Supporting Information for the manuscript. Metastable interwoven mesoporous metal-organic frameworks

Transcription

1 S1 Supporting Information for the manuscript Metastable interwoven mesoporous metal-organic frameworks Yabing He, ab Zhiyong Guo, b Shengchang Xiang, c Zhangjing Zhang, c Wei Zhou, d,e Frank R. Fronczek, f Sean Parkin, g Stephen T. Hyde, h Michael O Keeffe, i and Banglin Chen *b a College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 324, China b Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas , United States; Fax: (1) ; Banglin.Chen@utsa.edu; Homepage: c College of Chemistry and Material, Fujian Normal University, 3 Shangsan Road, Cangshang Region, Fuzhou 357, China d NIST Center for Neutron Research, Gaithersburg, Maryland , United States e Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 2742, United States f Department of Chemistry, Louisiana State University, Baton Rouge, LA , United States g Department of Chemistry, University of Kentucky, Lexington, KY, , United States h Department of Applied Mathematics, Australian National University, Canberra, Australia i Department of Chemistry and Biochemistry, Arizona State University Tempe, Arizona , United States

2 S2 As-synthesized Simulated Figure S1. PXRD pattern of as-synthesized UTSA-28-Cu (red) along with the simulated XRD pattern from single-crystal X-ray structure (black).

3 S3 As-synthesized Simulated / o Figure S2. PXRD pattern of as-synthesized UTSA-28-Zn (green) along with the simulated XRD pattern from single-crystal X-ray structure (black). As-synthesized Simulated / o Figure S3. PXRD pattern of as-synthesized UTSA-28-Mn (blue) along with the simulated XRD pattern from single-crystal X-ray structure (black).

4 S4 8 UTSA-28-Cu UTSA-28-Zn UTSA-28-Mn Weight (%) T ( o C) Figure S4. TGA curves of as-synthesized UTSA-28-Cu (red), UTSA-28-Zn (green) and UTSA-28-Mn (blue) under a nitrogen atmosphere. N 2 uptake (cm 3 g -1, STP) P/P o Figure S5. N 2 sorption isotherms of the activated, UTSA-28e-Cu (b), and UTSA-1f-Cu (c) at 77 K. The as-prepared samples were guest-exchanged with dry acetone, and then outgassed under high vacuum at 296 K, 333 K, and 393 K to yield the activated, UTSA-28e-Cu, and UTSA-1f-Cu, respectively. It can be seen that further increasing the activation temperature deteriorates the porosity. (b) (c)

5 (b) Figure S6. Photographs of single crystals UTSA-28-Zn, and (b) metal ion exchanged samples UTSA-28-Zn(Cu). Simulated UTSA-28-Zn(Cu) UTSA-28a-Zn(Cu) Intensity / o Figure S7. PXRD patterns of UTSA-28-Zn(Cu) (red) and UTSA-28a-Zn(Cu) (blue), together with the simulated XRD pattern from cif file of UTSA-28-Zn. S5

6 S6 Transimittance Cu(NO 3 ) 2 2.5H 2 O UTSA-28a-Zn(Cu) Wavenumber (cm -1 ) Figure S8. FTIR spectrum of UTSA-28a-Zn(Cu). The absence of NO - 3 stretching bands at 1385 and 825 cm -1 in the FTIR spectrum of UTSA-28a-Zn(Cu) indicated that no Cu 2+ ions were absorbed in the pores of framework. H 2 uptake (wt%) Excess 77 K 87 K K H 2 uptake (wt%) (b) Absolute 77 K 87 K K Figure S9. High pressure excess and absolute (b) H 2 sorption isotherms of. The solid and open symbols represent adsorption and desorption data, respectively.

7 S7 CH 4 uptake (cm 3 g -1, STP) Excess 24 K 27 K 29 K 3 K CH 4 uptake (cm 3 g -1, STP) (b) Absolute 24 K 27 K 29 K 3 K Figure S1. High pressure CH 4 excess and absolute (b) sorption isotherms of. The solid and open symbols represent adsorption and desorption data, respectively. CO 2 uptake (cm 3 g -1, STP) Excess 6 24 K 27 K 5 29 K 4 3 K CO 2 uptake (cm 3 g -1, STP) Absolute 6 (b) 24 K 27 K 5 29 K 4 3 K Figure S11. High pressure excess and absolute (b) CO 2 sorption isotherms of. The solid and open symbols represent adsorption and desorption data, respectively.

