Hydrogen Storage in the Expanded Pore Metal-Organic Frameworks M 2 (dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn)

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1 Supporting Information for: Hydrogen Storage in the Expanded Pore Metal-Organic Frameworks M 2 (dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn) David Gygi, Eric D. Bloch, Jarad A. Mason, Matthew R. Hudson, Miguel I. Gonzalez, Rebecca L. Siegelman, Tamim A. Darwish, Wendy L. Queen, Craig M. Brown, Jeffrey R. Long* * jrlong@berkeley.edu Chemistry of Materials S1

2 List of Contents 77K and 87K H 2 isotherms for M 2 (dobpdc)....s3-s5 Isotherm Fitting...S6-S12 Linear BET plots for M 2 (dobpdc)....s13-s15 Table of performance metrics and physical properties of M 2 (dobpdc)...s16 77K H 2 adsorption comparison of Ni 2 (dobdc) and Ni 2 (dobpdc) s16 Atomic parameters from Rietveld refinement of Fe 2 (dobpdc) s17-19 Rietveld refinements of the neutron diffraction pattern of Fe 2 (dobpdc) s19-s21 Single Crystal Synthesis and X-Ray Diffraction.....S22-S23 NMR spectra and ESI-MS spectrum for deuteration procedure..s24-s25 Inelastic Neutron Scattering (INS)...S26 References S27 S2

3 Figure S1. H 2 isotherms at 77K and 87K for Mg 2 (dobpdc) Figure S2. H 2 isotherms at 77K and 87K for Mn 2 (dobpdc) S3

4 Figure S3. H 2 isotherms at 77K and 87K for Fe 2 (dobpdc) Figure S4. H 2 isotherms at 77K and 87K for Co 2 (dobpdc) S4

5 Figure S5. H 2 isotherms at 77K and 87K for Ni 2 (dobpdc) Figure S6. H 2 isotherms at 77K and 87K for Zn 2 (dobpdc) S5

6 Isotherm Fitting The 77 and 87 K H 2 adsorption isotherms were independently fit with either a dual- or triple-site Langmuir model (Eqn 1), where n is the amount adsorbed in mmol/g, P is the pressure in bar, n sat,i is the saturation capacity in mmol/g, and b i is the Langmuir parameter in bar 1 for up to three sites 1, 2, and 3. The fitted parameters for each adsorption isotherm can be found in Table S1. Plots of the absolute adsorption isotherms with the corresponding dual-site Langmuir- Freundlich fits can be found in Figures S8-S15. Note that the pure component isotherms for Ni 2 (dobdc) have been recently published, but they were refit in this work. 1 n= n b P sat, b 1 P + n b P sat, b 2 P + n b P sat, b 3 P (1) The Clausius-Clapeyron equation (Eqn 2) was used to calculate the isosteric heats of adsorption (differential enthalpy), H ads, for each compound using the dual- or triple-site Langmuir- Freundlich fits at 77 and 87 K. ln P= H ads R 1 +C (2) T Here, P is the pressure, n is the amount adsorbed, T is the temperature, R is the universal gas constant, and C is a constant. The isosteric heats of adsorption were obtained from the slope of plots of (ln P) n versus 1/T. High-Pressure Adsorption Experimentally measured excess adsorption, n ex, was converted to total adsorption, n tot, using total pore volumes (V p ; Table S2), as determined from N 2 isotherms at 77 K (P/P 0 = ~0.9), and the bulk gas density, bulk, at each temperature and pressure from the NIST Refprop database (Eqn 3). 2,3 n tot = n ex +V p ρ bulk ( P,T) (3) S6

7 Table S1. Dual- or triple-site Langmuir fit parameters. T (K) n sat, 1 b 1 n sat, 2 b 2 n sat, 3 b 3 Mg 2 (dobpdc) Mn 2 (dobpdc) Fe 2 (dobpdc) Co 2 (dobpdc) Ni 2 (dobpdc) Zn 2 (dobpdc) Ni 2 (dobdc) Ni 2 (dotpdc) Table S2. Pore volumes and crystallographic densities used in total adsorption calculations. pore volume (cm 3 /g) crystallographic density (g/cm 3 ) Mg 2 (dobpdc) Mn 2 (dobpdc) Fe 2 (dobpdc) Co 2 (dobpdc) Ni 2 (dobpdc) Zn 2 (dobpdc) Ni 2 (dobdc) S7

