Functionalizing the well-known MIL-53(Al) metal-organic framework with amino groups increases its selectivity in CO(2)/CH(4) separations by orders of magnitude while maintaining a very high capacity for CO(2) capture.
Some Metal Organic Frameworks (MOFs) show excellent performance in extracting carbon dioxide from different gas mixtures. The origin of their enhanced separation ability is not clear yet. Herein, we present a combined experimental and theoretical study of the amino-functionalized MIL-53(Al) to elucidate the mechanism behind its unusual high efficiency in CO(2) capture. Spectroscopic and DFT studies point out only an indirect role of amine moieties. In contrast to other amino-functionalized CO(2) sorbents, no chemical bond between CO(2) and the NH(2) groups of the structure is formed. We demonstrate that the functionalization modulates the "breathing" behavior of the material, that is, the flexibility of the framework and its capacity to alter the structure upon the introduction of specific adsorbates. The absence of strong chemical interactions with CO(2) is of high importance for the overall performance of the adsorbent, since full regeneration can be achieved within minutes under very mild conditions, demonstrating the high potential of this type of adsorbents for PSA like systems.
The metal-organic frameworks MIL-47 (V(IV)O{O(2)C-C(6)H(4)-CO(2)}) and MIL-53(Al) (Al(III)(OH)·{O(2)C-C(6)H(4)-CO(2)}) are capable of separating ethylbenzene and styrene. Both materials adsorb up to 20-24 wt % of both compounds. Despite the fact that they have identical building schemes, the reason for preferential adsorption of styrene compared to ethylbenzene is very different for the two frameworks. For MIL-47, diffraction experiments reveal that styrene is packed inside the pores in a unique, pairwise fashion, resulting in separation factors as high as 4 in favor of styrene. These separation factors are independent of the total amount of adsorbate offered. This is due to co-adsorption of ethylbenzene in the space left available between the packed styrene pairs. The separation is of a non-enthalpic nature. On MIL-53, the origin of the preferential adsorption of styrene is related to differences in enthalpy of adsorption, which are based on different degrees of framework relaxation. The proposed adsorption mechanisms are in line with the influence of temperature on the separation factors derived from pulse chromatography: separation factors are independent of temperature for MIL-47 but vary with temperature for MIL-53. Finally, MIL-53 is also capable of removing typical impurities like o-xylene or toluene from styrene-ethylbenzene mixtures.
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