8 S8 12 C 2 H 2, 273 K Uptake (cm 3 g -1, STP) (b) Uptake (cm 3 g -1, STP) 8 C 2 H 4 C 2 H 6 CH P (mmhg) 8, 296 K C 2 H 2 7 C 2 H 4 6 C 2 H 6 5 CH P (mmhg) Figure S12. C 2 H 2, C 2 H 4, C 2 H 6 and CH 4 sorption isotherms of at 273 K and 296 K (b). The solid and open symbols represent adsorption and desorption data, respectively.

9 S9 Ligand UTSA-28-Cu UTSA-28-Zn UTSA-28-Mn Transimittance Wavenumber (cm -1 ) Figure S13. FTIR spectra of the organic ligand (black), UTSA-28-Cu (red), UTSA-28-Zn (green) and UTSA-28-Mn (blue). Table S1. Sorption data under different activation methods. Compounds Activation Solvent Activation Temperature (K) BET (m 2 /g) Langmuir (m 2 /g) Vp (cm 3 /g) Acetone UTSA-28b-Cu CH 2 Cl UTSA-28c-Cu MeOH UTSA-28d-Cu Freeze drying UTSA-28e-Cu Acetone UTSA-28f-Cu Acetone UTSA-28a-Zn Acetone UTSA-28b-Zn CH 2 Cl UTSA-28c-Zn MeOH UTSA-28d-Zn Freeze drying 2 3. UTSA-28a-Mn Acetone UTSA-28b-Mn CH 2 Cl UTSA-28c-Mn MeOH UTSA-28d-Mn Freeze drying UTSA-28a-Zn(Cu) Acetone UTSA-28a-Mn(Cu) Acetone

10 S1 Table S2. Virial analyses data for and separation selectivities of C 2 hydrocarbons over methane. Adsorbate C 2 H 2 C 2 H 4 C 2 H 6 CH 4 T (K) A [In(mol g -1 Pa -1 ] A 1 (g mol -1 ) R 2 K H (mol -1 g -1 Pa -1 ) S i/ch Q st, n = (kj mol -1 )

11 S11 Table S3. Crystal data and structure refinement for UTSA-28-Cu, UTSA-28-Zn, and UTSA-28-Mn. Identification code UTSA-28-Cu UTSA-28-Zn UTSA-28-Mn Empirical formula C 39 H 24 Cu 1.5 O 7.5 C 26 H 16 O 5 Zn C 156 H 96 Mn 6 O 3 Formula weight Temperature (K) 293(2) 9(2) 243(2) Wavelength (Å) Crystal system, space group Cubic, Pn-3n Cubic, Pn-3n Cubic, Pn-3n a = 32.99(2) Å b = 32.99(2) Å a = (15) Å b = (15) Å a = (18) Å b = (18) Å Unit cell dimensions c = 32.99(2) Å c = (15) Å c = (18) Å α = 9 o α = 9 o α = 9 o γ = 9 β = 9 o γ = 9 β = 9 o γ = 9 β = 9 o Volume (Å 3 ) 3594(4) 35496(3) 37635(4) Z, Calculated density (g cm -3 ) 16, , ,.496 Absorption coefficient (mm -1 ) F() Crystal size (mm) θ range for data collection ( o ).87 to to to Limiting indices -4 h 4-39 = k 4-4 l 2-39 h 2-27 k 39-3 l h 6-3 k l 9 Reflections collected / unique / / / 4527 (R int =.92) (R int =.392) (R int =.823) Completeness to θ = o. % 99.7 % 99.7 % Absorption correction Semi-empirical from Semi-empirical from Semi-empirical from equivalents equivalents equivalents Max. and min. transmission.956 and and and.965 Refinement method Full-matrix Full-matrix Full-matrix least-squares on F 2 least-squares on F 2 least-squares on F 2 Data / restraints / parameters 5973 / 1 / / / / / 146 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 =.85 wr 2 =.2385 R 1 =.654 wr 2 =.2442 R 1 =.74 wr 2 =.1773 R indices (all data) R 1 =.1737 wr 2 =.2846 R 1 =.754 wr 2 =.2584 R 1 =.1184 wr 2 =.1926 Largest diff. peak and hole (e.å -3 ).516 and and and CCDC