8 Figure S7. Excess equilibrium H 2 isotherms for M 2 (dobpdc) and Ni 2 (dobdc) at 25 C. Figure S8. Equilibrium H 2 adsorption isotherms for Mg 2 (dobpdc) at 77 and 87 K along with the corresponding dual-site Langmuir fit. S8

9 Figure S9. Equilibrium H 2 adsorption isotherms for Mn 2 (dobpdc) at 77 and 87 K along with the corresponding dual-site Langmuir fit. Figure S10. Equilibrium H 2 adsorption isotherms for Fe 2 (dobpdc) at 77 and 87 K along with the corresponding dual-site Langmuir fit. S9

10 Figure S11. Equilibrium H 2 adsorption isotherms for Co 2 (dobpdc) at 77 and 87 K along with the corresponding dual-site Langmuir fit. Figure S12. Equilibrium H 2 adsorption isotherms for Ni 2 (dobpdc) at 77 and 87 K along with the corresponding triple-site Langmuir fit. S10

11 Figure S13. Equilibrium H 2 adsorption isotherms for Zn 2 (dobpdc) at 77 and 87 K along with the corresponding dual-site Langmuir fit. Figure S14. Equilibrium H 2 adsorption isotherms for Ni 2 (dobdc) at 77 and 87 K along with the corresponding triple-site Langmuir fit. S11

12 Figure S15. Equilibrium H 2 adsorption isotherms for Ni 2 (dotpdc) at 77 and 87 K along with the corresponding triple-site Langmuir fit. S12

13 Figure S16. Linear BET plot for Mg 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. Figure S17. Linear BET plot for Mn 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. S13

14 Figure S18. Linear BET plot for Fe 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. Figure S19. Linear BET plot for Co 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. S14

15 Figure S20. Linear BET plot for Ni 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. Figure S21. Linear BET plot for Mn 2 (dobpdc) used to ensure that the BET calculations were done correctly and in the right pressure range. S15

16 Table S3. Additional performance metrics and physical properties of M 2 (dobpdc) M 2(dobpdc) Gravimetric Metal Density Weight Percent Hydrogen Volumetric Metal Density Crystallographic Density a (Å) c (Å) Volume (Å 3 ) (mmol M 2+ /g) (1 H 2 / M 2+ ) (mmol M 2+ /cm 3 ) (g/cm 3 ) Mg % (4) 6.824(2) 2718 Mn % (3) 6.958(2) 2819(1) Fe % Co % (3) 6.798(2) 2731(1) Ni % (3) 6.809(3) 2745(1) Zn % (1) (7) (4) Figure S22. Plot of low pressure 77K H 2 adsorption measurements for Ni 2 (dobdc) and Ni 2 (dobpdc) (left). Plot of strength of hydrogen binding (enthalpy of adsorption) measurements for Ni 2 (dobdc) and Ni 2 (dobpdc) (right). S16

17 Table S4. Atomic parameters from Rietveld refinement of desolvated Fe 2 (dobpdc) at 10 K, P3 2 21, a = (4) Å, c = 6.814(3) Å, V = 2817.(1) Å 3. Values in parentheses indicate one standard deviation in the refined value. Goodness-of-fit parameters: χ 2 = 1.686; wrp = 4.53 %; Rp = 3.83 %. Refined composition: Fe 1 C 7 O 3 H 0.98 D 2.02 Atom X Y Z Occupancy U (ISO) (Å 2 ) Multiplicity Fe (1) 0.278(1) 1.138(4) (7) 6 O (3) 0.239(2) 0.935(7) (7) 6 O (2) 0.355(3) 0.907(7) (7) 6 O (2) 0.205(2) 1.362(7) (7) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 D (1) 6 D (1) 6 D (3) 0.05(1) 6 H (3) 0.05(1) 6 Table S5. Atomic parameters from Rietveld refinement of Fe 2 (dobpdc) at a loading of 0.75 D 2 per Fe 2+ and 10 K, P3 2 21, a = (4) Å, c = 6.854(2) Å, V = 2829.(1) Å 3. Values in parentheses indicate one standard deviation in the refined value. Goodness-of-fit parameters: χ 2 = 1.764; wrp = 4.90 %; Rp = 4.13 %. Refined composition: Fe 1 C 7 O 3 H 1 D 2 : D 2 (0.87) Atom X Y Z Occupancy U (ISO) (Å 2 ) Multiplicity Fe (1) 0.280(1) 1.138(4) (7) 6 O (3) 0.237(2) 0.935(7) (8) 6 O (2) 0.360(2) 0.928(7) (8) 6 O (2) 0.205(2) 1.367(7) (8) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 D (1) 6 D (1) 6 H (1) 6 D (1) 0.504(1) 0.023(3) 1.74(4) 0.07(1) 6 S17

