Storage of hydrogen, methane, and carbon dioxide in highly porous covalent organic frameworks for clean energy applications.

Dihydrogen, methane, and carbon dioxide isotherm measurements were performed at 1-85 bar and 77-298 K on the evacuated forms of seven porous covalent organic frameworks (COFs). The uptake behavior and capacity of the COFs is best described by classifying them into three groups based on their structural dimensions and corresponding pore sizes. Group 1 consists of 2D structures with 1D small pores (9 A for each of COF-1 and COF-6), group 2 includes 2D structures with large 1D pores (27, 16, and 32 A for COF-5, COF-8, and COF-10, respectively), and group 3 is comprised of 3D structures with 3D medium-sized pores (12 A for each of COF-102 and COF-103). Group 3 COFs outperform group 1 and 2 COFs, and rival the best metal-organic frameworks and other porous materials in their uptake capacities. This is exemplified by the excess gas uptake of COF-102 at 35 bar (72 mg g(-1) at 77 K for hydrogen, 187 mg g(-1) at 298 K for methane, and 1180 mg g(-1) at 298 K for carbon dioxide), which is similar to the performance of COF-103 but higher than those observed for COF-1, COF-5, COF-6, COF-8, and COF-10 (hydrogen at 77 K, 15 mg g(-1) for COF-1, 36 mg g(-1) for COF-5, 23 mg g(-1) for COF-6, 35 mg g(-1) for COF-8, and 39 mg g(-1) for COF-10; methane at 298 K, 40 mg g(-1) for COF-1, 89 mg g(-1) for COF-5, 65 mg g(-1) for COF-6, 87 mg g(-1) for COF-8, and 80 mg g(-1) for COF-10; carbon dioxide at 298 K, 210 mg g(-1) for COF-1, 779 mg g(-1) for COF-5, 298 mg g(-1) for COF-6, 598 mg g(-1) for COF-8, and 759 mg g(-1) for COF-10). These findings place COFs among the most porous and the best adsorbents for hydrogen, methane, and carbon dioxide.