Computationally directed manipulation of cross-linked covalent organic frameworks for membrane applications

Two-dimensional covalent organic frameworks (2D-COFs) exhibit characteristics ideal for membrane applications, such as high stability, tunability and porosity along with well-ordered nanopores. However, one of the many challenges with fabricating these materials into membranes is that membrane wetting can result in layer swelling. This allows molecules that would be excluded based on pore size to flow around the layers of the COF, resulting in reduced separation. Cross-linking between these layers inhibits swelling to improve the selectivity of these membranes. In this work, computational models were generated for a quinoxaline-based COF cross-linked with oxalyl chloride (OC) and hexafluoroglutaryl chloride (HFG). Enthalpy of formation and cohesive energy calculations from these models show that formation of these COFs is thermodynamically favorable and the resulting materials are stable. The cross-linked COF with HFG was synthesized and characterized with Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis with differential scanning calorimetry (TGA-DSC), and water contact angles. Additionally, these frameworks were fabricated into membranes for permeance testing. The experimental data supports the presence of cross-linking and demonstrates that varying the amount of HFG used in the reaction does not change the amount of cross-linking present. Computational models indicate that varying the cross-linking concentration has a negligible effect on stability and less cross-linking still results in stable materials. This work sheds light on the nature of the cross-linking in these 2D-COFs and their application in membrane technologies. A quinoxaline-based covalent organic framework (COF) was synthetically cross-linked and investigated for membrane applications. Ab initio calculations were conducted to investigate the stability of cross-linked COFs.