsorption data for BeBTB at 313 K (pore volume = ml/g). CO 2 H 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-9

10 Table S2 (continued) CO 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-10

11 Table S3. Adsorption data for CoBDP at 313 K (pore volume = 0.93 ml/g). 6 CO 2 H 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-11

12 Table S4. Adsorption data for CuBTTri at 313 K (pore volume = ml/g). 7 CO 2 H 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-12

13 Table S4 (continued) CO 2 Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) S-13

14 Table S5. Adsorption data for Mg 2 (dobdc) at 313 K (pore volume = ml/g). CO 2 H 2 Pressure (bar) Excess Uptake (mmol/g) TotalUptake (mmol/g) Pressure (bar) Excess Uptake (mmol/g) Total Uptake (mmol/g) 4.89E S-14

15 Table S5 (continued) CO 2 Pressure (bar) Excess Uptake (mmol/g) TotalUptake (mmol/g) S-15

16 Table S6. Fit parameters used in this study for CO 2 (equation 3) and H 2, where n is gas uptake in mmol/g. BPL Carbon Activated Carbon JX101 Zeolite5A Zeolite13X Mg 2 (dobdc) MOF 177 Be BTB Co(BDP) Cu BTTri a b c d e f CO H CO H CO H CO H CO H CO * H * CO H CO * H * CO * H * n = a * b* p1/c 1+ b* p 1/c + d *e* p1/ f 1+ e* p 1/ f (3) S-16

17 Table S7. Tabulated surface area and approximate pore volume data for the five metal organic frameworks investigated in this study. Mg 2 (dobdc) PoreVolume (cm 3 /g) LangmuirSurface Area(m 2 /g) BETSurfaceArea (m 2 /g) MOF Be BTB Co(BDP) Cu BTTri S-17

18 Figure S1. Adsorption isotherm for N 2 in MOF-177 at 77 K. Black and red circles represent experimental and previously reported literature data, respectively. 10 S-18

19 Figure S2. Adsorption isotherm for N 2 in Be-BTB at 77 K. Black circles represent previously reported literature data on the same sample used in this study. 5 S-19

20 Figure S3. Adsorption isotherm for N 2 in Co-BDP at 77 K. Black and red circles represent experimental and previously reported literature data, respectively. 6 S-20

21 Figure S4. Adsorption isotherm for N 2 in Cu-BTTri at 77 K. Black and red circles represent experimental and previously reported literature data, respectively. 7 S-21

22 Figure S5. Adsorption isotherm for N 2 in Mg 2 (dobdc) at 77 K. Black and red circles represent experimental and previously reported literature data, respectively. 8b S-22

23 Figure S6. Gas adsorption isotherms for CO 2 on Mg 2 (dobdc). Green triangles represent the isotherms measured for this study at 313 K and black diamonds are data recorded at 303 K by Dietzel et al. 21 S-23

24 Figure S7. Gas adsorption isotherms for CO 2 on Mg 2 (dobdc). Green triangles represent the isotherms measured for this study at 313 K and black diamonds 22 and blue circles 11 are data recorded at 298 K by Yaghi and coworkers. S-24

25 Figure S8. Total adsorption isotherms for CO 2 (green triangles) and H 2 (blue circles) at 313 K in Be-BTB. S-25

26 Figure S9. Absolute adsorption isotherm for CO 2 (green triangles) at 313 K in Mg 2 (dobdc) expressed in mmol/g and molecules of CO 2 per magnesium site. S-26

27 Figure S10. Absolute adsorption isotherm for CO 2 (green triangles) at 313 K in Cu-BTTri expressed in mmol/g and molecules of CO 2 per magnesium site. S-27

28 Figure S11. Configurational-Bias Monte Carlo simulations of absolute pure-component adsorption isotherms for CO 2 (green triangles) and H 2 (blue circles) at 313 K in MOF-177. The continuous solid lines are the dual-site Langmuir Freundlich fits of the pure component isotherms. S-28

29 Figure S12. The component loadings in an 80:20 H 2 :CO 2 mixture for CO 2 (green triangles) and H 2 (blue circles) at 313 K in MOF-177 determined using CBMC simulations. The continuous solid lines are the IAST estimations of the same mixture using the dual-site Langmuir Freundlich fits of the pure component isotherms. S-29

30 Figure S13. Absolute adsorption of CO 2 and H 2 at 303 K (red circles and green diamonds respectively) and 323 K (orange triangles and purple squares respectively) on zeolite 13X reported by Belmabkhout et al. 15 Solid lines are interpolated 313 K data from this study using dual-site Langmuir Freundlich fits of the averages of the 303 K and 323 K data for CO 2 (blue) and H 2 (black). S-30

