Computer-Aided Discovery of MOFs with Calixarene-Analogous Microenvironment for Exceptional SF₆ Capture

Abstract

Finding optimal adsorbents to achieve an efficient capture and recovery of sulfur hexafluoride (SF 6 ) from SF 6 /N 2 mixture is of great industrial importance. To address this key challenge, here we present a materials-genomics-accelerated strategy by integrating high-throughput computational screening with subsequent synthesis and adsorption/separation testing of the identified promising material. From over 10140 metal−organic frameworks (MOFs), those with calixarene-analogous pore feature were computationally identified as optimal adsorbents with exceptional SF 6 /N 2 selectivity and SF 6 uptake. The separation mechanism was revealed to be thermodynamically driven owing to the synergistic contribution of multiple hydrogen-bond and van der Waals-type SF 6 /MOF pore wall interactions. As a proof-ofconcept, one of the discovered MOFs was further synthesized, and equilibrium adsorption measurements demonstrated both record SF 6 adsorption capacity as a single component at 0.1 bar (3.39 mmol g −1 ) and SF 6 /N 2 IAST-predicted selectivity (∼266) under ambient conditions. Besides its excellent regeneration and cycling performance, dynamic breakthrough experiments further confirmed the attractiveness of this MOF for SF 6 capture under working conditions.

Amino-Functionalized Microporous MOFs for Capturing Greenhouse Gases CF4 and NF3 with Record Selectivity

“…Pressure swing adsorption (PSA) based on adsorbents has shown advantages for gas separation due to its operational simplicity and energy efficiency. − The adsorbent is the key to the PSA process, which is supposed to possess high capacity and selectivity . It has been reported that SF 6 capture and SF 6 /N 2 selectivity are high. − However, the values of CF 4 sorption and CF 4 /N 2 selectivity are generally very low. ,, Also, the separation of CF 4 /N 2 and NF 3 /N 2 is more challenging than that of SF 6 /N 2 due to the smaller kinetic diameters of CF 4 and NF 3 (4.6 Å for CF 4 , 3.6 Å for NF 3 , 5.1 Å for SF 6 ) …”

Spray drying-assisted construction of hierarchically porous ZIF-8 for controlled release of doxorubicin

“…Metal–organic frameworks (MOFs), a class of hybrid porous coordination materials assembled with metal centers and organic ligands, 1,2 have attracted extensive attention and exhibit promising applications in storage, 3,4 adsorption and separation, 5–9 catalysis, 10–15 sensing, 16–18 and drug delivery 19–23 owing to their structural diversity, large surface area, and high porosity. As a potential drug carrier, compared with other traditional materials such as polymeric micelles, liposomes and inorganic nanoparticles, 24–26 some MOFs are advantageous on account of their high loading capacity, biodegradability, and nontoxicity when specific ligands and metals (Fe, Zn, Ca, etc .)…”

A Stable Cu(I)-Based Ultramicroporous NKMOF-8-Br with High CH4 Uptake for Efficient Separation of CH4/N2 Mixtures

“…Unfortunately, these traditional adsorbents are constrained by the low CH 4 adsorption capacity and CH 4 /N 2 selectivity. Metal–organic frameworks (MOFs) are composed of metal ions and organic ligands bridged through a self-assembly process to form periodically structured porous materials. − It has been widely used in gas adsorption and separation, − catalysis, − sensing, − and other fields. , MOFs show significant advantages compared to other adsorbents in gas adsorption and separation because their pore sizes and chemical properties can be designed and controlled from the first principles. ,− Researchers have been dedicated to developing high-performance MOFs to capture CH 4 from CH 4 /N 2 mixtures in the past decades, such as Al-CDC (13.1), SBMOF-1 (11.5), and Co 3 (C 4 O 4 ) 2 (OH) 2 (12.5) . From the practical point of view, the ideal MOFs for CH 4 /N 2 separation should have high CH 4 /N 2 selectivity and excellent adsorption capacity of CH 4 , which has an important impact on the purity and yield.…”