18 Table S6. Atomic parameters from Rietveld refinement of Fe 2 (dobpdc) at a loading of 1.5 D 2 per Fe 2+ and 10 K, P3 2 21, a = (4) Å, c = 6.870(2) Å, V = 2833.(1) Å 3. Values in parentheses indicate one standard deviation in the refined value. Goodness-of-fit parameters: χ 2 = 1.759; wrp = 4.61 %; Rp = 3.75 %. Refined composition: Fe 1 C 7 O 3 H 1 D 2 : D 2 (1.6) Atom X Y Z Occupancy U (ISO) (Å 2 ) Multiplicity Fe (1) 0.282(1) 1.143(3) (5) 6 O (2) 0.238(2) 0.947(4) (6) 6 O (2) 0.365(2) 0.925(5) (6) 6 O (2) 0.207(1) 1.373(4) (6) 6 C (1) 6 C (1) 6 C (1) 6 C (1) 6 C (1) 6 C (1) 6 C (1) 6 D (7) 6 D (7) 6 H (7) 6 D (2) 0.504(1) 0.041(5) (2) 6 D (1) 0.481(2) 0.459(5) 1.20(4) 0.03(1) 6 Table S7. Atomic parameters from Rietveld refinement of Fe 2 (dobpdc) at a loading of 2.75 D 2 per Fe 2+ and 10 K, P3 2 21, a = (5) Å, c = 6.869(2) Å, V = 2830.(1) Å 3. Values in parentheses indicate one standard deviation in the refined value. Goodness-of-fit parameters: χ 2 = 2.628; wrp = 4.82 %; Rp = 3.73 %. Refined composition: Fe 1 C 7 O 3 H 1 D 2 : D 2 (2.82) Atom X Y Z Occupancy U (ISO) (Å 2 ) Multiplicity Fe (2) 0.281(2) 1.145(4) (8) 6 O (3) 0.243(2) 0.958(8) (8) 6 O (3) 0.358(3) 0.922(7) (8) 6 O (2) 0.205(2) 1.370(7) (8) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 C (3) 6 D (2) 6 D (2) 6 H (2) 6 D (2) 0.506(2) 0.042(7) 1.7(1) 0.18(4) 6 D (1) 0.481(2) 0.445(5) 2.05(7) 0.07(1) 6 D3' 0.382(4) 0.267(4) 1.052(9) 0.87(6) 0.11(1) 6 D (3) 0.071(3) 0.858(9) 0.99(5) 0.11(1) 6 S18

