A microporous water stable MOF for consistent and selective C2H2/C2H4 separation

[Display omitted] •A microporous (∼4.5 × 4.5 Å2) new water-stable 3D MOF is synthesized.•Prolonged moisture stability (97% RH for 15 days).•Excellent C2H2/C2H4 uptake ratio and IAST separation selectivity.•Complete separation with column breakthrough experiment.•Highly regenerable with consistent loading over multiple breakthrough cycles. Polymer-grade ethylene production requires the removal of trace acetylene, which possesses an intractable industrial separation task. Metal-organic frameworks (MOFs) having stability in water/moisture-containing environments are the promising alternative physisorbent material for the purification of C2H4 from C2H2-containing mixtures. In this study, a three-dimensional MOF (IITKGP-30) with narrow pore channels (∼4.5 × 4.5 Å2) is developed for C2H2/C2H4 separation exhibiting excellent IAST separation selectivity of 3.3 (1:99) and 6.2 (50:50) at 295 K under 1 bar. Theoretical investigation revealed preferentially binding of acetylene molecules to the metal site in an end-on fashion equivalent to 4.76 kJ mol−1 more binding energy than ethylene. Dynamic breakthrough experiments with 1:99 (v/v) C2H2/C2H4 mixtures at 298 K revealed a complete separation of the binary mixture with excellent breakthrough selectivity of 2.4 and the ethylene productivity of 10.4 mL g−1. It is highly stable under 97% RH as long as 15 days and in the presence of water, can maintain a C2H2 uptake and retention time minimum up to three breakthrough cycles with ease of regenerability, thus showing its great promise for practical deployment.