The selective adsorption and separation of C2 hydrocarbons have been achieved in a “flexible-robust” MOF based on a guest-dependent gate-opening effect.
The development of ethane (C 2 H 6 )-selective adsorbents for ethylene (C 2 H 4 ) purification, although challenging, is of prime industrial importance. Pillared-layer metal-organic frameworks (MOFs) possess facilely tunable pore structure and functionality, which means they have excellent potential for high-performance C 2 H 6 /C 2 H 4 separation applications. Herein, we report a family of isostructural pillared-layer MOFs with various metal centers M and co-ligands L, M 2 (D-cam) 4 L 2 (denoted M-cam-L; M = Cu, Co, Ni; L = pyz, apyz, dabco), with a variety of pore surface properties. All of the M-cam-L materials exhibit preferential adsorption for C 2 H 6 over C 2 H 4 . In particular, Ni-cam-pyz exhibits the highest C 2 H 6 capture capacity (68.75 cm 3 g À1 at 1 bar and 298 K), Cu-cam-dabco possesses the greatest C 2 H 6 /C 2 H 4 adsorption selectivity (2.3), and the lowest isosteric heat of adsorption is demonstrated for Cu-cam-pyz (20.1 kJ mol À1 ).Dynamic column breakthrough experiments also confirmed the excellent separation performance of M-cam-pyz and M-cam-dabco materials. The synthesis route of the M-cam-L materials is easily scaled-up under laboratory conditions, and hence this class of MOFs is promising for practical C 2 H 4 purification.
The separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) and methane (CH 4 ) is of great significance, but remains challenging, because of their similar physicochemical properties, and it currently has received substantial research interest by using adsorptive separation based on metal−organic frameworks (MOFs). Herein, a new microporous Cu-MOF, [Cu(5-OH-IPA 2− )-(DPYA)(H 2 O)] (BUT-318, where 5-OH-IPA 2− = 5-hydroxyisophthalate and DPYA = 4,4′-dipyridylamine) has been synthesized successfully under solvothermal conditions, which exhibits excellent separation performance for C 2 H 2 /CO 2 and C 2 H 2 /CH 4 gas mixtures. The presence of Cu(II) open metal sites and different Lewis base sites (−OH and −NH) make the activated BUT-318 efficiently bind C 2 H 2 and exhibit high adsorption capacity under low pressure (24.52 and 9.1 cm 3 g −1 under 0.01 bar, at 273 and 298 K, respectively). The corresponding IAST (ideal adsorbed solution theory) selectivity was 9.8 and 244.3 at 273 K and 1 bar for an equimolar C 2 H 2 /CO 2 and C 2 H 2 /CH 4 mixture. The separation performance and reusability under dynamic conditions were also confirmed by column breakthrough experiments, making BUT-318a a promising candidate for the practical C 2 H 2 separation.
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