Fully Modifiable, Two-Dimensional Covalent Organic Frameworks—Self-Assembling Systems Enabling Pore Size and Functional Group Modification for Applications in Nanoscale Filtration

Covalent organic frameworks (COFs)offer the ability to construct highly-ordered nanoporous two-dimensional materials with interesting and attractive properties. These materials have been shown to be ideal for nanoscale separations, an area that we have recently focused on.^1-7In this presentation, we present new highly ordered, and highly-conjugated 2D-COFs synthesized using new organic transformations, which enable variations in pore size from 0.5-2.5 nm. These COFs can be functionalized, either pre or post synthesis, with an extensive range of funtional groups. Membranes fabricated with these materials demonstrate both high solvent throughput and high selectivity to a wide range of mixtures including gases. Pores with functional groups to either increase or reduce pore size or induce cross-linking between layers are also easily constructed. Our self-assembling system of a single monomer will be highlighted.¹<br/>1. Spaulding, V.; Zosel, K. Duong, P. H. H.; Li-Oakey, K. D.; Parkinson, B. A.; Gomez-Gualdron, D. A.; Hoberg, J. O. “A self-assembling, biporous, metal-binding covalent organic framework and its application for gas separation” <i>Mater. Adv. <b>2021</b>, 2, 3362.</i><br/>2. Kuehl, V. A.; Duong, P. H. H.; Sadrieva, D.; Amin, S. A.; She, Y.; Li-Oakey, K. D.; Yarger, J. L.; Parkinson, B. A.; Hoberg, J. O.“Synthesis, Postsynthetic Modifications, and Applications of the First Quinoxaline-Based Covalent Organic Framework” <i>ACS Appl. Mater. Interfaces </i><b>2021</b>, <i>13, 37494.</i><br/>3. Duong, P. H. H.; Shin, Y. K.; Kuehl, V. A.; Afroz, M. M.; Hoberg, J. O.; Parkinson, B. A.; van Duin, A. C. T.; Li-Oakey, K. D. “Molecular Interactions and Layer Stacking Dictate Covalent Organic Framework Effective Pore Size” <i>ACS App. Mater. Interfaces </i><b>2021</b>, <i>13, 42164.</i><br/>4. Kuehl, V. A.; Wenzel, M. J.; Parkinson, B. A.; Sousa Oliveira, L. de; Hoberg, J. O. “Pitfalls in the Synthesis of Polyimide-Linked Two-Dimensional Covalent Organic Frameworks” <i>J. Mater. Chem. A </i><b>2021</b>, <i>9</i>, 15301.<br/>5. Brophy, J.; Summerfield, K.; Yin, J.; Kephart, J.; Stecher, J.T.; Adams, J.; Yanase, T.; Brant, J.; Li<b> </b>Oakey, K.D.; Hoberg, J.O.; Parkinson, B. A. “The influence of disorder in the synthesis, characterization and applications of a modifiable two<b> </b>dimensional Covalent Organic Framework” <i>Materials </i><b>2021</b>, <i>14</i>, 71.<br/>6. Duong, P. H. H.; Kuehl, V. A.; Mastorovich, B.; Hoberg, J. O.; Parkinson, B. A.; Li-Oakey, K. D. “Carboxyl-functionalized covalent organic framework as a two-dimensional nanofiller for mixed-matrix ultrafiltration membranes” <i>J. Membr. Sci. </i><b>2019</b><i>,</i><i>574</i>, 338.<br/>7. Kuehl, V. A.; Yin, J.; Duong, P. H. H.; Mastorovich, B.; Newell, B.; Li-Oakey, K. D.; Parkinson, B. A.; Hoberg, J. O. “A highly-ordered nanoporous, two-dimensional covalent organic framework with modifiable pores, and its application in water purification and ion sieving.” <i>J. Am. Chem. Soc. </i><b>2018</b><i>,</i><i>140</i>, 18200.