Insertion of CO 2 in metal ion-doped two-dimensional covalent organic frameworks

• Published in: Proceedings of the National Academy of Sciences - PNAS 2023-02, Vol.120 (9), p.e2217081120
• Main Authors: Kang, Chengjun, Zhang, Zhaoqiang, Xi, Shibo, Li, He, Usadi, Adam K, Calabro, David C, Baugh, Lisa Saunders, Wang, Yuxiang, Zhao, Dan
• Format: Article
• Language: English
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.2217081120

Carbon capture is one of the essential low-carbon technologies required to achieve societal climate goals at the lowest cost. Covalent organic frameworks (COFs) are promising adsorbents for CO capture because of their well-defined porosity, large surface area, and high stability. Current COF-based CO capture is mainly based on a physisorption mechanism, exhibiting smooth and reversible sorption isotherms. In the present study, we report unusual CO sorption isotherms featuring one or more tunable hysteresis steps with metal ion (Fe , Cr , or In )-doped Schiff-base two-dimensional (2D) COFs (Py-1P, Py-TT, and Py-Py) as adsorbents. Synchrotron X-ray diffraction, spectroscopic and computational studies indicate that the sharp adsorption steps in the isotherm originate from the insertion of CO between the metal ion and the N atom of the imine bond on the inner pore surface of the COFs as the CO pressure reaches threshold values. As a result, the CO adsorption capacity of the ion-doped Py-1P COF is increased by 89.5% compared with that of the undoped Py-1P COF. This CO sorption mechanism provides an efficient and straightforward approach to enhancing the CO capture capacity of COF-based adsorbents, yielding insights into developing chemistry for CO capture and conversion.