Microporous Metal–Organic Frameworks with High Gas Sorption and Separation Capacity

Abstract The design, synthesis, and structural characterization of two microporous metal–organic framework structures, M(bdc)(ted) 0.5 ·2 DMF·0.2 H 2 O (M = Zn ( 1 ), Cu ( 2 ); H 2 bdc = 1,4‐benzenedicarboxylic acid; ted = triethylenediamine; DMF: N , N ‐dimethylformamide) is reported. The pore characteristics and gas sorption properties of these compounds are investigated at cryogenic temperatures, room temperature, and higher temperatures by experimentally measuring argon, hydrogen, and selected hydrocarbon adsorption/desorption isotherms. These studies show that both compounds are highly porous with a pore volume of 0.65 ( 1 ) and 0.52 cm 3 g – 1 ( 2 ). The amount of the hydrogen uptake, 2.1 wt % ( 1 ) and 1.8 wt % ( 2 ) at 77 K (1 atm; 1 atm = 101 325 Pa), places them among the group of metal–organic frameworks (MOFs) having the highest H 2 sorption capacity. Zn(bdc)(ted) 0.5 ·2 DMF·0.2 H 2 O adsorbs a very large amount of hydrocarbons, including methanol, ethanol, dimethylether (DME), n ‐hexane, cyclohexane, and benzene, giving the highest sorption values among all metal–organic based porous materials reported to date. In addition, these materials hold great promise for gas separation.