Hierarchically porous metal-organic frameworks: rapid synthesis and enhanced gas storage.

Abstract

Large pore sizes, high pore volumes, facile synthesis conditions, and high space-time yields are recognized as four crucial criteria in the fabrication of metal-organic frameworks (MOFs). However, these four objectives are rarely realized together. Herein, we have developed a simple and versatile method that employs 1,4-butanediamine (BTDM) as a template for rapidly fabricating four stable hierarchically porous MOFs (H-MOFs), including HKUST-1, ZIF-8, ZIF-67, and ZIF-90. The synthesis conditions are simple and facile at room temperature and ambient pressure, and the synthesis time can be shortened to 1 min. The resultant H-MOFs exhibit multimodal hierarchically porous structures with meso- and macropores interconnected with micropores, as well as high pore volumes (0.76 cm3 g-1). The maximum space-time yield for the hierarchically porous HKUST-1 reaches 7.4 × 104 kg m-3 d-1, at least one order of magnitude higher than previous reported yields. Notably, the additive BTDM not only facilitates crystal growth but also guides the formation of meso- and macropores. The synthesis route is highly versatile, as analogues (e.g., tetramethyl-1,3-diaminopropane and tetramethyldiaminomethane) can also be employed as templates to prepare diverse H-MOFs. Furthermore, the porosities of the H-MOFs are readily tuned by controlling the metal source, template amount and type of template. The as-synthesized H-MOFs act as adsorbents with significantly improved performances relative to those of microporous MOFs used for CH4 and CO2 gas storage. This strategy may aid in the large-scale industrial synthesis of desirable H-MOFs for gas storage.