Enhanced CO₂ capture in partially interpenetrated MOFs: Synergistic effects from functional group, pore size, and...

Excessive CO₂ emissions have contributed to global environmental issues, driving the development of CO₂ capture adsorbents. Among various candidates, metal-organic frameworks (MOFs) are considered the most promising due to their unique microporous structure. Herein, a series of partially interpenetrated MOFs named UPC-XX were built to investigate the continuous enhancement in CO₂ capture performance via synergistic effects from functional group, pore size, and steric-hindrance using theoretical calculations. It's showed that the introduction of functional groups improved the structure polarity and created more adsorption sites, thus, enhanced CO₂ capture capacity. The pore size modification augments the exposure of adsorption sites to mitigate the negative impact of pore space and surface area reduction caused by the introduction of functional groups, thereby further increasing the CO₂ capture capacity. The steric-hindrance effect optimized the adsorption sites distribution, which hasn't been considered in the previous two regulation strategies, thus, further increased the CO₂ capture capacity. The results underscore UPC-MOFs as outstanding adsorbent materials, among the UPC-MOFs, UPC-OSO₃-steric exhibited the highest CO₂ capture capacity of 12.69 mmol/g with selectivities of 1142.41 (CO₂ over N₂) and 507.42 (CO₂ over CH₄) at 1.0 bar, 298 K. And the synergistic effect mechanisms of functional group, structure size, and steric hindrance were elucidated through theoretical calculations analyzing pore characteristics, gas distribution, isosteric heat, and van der Waals/Coulomb interactions.