Selective Ethane/Ethylene Separation in a Robust Microporous Hydrogen-Bonded Organic Framework.

The separation of ethane (C2H6) from ethylene (C2H4) is of prime importance in the production of polymer-grade C2H4 for industrial manufacturing. It is very challenging and still remains unexploited to fully realize efficient C2H6/C2H4 separa-tion in the emerging hydrogen-bonded organic frameworks (HOFs) due to the weak nature of hydrogen bonds. We here-in report the benchmark example of a novel ultra-robust HOF adsorbent (termed as HOF-76a) with a Brunauer-Emmett-Teller surface area exceeding 1100 m2 g-1, exhibiting the preferential binding of C2H6 over C2H4 and thus highly selective separation of C2H6/C2H4. Theoretical calculations indicate the key role of the non-polar surface and the suitable triangular channel-like pores in HOF-76a to sterically "match" better with the nonplanar C2H6 molecule than the planar C2H4, thus affording overall stronger multipoint van der Waals interactions with C2H6. The exceptional separation performance of HOF-76a for C2H6/C2H4 separation was clearly demonstrated by gas adsorption isotherms, ideal adsorbed solution theory calculations, and simulated and experimental breakthrough curves. Breakthrough experiments on HOF-76a reveal that polymer-grade ethylene gas can be straightforwardly produced from 50/50 (v/v) C2H6/C2H4 mixtures during the first ad-sorption cycle with a high productivity of 7.2 L/kg at 298 K and 1 .01 bar, and 18.8 L/kg at 298 K and 5.0 bar, respectively.