19 Table S8. Atomic parameters from Rietveld refinement of Fe 2 (dobpdc) at a loading of 4.5 D 2 per Fe 2+ and 10 K, P3 2 21, a = (5) Å, c = 6.873(2) Å, V = 2841.(1) Å 3. Values in parentheses indicate one standard deviation in the refined value. Goodness-of-fit parameters: χ 2 = 2.413; wrp = 5.46 %; Rp = 4.41 %. Refined composition: Fe 1 C 7 O 3 H 1 D 2 : D 2 (4.57) Atom X Y Z Occupancy U (ISO) (Å 2 ) Multiplicity Fe (2) 0.285(2) 1.156(5) (1) 6 O (4) 0.242(3) 0.966(9) (1) 6 O (3) 0.363(3) 0.916(9) (1) 6 O (3) 0.205(3) 1.359(8) (1) 6 C (6) 6 C (6) 6 C (6) 6 C (6) 6 C (6) 6 C (6) 6 C (6) 6 D (2) 6 D (2) 6 H (2) 6 D (3) 0.506(3) 0.043(7) 2.0(2) 0.21(5) 6 D (2) 0.478(2) 0.456(4) 2.0(1) 0.02(1) 6 D3' 0.378(2) 0.276(2) 1.037(6) 2.0(1) 0.12(3) 6 D (4) 0.086(5) 0.837(9) 2.0(2) 0.30(6) 6 D5' 0.635(5) 0.635(5) (4) 0.5(1) 3 Figure S23. Rietveld refinement of the experimental neutron diffraction pattern (10 K) of evacuated Fe 2 (dobpdc) as described in the text. The calculated pattern (red trace) is in good agreement with the experimental data (circles) as evidenced by the difference pattern (blue trace) between calculated and experimental data. Final Rietveld fit parameter was χ 2 = S19

20 Figure S24. Rietveld refinement of the experimental neutron diffraction pattern (10 K) of Fe 2 (dobpdc) at a loading of 0.75 D 2 per Fe 2+ as described in the text. The calculated pattern (red trace) is in good agreement with the experimental data (circles) as evidenced by the difference pattern (blue trace) between calculated and experimental data. Final Rietveld fit parameter was χ 2 = Figure S25. Rietveld refinement of the experimental neutron diffraction pattern (10 K) of Fe 2 (dobpdc) at a loading of 1.5 D 2 per Fe 2+ as described in the text. The calculated pattern (red trace) is in good agreement with the experimental data (circles) as evidenced by the difference pattern (blue trace) between calculated and experimental data. Final Rietveld fit parameter was χ 2 = S20

21 Figure S26. Rietveld refinement of the experimental neutron diffraction pattern (10 K) of Fe 2 (dobpdc) at a loading of 2.75 D 2 per Fe 2+ as described in the text. The calculated pattern (red trace) is in good agreement with the experimental data (circles) as evidenced by the difference pattern (blue trace) between calculated and experimental data. Final Rietveld fit parameter was χ 2 = Figure S27. Rietveld refinement of the experimental neutron diffraction pattern (10 K) of Fe 2 (dobpdc) at a loading of 4.5 D 2 per Fe 2+ as described in the text. The calculated pattern (red trace) is in good agreement with the experimental data (circles) as evidenced by the difference pattern (blue trace) between calculated and experimental data. Final Rietveld fit parameter was χ 2 = S21

22 Synthesis of Co 2 (dobpdc)(def) 2 Single Crystals. H 4 (dobpdc) (425 mg, 1.46 mmol), Co(NO 3 ) 2 6H 2 O (160 mg, 0.58 mmol), and 20 ml of 1:1:1 diethylformamide (DEF)/ethanol/ water were placed into a 100 ml Pyrex jar with a Teflon cap. The solution was sonicated for 1 min and then placed in an oven that was preheated to 120 C for 60 h, yielding clusters of pink, needle-shaped crystals. Single-Crystal X-ray Diffraction. Single-crystal X-ray diffraction data for Co 2 (dobpdc)(def) 2 were collected at Beamline at the Advanced Light Source at Lawrence Berkeley National Laboratory using synchrotron radiation (λ = Å) with a Bruker PHOTON 100 CMOS detector on a Bruker AXS D8 diffractometer through a combination of 4 phi and 1 phi and omega scans. Data were collected from a single crystal mounted on a MiTeGen loop with Paratone-N oil and frozen at 100 K by an Oxford Cryosystems Cryostream 700 Plus. Bruker AXS SAINT software 4 was used to integrate the raw data and correct for Lorentz and polarization effects, and SADABS 5 was used to apply absorption corrections. Space group assignment of P was made based on prior single-crystal solution of the isostructural Zn 2 (dobpdc) framework and was verified by examination of systematic absences, E-statistics, and successive structure refinement. SHELXT 6,7,8 was used to solve the structure using direct methods, and SHELXL 9 was used for refinement within the OLEX2 10 interface. All non-hydrogen atoms were refined anisotropically, and a riding model was used to refine their positions. Owing to the calculated Flack parameter of 0.49, the structure was refined as an inversion twin. Diethylformamide (DEF) solvent molecules oriented into the pores of the structure were refined as disordered over two positions and required restraints. Residual electron density in the pores could not be modeled and is likely due to disordered solvent molecules. S22

