Enhancing of CO Uptake in Metal-Organic Frameworks by Linker Functionalization: A Multi-Scale Theoretical Study

In the present work, interaction strength of Carbon Monoxide (CO) with a set forty-two, strategically selected, functionalized benzenes was calculated. Our ab initio calculations at MP2/6-311++G** level theory reveal that phenyl hydrogen sulfate (-OSO3H) showed highest CO (?19.5 kJ/mol), which approximately three times stronger compared unfunctionalized benzene (?5.3 kJ/mol). Moreover, top-performing functional groups (-OSO3H, -OPO3H2, -SO3H) were selected to modify organic linker IRMOF-8 and test their ability capture 298 K for wide pressure range. Grand Canonical Monte Carlo (GCMC) simulations significant increase in uptake MOFs parent IRMOF-8. It is distinctive volumetric uptake, 60× observed 1 bar 2× 100 bar. The proposed functionalization strategy can be applied improving performance not only but also various other porous materials.