Programmed fluorine binding engineering in anion-pillared metal-organic framework for record trace acetylene capture from ethylene

Porous physisorbents are attractive candidates for selective capture of trace gas or volatile compounds due to their low energy footprints. However, many physisorbents suffer from insufficient sorbate-sorbent interactions, resulting in low uptake or inadequate selectivity when gases are present at trace levels. Here, we report a strategy of programmed fluorine binding engineering in anion-pillared metal-organic frameworks to maximize C2H2 binding affinity for benchmark trace C2H2 capture from C2H4. A robust material (ZJU-300a) was elaborately designed to provide multiple-site fluorine binding model, resulting in an ultrastrong C2H2 binding affinity. ZJU-300a exhibits a record-high C2H2 uptake of 3.23 millimoles per gram (at 0.01 bar and 296 kelvin) and one of the highest C2H2/C2H4 selectivity (1672). The adsorption binding of C2H2 and C2H4 was visualized by gas-loaded ZJU-300a structures. The separation capacity was confirmed by breakthrough experiments for 1/99 C2H2/C2H4 mixtures, affording the maximal dynamic selectivity (264) and C2H4 productivity of 436.7 millimoles per gram.