31 Figure S14. IAST-calculated selectivities for an 80:20 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-31

32 Figure S15. IAST-calculated selectivities for a 60:40 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-32

33 Figure S16. IAST-calculated gravimetric working capacities for an 80:20 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-33

34 Figure S17. IAST-calculated volumetric working capacities for an 80:20 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-34

35 Figure S18. IAST-calculated gravimetric working capacities for a 60:40 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-35

36 Figure S19. IAST-calculated volumetric working capacities for a 60:40 H 2 :CO 2 mixture. References for literature data are mentioned in the text. S-36

37 Figure S20. Literature values for the heat of adsorption of CO 2 on Mg 2 (dobdc) 8a (red line) and Cu-BTTri 7 (blue circles). S-37

38 References (1) Armarego, W. L. F.; Chai, C. L. L. Purification of Laboratory Chemicals, 5th ed.; Elsevier. Online version available at: KNOVEL_DISPLAY_bookid=899&VerticVer=O. (2) Hu, H.; Zhang, A.; Ding, L.; Lei, X.; Zhang, L. J. Chem. Res. 2007, 720. (3) Kim, J.; Chen, B.; Reineke, T. M.; Li, H.; Eddaoudi, M.; Moler, D. B.; O Keefe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2001, 123, (4) Vajo, J.; Pinkerton, F.; Stetson, N. Nanotechnology 2009, 20, (5) Sumida, K.; Hill, M. R.; Horkie, S.; Dailly, A.; Long, J. R. J. Am. Chem. Soc. 2009, 131, (6) Choi, H. J.; Dincă, M.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 784 (7) Demessence, A.; D Allessandro, D.; Foo, M. L.; Long, J. R. J. Am. Chem. Soc. 2009, (8) (a) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem. Soc 2008, 130, (b) Sumida, K.; Brown, C. M.; Herm, Z. R.; Chavan, S.; Bordiga, S.; Long, J. R. Chem. Commun. 2010, in press. (9) Kaye, S. S.; Dailly, A.; Yaghi, O. M.; Long, J. R. J. Am. Chem. Soc. 2007, 129, (10) Furukawa, H.; Miller, M. A.; Yaghi, O. M. J. Mater. Chem. 2007, 17, (11) Chae, H. K.; Siberio-Pérez, D. Y.; Kim. J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O Keefe, M.; Yaghi, O. M. Nature 2004, 427, 523. (12) Walton, K. S.; Snurr, R. Q. J. Am. Chem. Soc. 2007, 129, (13) Düren, T.; Millange, F.; Férey, G.; Walton, K. S.; Snurr, R. Q. J. Phys. Chem C 2007, 111, (14) Lemmon, E. W.; McLinden, M.O.; Friend, D. G. Thermophysical Properties of Fluid Systems. In NIST Chemistry WebBook, NIST Standard Reference Database Number 69: Linstrom, P. J.; Mallard, W. G., Eds.; National Institute of Standards and Technology: Gaithersburg MD (15) Belmabkhout, Y,; Pirngruber, G.; Jolimaitre, E.; Melthevier, A. Adsorption 2007, 13, 341. (16) Myers, A. L.; Prausnitz, J. M. AIChE J. 1965, 11, 121. (17) Tien, C. Adsorption Calculations and Modeling. Butterworth-Heineman: Boston, 1994; pp (18) Wolfram Research, Inc., Mathematica, Version 7.0, Champaign, IL: S-38

39 (19) (a) Krishna, R.; Calero, S.; Smit, B. Chem. Eng. J. 2002, 88, 81. (b) Krishna, R.; van Baten, J. M. Chem. Eng. J. 2007, 133, 121. (20) Krishna, R.; van Baten, J. M. J. Membr. Sci. 2010, 360, 323. (21) Dietzel, P. D. C.; Besikiotis, V.; Blom, R. J. Mater. Chem. 2009, 19, (22) Walton, K. S.; Millward, A. R.; Dubbeldam, D,; Frost, H.; Low, J. J.; Yaghi, O. M.; Snurr, R. Q. J. Am. Chem. Soc. 2008, 130, 406. S-39

Supporting Information

Supporting Information Hydrogen Storage in the Dehydrated Prussian Blue Analogues M 3 [Co(CN) 6 ] 2 (M = Mn, Fe, Co, Ni, Cu, Zn) Steven S. Kaye and Jeffrey R. Long* Dept. of Chemistry, University of California,