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Development of computation‐ready metal–organic framework databases (MOF DBs) has accelerated high‐throughput computational screening (HTCS) of materials to identify the best candidates for gas storage and separation. These DBs were constructed using structural curations to make MOFs directly usable for molecular simulations, which caused the same MOF to be reported with different structural features in different DBs. We examined thousands of common materials of the two recently updated, very widely used MOF DBs to reveal how structural discrepancies affect simulated CH4, H2, CO2 uptakes and CH4/H2 separation performances of MOFs. Results showed that DB selection has a significant effect on the calculated gas uptakes and ideal selectivities of materials at low pressure. A detailed analysis on the curated structures was provided to isolate the critical elements of MOFs determining the gas uptakes. Identification of the top‐performing materials for gas separation was shown to strongly depend on the DB used in simulations., We examined thousands of common materials in two widely used computation‐ready metal–organic framework databases (MOF DBs) to reveal how structural discrepancies affect simulated CH4, H2, CO2 uptakes and CH4/H2 separation performances of MOFs. Identification of the top‐performing materials for gas separation was shown to strongly depend on the DB used in simulations.

Separating CH4/N2 mixture is challenging, and performance of the existing materials is still open to improvement. In this study, we examined both the adsorption- and membrane-based CH4/N2 separation performances of 5034 different materials, including metal organic frameworks (MOFs), covalent organic frameworks (COFs), ionic liquid (IL)/MOF composites, MOF/polymer composites, and COF/polymer composites by performing high-throughput computational screening and molecular simulations. The top performing adsorbents and membranes were identified by computing several performance evaluation metrics. Investigation of the interactions between the gas molecules, the IL, and the top MOF was performed by density functional theory (DFT) calculations. Results pointed out that the interactions between the gas molecules and the linker fragments of the MOF are stronger than their interactions with the IL. Thus, as the IL molecules are loaded into the selected top MOF, they occupy the adsorption sites of the gases, decreasing CH4 and N2 uptakes and increasing the CH4/N2 selectivity. Our results revealed that MOFs offer great potential for adsorption-based CH4/N2 separation, and IL incorporation into MOFs remarkably increases their CH4/N2 selectivities. More than 25% of MOF and 70% of the COF membranes surpassed Robeson's upper bound because of high N2 permeabilities and outperformed conventional polymeric membranes. N2 permeabilities and selectivities of MOF/polymer and COF/polymer composites were found to be significantly higher than those of pure polymers. Our results emphasize the promises of the design and development of new MOF and COF adsorbents, membranes, and their composites with ILs and polymers for efficient CH4/N2 separation., European Union (EU); Horizon 2020; European Research Council (ERC); ERC-2017-Starting Grant; Research and Innovation Programme; COSMOS

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 CO2/N-2, CO2/CH4, and CH4/N-2 separations. Results demonstrate that [BMPyrr][DCA]/UiO-66 offers an extraordinary gas separation performance, with practically infinite CO2 and CH4 selectivities over N-2 at 15 degrees 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., Scientific and Technological Research Council of Turkey (TÜBİTAK); 1001-Scientific and Technological Research Projects Funding Program; European Research Council (ERC); Europian Union (EU); Horizon 2020; ERC-2017-Starting Grant; Research and Innovation Programme; COSMOS; HEC Pakistan Scholarship

1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM][DEP]) was incorporated into copper benzene-1,3,5-tricarboxylate, CuBTC. Consequences of molecular interactions on the CO2 separation performance of CuBTC were investigated. Scanning electron microscopy and X-ray diffraction results showed that the surface morphology and crystal structure of CuBTC remained intact upon the incorporation of the ionic liquid (IL); and the results of thermogravimetric analysis and infrared spectroscopy indicated the presence of interactions between the anion of the IL and the open metal sites of CuBTC. Gas adsorption measurements for the pristine CuBTC and IL-incorporated CuBTC were performed at 25 °C in a pressure range of 0.1–1 bar. Data showed that ideal CO2/CH4 and CO2/N2 selectivities of IL-incorporated CuBTC were 1.6- and 2.4-times higher compared to those of the pristine CuBTC at 0.01 bar, respectively. Moreover, for the CO2/CH4:50/50 and CO2/N2:15/85 mixtures, the corresponding selectivities were improved by more than 1.5- and 1.9-times compared to that of pristine CuBTC at 0.01 bar, respectively., Scientific and Technological Research Council of Turkey (TÜBİTAK); 1001- Scientific and Technological Research Projects Funding Program; European Union (EU); Horizon 2020; European Research Council (ERC) Research and Innovation Programme; COSMOS; Koç University Seed Fund Program; TARLA; HEC Pakistan Scholarship; METU Mustafa Parlar Foundation of Science and Education Incentive Award

Modification of the physicochemical properties of porous materials by using ionic liquids (ILs) has been widely studied for various applications. The combined advantages of ILs and porous materials provide great potential in gas adsorption and separation, catalysis, liquid-phase adsorption and separation, and ionic conductivity owing to the superior performances of the hybrid composites. In this review, we aimed to provide a perspective on the evolution of IL/porous material composites as a research field by discussing several different types of porous materials, including metal organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, and carbonaceous-materials. The main challenges and opportunities in synthesis methods, characterization techniques, applications, and future opportunities of IL/porous materials are discussed in detail to create a road map for the area. Future advances of the field addressed in this review will provide in-depth insights into the design and development of these novel hybrid materials and their replacement with conventional materials., Scientific and Technological Research Council of Turkey (TÜBİTAK); 1001-Scientific and Technological Research Projects; Koç University Seed Fund Program; European Union (EU); Horizon 2020; European Research Council (ERC); ERC-2017-Starting Grant; COSMOS; TARLA