Molecular Sieving of C2 -C3 Alkene from Alkyne with Tuned Threshold Pressure in Robust Layered Metal-Organic Frameworks.

C2 -C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving of alkenes from alkynes remains challenging. Now, two hydrolytically stable layered MOFs, [Cu(dps)2 (GeF6 )] (GeFSIX-dps-Cu, dps=4,4'-dipyridylsulfide) and [Zn(dps)2 (GeF6 )] (GeFSIX-dps-Zn), can achieve almost complete exclusion of both C3 H6 and C2 H4 from their alkyne analogues. GeFSIX-dps-Cu displays a notable advanced threshold pressure for alkynes adsorption and thus substantial uptakes at lower pressures, providing record C3 H4 /C3 H6 uptake ratios and capacity-enhanced C2 H2 /C2 H4 sieving for a wide composition range. Metal substitution (Zn to Cu) affords fine tuning of linker rotation and layer stacking, creating slightly expanded pore aperture and interlayer space coupled with multiple hydrogen-bonding sites, allowing easier entrance of alkyne while excluding alkene. Breakthrough experiments confirmed tunable sieving by these MOFs for C3 H4 /C3 H6 and C2 H2 /C2 H4 mixtures.