Hexagonally ordered covalent organic frameworks (COFs) are interesting new crystalline porous materials that have massive potential for application in gas storage. Herein, we report the synthesis of two series of two-dimensional hexagonally ordered COFs - TPA-COFs and TPT-COFs - through one-pot polycondensations of tris(4-aminophenyl)amine (TPA-3NH2) and 2,4,6-tris(4-aminophenyl)triazine (TPT-3NH2), respectively, with triarylaldehydes featuring different degrees of planarity, symmetry, and nitrogen content. All the synthesized COFs exhibited high crystallinity, large BET surface areas (up to 1747 m2 g-1), excellent thermal stability, and pore size distributions from 1.80 to 2.55 nm. The symmetry and planarity of the monomers strongly affected the degrees of crystallinity and the BET surface areas of the resultant COFs. In addition, these COFs displayed excellent CO2 uptake efficiencies of up to 65.65 and 92.38 mg g-1 at 298 and 273 K, respectively. The incorporation of the more planar and higher-nitrogen-content triaryltriazine unit into the backbones of the TPA-COFs and TPT-COFs enhanced the interactions with CO2, leading to higher CO2 uptakes. Moreover, the synthesized COFs exhibited electrochemical properties because of their conjugated structures containing redox-active triphenylamine groups. This study exposes the importance of considering the symmetry and planarity of the monomers when designing highly crystalline COFs; indeed, the structures of COFs can be tailored to vary their functionalities for specific applications.
Bibliographical noteFunding Information:
This study was supported nancially by the Ministry of Science and Technology, Taiwan, under contracts MOST 106-2221-E-110-067-MY3 and 105-2221-E-110-092-MY3. This work was supported by the Australian Research Council (ARC) Future Fellow (FT150100479), JSPS KAKENHI (17H05393 and 17K19044), and the research fund by the Suzuken Memorial Foundation. The authors would like to thank New Innovative Technology (NIT) for helpful suggestions and discussions.
© The Royal Society of Chemistry.
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)