Eur. J. Inorg. Chem. 2016 · ISSN 1099–0682 SUPPORTING

Eur. J. Inorg. Chem. 2016 · ISSN 1099–0682 SUPPORTING INFORMATION DOI: 10.1002/ejic.201600410 Title: Observing the Effects of Shaping on Gas Adsorption in Metal-Organic Frameworks Author(s): Nicolas Chanut, Andrew D. Wiersum, U-Hwang Lee, Young Kyu Hwang, Florence Ragon, Hubert Chevreau, Sandrine Bourrelly, Bogdan Kuchta, Jong-San Chang, Christian Serre, Philip L. Llewellyn*

List of Contents 1.

Experimental ………………………………………………………………………… S-3 Synthesis of adsorbents ……………………………………………………………. S-3 Characterization of the adsorbents ………………………………………………. S-5

2.

Thermogravimetric Analysis……………………………………………………….. S-6

3.

Nitrogen Adsorption at 77K ……………………………………………………….. S-7

4.

X-ray diffraction ……………………………………………………………………. S-8

5.

Room temperature gas adsorption on UiO-66(Zr)………………………………… S-10

6.

Room temperature gas adsorption on UiO-66(Zr)_NH2………………………….. S-13

7.

Room temperature gas adsorption on MIL-100(Fe) ……………………………… S-16

8.

Room temperature gas adsorption on MIL-127(Fe) ……………………………… S-19

S-2

1. Experimental

Synthesis of adsorbents

Synthesis of UiO-66(Zr) Synthesis of UiO-66(Zr) was carried out in a 5 L glass reactor (Reactor Master, Syrris, equipped with reflux condenser and Teflon-lined mechanical stirrer) according to a previously reported method.[1] In brief, 462 g (2.8 mol) of H2BDC (98%) was initially dissolved in 2.5 L of dimethyl formamide (DMF, 2.36 kg, 32.3 mol) at room temperature. Then, 896 g (2.8 mol) of ZrOCl2·8H2O (98%) and 465 mL of 37% HCl (548 g, 15 mol) were added to the mixture. The reaction mixture was vigorously stirred to obtain a homogeneous gel. The mixture was then heated to 423 K at a rate of 1 K.min−1 and maintained at this temperature for 6 h in the reactor without stirring, leading to a crystalline UiO-66(Zr) solid. The resulting product (about 510 g) was recovered from the slurry by filtration, re-dispersed in 7 L of DMF at 333 K for 6 h under stirring, and recovered by filtration. The same procedure was repeated twice, using MeOH instead of DMF. The solid product was finally dried at 373 K overnight.

Synthesis of UiO-66(Zr)-NH2 UiO-66(Zr)-NH2 was synthesized by a reflux method. Initially, 250 mL of DMF was taken into a 500 ml round-bottom flask. Next, ZrOCl2.8H2O (16.11 g, 0.05 mol), 2-amino-1,4-benzenedicarboxylic acid (9.06 g, 0.05 mol) and HCl (8.35 ml, 0.27 mol) were added to the round-bottom flask containing DMF. The reaction solution was heated to 426 K and holds at this temperature for 24 h. After cooling down to room temperature, the yellow precipitate was filtered off and washed with DMF followed by methanol (twice) at 333 K for 2 h to remove unreacted ligand moiety from the pores. The purified yellowish powder was then dried at 373 K in oven for 12 h.

Synthesis of MIL-100(Fe) MIL-100(Fe) was synthesized by a synthesis protocol previously reported elsewhere.[2] It was prepared from a hydrothermal reaction of trimesic acid (1,3,5-benzenetricarboxylic acid or 1,3,5-BTC) with metallic iron, HF, nitric acid, and H2O. The composition of the reaction mixture was 1.0 Fe : 0.67 1,3,5-BTC : 2.0 HF : 0.6 HNO3 : 277 H2O. The reaction mixture was loaded into a Teflon autoclave, heated to 423 K, and held at this temperature for 12 h. The reaction mixture remained acidic throughout the preparation. After 12 h, the resulting light orange solid was recovered by filtration, and washed with deionised water. The resulting MIL-100(Fe) was purified further via a twostep process using hot water and ethanol. Finally, the resulting solid was dried overnight below 373 K under a nitrogen atmosphere.

Synthesis of MIL-127(Fe) MIL-127(Fe) was synthesized by reaction of 3.27 g of Fe(ClO4)3.6H2O (9.2 mmol), 3.3 g of C16N2O8H6 in 415 mL of DMF and 2.7 mL of hydrofluoric acid 5M at 423 K in a Teflon flask. The obtained orange crystals were placed in DMF (100 mL) under stirring for 5 h at ambient temperature. The final product was kept overnight at 373 K.

S-3

Shaping of adsorbents As previously reported,[3] spherical shapes of MOFs were prepared using a granulation method. Typically, MOF powder (5 g) was first mixed with an ethanolic solution (50 mL) of 3 wt % polymer binder mixture containing polyvinyl groups such as polyvinyl alcohol and polyvinyl butyral. The mixture of the MOF powder and binder was then shaped by a homemade pan-type granulator. Before the granulation, the powder sample was finely ground to achieve a narrow and similar particle size (