Recent Progress in the Development of Hyper-Cross-Linked Polymers for Adsorption of Gaseous Volatile Organic Compounds

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.

Conjugated microporous polymers (CMPs) are a unique class of materials that combine extended π-conjugation with a permanently microporous skeleton. Since their discovery in 2007, CMPs have become established as an important subclass of porous materials. A wide range of synthetic building blocks and network-forming reactions offers an enormous variety of CMPs with different properties and structures. This has allowed CMPs to be developed for gas adsorption and separations, chemical adsorption and encapsulation, heterogeneous catalysis, photoredox catalysis, light emittance, sensing, energy storage, biological applications, and solar fuels production. Here we review the progress of CMP research since its beginnings and offer an outlook for where these materials might be headed in the future. We also compare the prospect for CMPs against the growing range of conjugated crystalline covalent organic frameworks (COFs).