An Integrated Computational–Experimental Hierarchical Approach for the Rational Design of an IL/UiO‐66 Composite Offering Infinite CO₂ Selectivity

Abstract

Owing to the possibility of generating theoretically unlimited numbers of ionic liquid (IL)-metal-organic framework (MOF) combinations, experimental studies on IL/MOF composites for gas separation applications are mostly conducted on a trial-and-error basis. To address this problem, an integrated computational-experimental hierarchical approach is presented for selecting the best IL-MOF combination for a target gas separation application. For this purpose, UiO-66 and pyrrolidinium-based ILs are chosen as the parent MOF and IL family, respectively, and three powerful computational tools, Conductor-like Screening Model for Realistic Solvents calculations, density functional theory calculations, and grand canonical Monte Carlo simulations, are integrated to identify the most promising IL-UiO-66 combination as 1-n-butyl-1-methylpyrrolidinium dicyanamide/UiO-66, [BMPyrr][DCA]/UiO-66. Then, this composite is synthesized, characterized in deep detail, and tested for CO 2 /N 2 , CO 2 /CH 4 , and CH 4 /N 2 separations. Results demonstrate that [BMPyrr][DCA]/UiO-66 offers an extraordinary gas separation performance, with practically infinite CO 2 and CH 4 selectivities over N 2 at 15 °C and at low pressures. The integrated hierarchical approach proposed in this work paves the way for the rational design and development of novel IL/MOF composites offering exceptional performance for any desired gas separation application.

Synthesis of UiO-66-Sal-Cu(OH)2 by a Simple and Novel Method: MOF-Based Metal Thin Film as a Heterogeneous Catalyst for Olefin Oxidation

“…The catalytic behavior of the sample was investigated. Also, a literature method was followed for the preparation of UiO-66 and UiO-66-NH 2 − crystals. The same method was used for UiO-66 and UiO-66-NH 2 , but it did not lead to the creation of a thin film of MOF.…”

“…One of the most significant batches of porous materials is metal–organic frameworks (MOFs). − Owing to a large surface area, adjustable attributes, and peerless topology, MOFs are extremely advantageous in gas adsorption, , catalysts, and other usages . The postsynthetic modification (PSM) of MOFs is an appropriate way of synthesizing functionalized MOFs and begetting numerous active positions. , Postimmobilized metal ions or metal nanoparticles thereon on a MOF scaffolding is a very powerful instrumentation for inorganic catalysts that merges the preponderances of simple separation and restoration of heterogeneous catalysts with the great catalytic activity of dissolved transition-metal complexes.…”

Incorporation of 1-ethyl-3-methyl-imidazolium acetate into UiO-66 as an efficient sorbent for carbon dioxide capture

“…The band at 742 cm À1 is assigned to the asymmetric Zr-O mode stretching frequencies, whereas the two intense peaks at 1393 and 1587 cm À1 belong to the symmetric and asymmetric (O-C-O) stretching vibrations of the carboxylate group, respectively. 39 However, compared with the pristine UiO-66, blue shifts in band positions were noticed, which can be explained by the strong interaction of the O atom of [Ac] À with the metal nodes of UiO-66. 40 For instance, the peaks at 742, 1393, and 1587 cm À1 were blue-shifted to 768, 1418, and 1597 cm À1 upon the incorporation of [Emim][Ac] (Fig.…”

Integrating Molecular Simulations with Machine Learning Guides in the Design and Synthesis of [BMIM][BF4]/MOF Composites for CO2/N2 Separation

“…The N 2 adsorption−desorption isotherm of the [BMIM][BF 4 ]/UiO-66 composite (Figure S8) showed a reduction in both the surface area and pore volume (Table S5) compared to that of pristine UiO-66, indicating the successful incorporation of IL molecules into the MOF pores, consistent with the studies of previously reported IL/MOF composites. 6,9,59 Moreover, conductor-like screening model for realistic solvents (COSMO-RS) solubility calculations (Figure S9) demonstrated that N 2 has almost negligible solubility in [BMIM][BF 4 ] at the BET measurement conditions.…”

“…Metal–organic frameworks (MOFs), consisting of metal nodes and organic linkers, have been widely studied for gas separation thanks to their tunable pore sizes and chemical functionalities. − One of the major advancements in this field is the incorporation of ionic liquids (ILs) into MOFs via post-synthesis modification techniques , to improve the selectivity of MOFs by tuning the relative affinity of composites for a specific molecule, such as CO 2 . Experimental studies have examined a very limited number of IL/MOF composites to date for CO 2 /N 2 , − CO 2 /CH 4 , − ,− ,− and CH 4 /N 2 − ,,, separations and revealed their high gas separation potentials. There may be many other IL/MOF composites that can outperform the existing porous materials in terms of gas separation performance.…”