Composite of MIL-101(Cr) with a Pyrrolidinium-Based Ionic Liquid Providing High CO(2) Selectivity

[Image: see text] Capturing CO(2) selectively from flue gas and natural gas addresses the criteria of a sustainable society. In this work, we incorporated an ionic liquid (IL) (1-methyl-1-propyl pyrrolidinium dicyanamide, [MPPyr][DCA]) into a metal organic framework (MOF), MIL-101(Cr), by wet impregnation and characterized the resulting [MPPyr][DCA]/MIL-101(Cr) composite in deep detail to identify the interactions between [MPPyr][DCA] molecules and MIL-101(Cr). Consequences of these interactions on the CO(2)/N(2), CO(2)/CH(4), and CH(4)/N(2) separation performance of the composite were examined by volumetric gas adsorption measurements complemented by the density functional theory (DFT) calculations. Results showed that the composite offers remarkably high CO(2)/N(2) and CH(4)/N(2) selectivities of 19,180 and 1915 at 0.1 bar and 15 °C corresponding to 1144- and 510-times improvements, respectively, as compared to the corresponding selectivities of pristine MIL-101(Cr). At low pressures, these selectivities reached practically infinity, making the composite completely CO(2)-selective over CH(4) and N(2). The CO(2)/CH(4) selectivity was improved from 4.6 to 11.7 at 15 °C and 0.001 bar, yielding a 2.5-times improvement, attributed to the high affinity of [MPPyr][DCA] toward CO(2), validated by the DFT calculations. These results offer broad opportunities for the design of composites where ILs are incorporated into the pores of MOFs for high performance gas separation applications to address the environmental challenges.