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

The design, synthesis, and structural characterization of two microporous metal–organic framework structures, [M(bdc)(ted)0.5]·2 DMF·0.2 H2O (M = Zn (1), Cu (2); H2bdc = 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 cm3 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 H2 sorption capacity. [Zn(bdc)(ted)0.5]·2 DMF·0.2 H2O 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. Microporous metal–organic framework structures [M(bdc)(ted)0.5]·2 DMF· 0.2 H2O (M = Zn (1), Cu (2); H2bdc = 1,4‐benzenedicarboxylic acid; ted = triethylenediamine; DMF: N,N‐dimethylformamide) exhibit very high gas storage and separation capability for hydrogen and selected hydrocarbons, such as alcohols and dimethylether (DME, see figure). 1 gives the highest sorption values among all metal–organic based porous materials reported to date.