Inducing hierarchical pores in nano-MOFs for efficient gas separation.

The synthesis of metal-organic frameworks (MOFs) and their processing into structures with tailored hierarchical porosity is essential for using MOFs in the adsorption-driven gas separation process. We report the synthesis of modified Cu-MOF nanocrystals for CO 2 separation from CH 4 and N 2 , prepared from DABCO (1,4-diazabicyclo[2.2.2] octane) and 9,10 anthracene dicarboxylic acid linkers with copper metal salt. The synthesis parameters were optimized to introduce mesoporosity in the microporous Cu-MOF crystals. The volumetric CO 2 adsorption capacity of the new hierarchical Cu-MOF was 2.58 mmol g -1 at 293 K and 100 kPa with a low isosteric heat of adsorption of 28 kJ mol -1 . The hierarchical Cu-MOF nanocrystals were structured into mechanically stable pellets with a diametral compression strength exceeding 1.2 MPa using polyvinyl alcohol (PVA) as a binder. The CO 2 breakthrough curves were measured from a binary CO 2 -CH 4 (45/55 vol%) gas mixture at 293 K and 400 kPa pressure on Cu-MOF pellets to demonstrate the role of hierarchical porosity in mass transfer kinetics during adsorption. The structured hierarchical Cu-MOF pellets showed stable cyclic CO 2 adsorption capacity during 5 adsorption-desorption cycles with a CO 2 uptake capacity of 3.1 mmol g -1 at 400 kPa and showed a high mass transfer coefficient of 1.8 m s -1 as compared to the benchmark zeolite NaX commercialized binderless granules, suggesting that the introduction of hierarchical porosity in Cu-MOF pellets can effectively reduce the time for CO 2 separation cycles.