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Molecular Sieving of C 2 ‐C 3 Alkene from Alkyne with Tuned Threshold Pressure in Robust Layered Metal–Organic Frameworks
Author(s) -
Ke Tian,
Wang Qingju,
Shen Jin,
Zhou Jingyi,
Bao Zongbi,
Yang Qiwei,
Ren Qilong
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003421
Subject(s) - alkyne , alkene , metal organic framework , stacking , metal , linker , chemistry , materials science , adsorption , crystallography , organic chemistry , catalysis , computer science , operating system
C 2 ‐C 3 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 (GeF 6 )] (GeFSIX‐dps‐Cu, dps=4,4′‐dipyridylsulfide) and [Zn(dps) 2 (GeF 6 )] (GeFSIX‐dps‐Zn), can achieve almost complete exclusion of both C 3 H 6 and C 2 H 4 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 C 3 H 4 /C 3 H 6 uptake ratios and capacity‐enhanced C 2 H 2 /C 2 H 4 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 C 3 H 4 /C 3 H 6 and C 2 H 2 /C 2 H 4 mixtures.