23 Table S9. Crystal Data and Structure Refinement for Co 2 (dobpdc)(def) 2. Empirical formula C 24 H 28 Co 2 N 2 O 8 Formula weight (g/mol) Temperature (K) 100(2) Crystal system trigonal Space group P a (Å) (5) b (Å) (5) c (Å) (2) α ( ) 90 β ( ) 90 γ ( ) 120 Volume (Å 3 ) (15) Z 3 ρ calc (g/cm 3 ) µ (mm -1 ) F(000) Crystal size (mm 3 ) Radiation synchrotron (λ = ) 2Θ range for data collection ( ) to Index ranges 24 h 24, 24 k 24, 7 l 7 Reflections collected Independent reflections 2857 [R int = , R sigma = ] Data/restraints/parameters 2857/63/204 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = Largest diff. peak/hole (e/å 3 ) 0.43/ 1.00 S23

24 Figure S28. Bottom (in red): 2 H NMR (400 MHz, acetone-d 6 ) Ph-D signals at 6.92 and 7.45 ppm. Top (in black): 1 H NMR (acetone-d6) showing proton residues. Figure S C NMR (in acetone-d6). Top (in black) is 13 C {1H} spectrum showing triplet for the carbon baring D, bottom (in red) is 13 C { 1 H, 2 H} where the triplet is resolved into singlet confirming C-D. S24

25 Figure S30. ESI-MS m/z: 193 [M-H] - overall 97.4% D levels with isotopic distribution d8 79.3%, d7 20.7%. S25

26 Figure S31. Background subtracted Inelastic Neutron Scattering spectrum of Fe 2 (dobpdc)-d 6 at D 2 loadings of 0.5 (black), 1.5 (blue), 3.0 (red), 4.5 (yellow), and 5.5 (green) H 2 /Fe. For interaction with the primary adsorption site at the Fe 2+ : The lowest peak is at 6.07(2) mev at 0.5 H 2 shifting to 5.74(2) mev by 3.0 H 2 and 5.02(6) mev by 5.5 H 2, a shift of 1.05(6) mev or 0.19 mev/h 2, about half that compared to Fe-MOF-74 which starts at 6.047(7) mev at 0.5 H 2 and moves to 4.67(3) mev by 3.75 H 2, a shift of 1.4(1) mev or 0.43 mev/h 2. S26

27 References (1) Kapelewski, M. T.; Geier, S. J.; Hudson, M. R.; Stück, D.; Mason, J. A.; Nelson, J. N.: Xiao, D. J.; Hulvey, Z.; Gilmour, E.; FitzGerald, S. A.; Head-Gordon, M.; Brown, C. M.; Long, J. R. J. Am. Chem. Soc. 2014, 136, (2) E. W. Lemmon, M. L. Huber and M. O. McLinden, NIST Standard Reference Database 23:Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 8.0, National Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, (3) U. Setzmann and W. Wagner, J. Phys. Chem. Ref. Data, 1991, 20, (4) SAINT and APEX 2 Software for CCD Diffractometers, Bruker Analytical X-ray Systems Inc., Madison, WI, USA, (5) Sheldrick, G. M. SADABS, Bruker Analytical X-ray Systems Inc., Madison, WI, USA, (6) Sheldrick, G. M. SHELXT, University of Göttingen, Germany, (7) Sheldrick, G. M. Acta Crystallogr., A, Found. Crystallogr. 2008, 64, (8) McDonald, T. M.; Lee, W. R.; Mason, J. A.; Wiers, B. M.; Hong, C. S.; Long, J. R. J. Am. Chem. Soc. 2012, 134, (9) Sheldrick, G. M. SHELXL, University of Göttingen, Germany, (10) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Cryst. 2009, 42, S27

Department of Chemistry, University of California, Berkeley, California, , USA. b

Department of Chemistry, University of California, Berkeley, California, , USA. b Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Information for: Structural characterization of framework gas