Abstract
A new metal–organic coordination polymer [Zn2(sedc)2(dabco)] (1se; sedc2− = selepophene-2,5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn2(OOCR)4N2} paddle wheels and is isoreticular to the family of [Zn2(bdc)2(dabco)] derivatives (1b; bdc2− = 1,4-benzenedicarboxylate) with pcu topology. The gas adsorption measurements revealed that 1se shows a 15% higher CO2 volumetric uptake at 273 K and 28% higher CO2 uptake at 298 K (both at 1 bar) compared to the prototypic framework 1b. Methane and nitrogen adsorption at 273 K was also investigated, and IAST calculations demonstrated a pronounced increase in CO2/CH4 and CO2/N2 selectivity for 1se, compared with 1b. For example, the selectivity factor for the equimolar CO2/CH4 gas mixture at 1 bar = 15.1 for 1se and 11.9 for 1b. The obtained results show a remarkable effect of the presence of selenium atom on the carbon dioxide affinity in the isoreticular metal–organic frameworks with very similar geometry and porosity.
Highlights
Carbon dioxide is a corrosive gas and a major atmospheric pollutant, causing a greenhouse effect
Family, such as IRMOF-1 [11,12,13], MIL-53 [14,15,16], or UiO-66 [17,18,19], which are typically based on the linear 1,4-benzenedicarboxylate linker
We report the synthesis and investigation of a new selenophenedicarboxylate-based porous metal–organic frameworks (MOFs) [Zn22] (1se), which is isoreticular to both [Zn22 dabco)] (1b) and [Zn22] (1t)
Summary
Carbon dioxide is a corrosive gas and a major atmospheric pollutant, causing a greenhouse effect. Selective capture and sequestration of carbon dioxide is one of the challenging problems in the modern chemical industry. Remarkable porosity, sufficient stability, as well as vast versatility of the structural and functional design make this class of porous materials among the most perspective adsorbents for selective CO2 capture from natural gas or industrial flue gas [5,6,7,8,9,10]. Modular design is a widely used principle to tailor structural and/or functional properties within a certain type of isostructural MOF family, such as IRMOF-1 [11,12,13], MIL-53 [14,15,16], or UiO-66 [17,18,19], which are typically based on the linear 1,4-benzenedicarboxylate (bdc2− ) linker. A number of research groups have shown that the incorporation of 2,5-furanedicarboxylate (fdc2− ) or Molecules 2020, 25, 4396; doi:10.3390/molecules25194396 www.mdpi.com/journal/molecules
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