Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic Frameworks for Catalytic CO2 Cycloaddition via Visible-Light-Induced Photothermal Conversion.

We report the construction of a porphyrin and imidazolium-ionic liquid (IL)-decorated and quinoline-linked covalent organic framework (COF, abbreviated as COF-P1-1) via a three-component one-pot Povarov reaction. After post-synthetic metallization of COF-P1-1 with Co(II) ions, the metallized COF-PI-2 is generated. COF-PI-2 is chemically stable and displays highly selective CO2 adsorption and good visible-light-induced photothermal conversion ability (ΔT = 26 °C). Furthermore, the coexistence of Co(II)-porphyrin and imidazolium-IL within COF-PI-2 has guaranteed its highly efficient activity for CO2 cycloaddition. Of note, the needed thermal energy for the reactions is derived from the photothermal conversion of the Co(II)-porphyrin COF upon visible-light irradiation. More importantly, the CO2 cycloaddition herein is a "window ledge" reaction, and it can proceed smoothly upon natural sunlight irradiation. In addition, a scaled-up CO2 cycloaddition can be readily achieved using a COF-PI-2@chitosan aerogel-based fixed-bed model reactor. Our research provides a new avenue for COF-based greenhouse gas disposal in an eco-friendly and energy- and source-saving way.