2025 AIChE Annual Meeting

(447b) Designed Vs Apparent Pore Size of Single Crystal Covalent Organic Framework: An Essential Step to Build a Predictive Digital Twin in 2D Membrane Material Discovery

Authors

Katie Li-Oakey - Presenter, University of Wyoming
Caleb Johannesmeyer, University of Wyoming
Beatrice Bartolomei, Northwestern University
Yun Kyung Shin, Pennsylvania State University
Adri van Duin, Pennsylvania State University
William Dichtel, Northwestern University
In contrast to an average-eclipsed structure with only angstrom-level stacking disorder predicated by theoretical models,1,2,3 electron ptychography recently revealed wide-spread stacking disorder in 3D pore structure for imine-linked 2D [TAPB: 1,3,5-tris(4-aminophenyl) benzene; DMPDA:2,5-dimethoxyterephthalaldehyde] (TAPB-DMPDA) single crystal covalent organic framework (COF) by Kharel et al.4 In this talk, we report COF membranes fabricated using the single crystal TAPB-DMPDA. Combined with a revised reactive force field (ReaxFF) model based on the electron ptychography results, the effect of interplanar stacking with the reported stacking disorder on membrane performance in permeance and selectivity is characterized using experimental filtration results and membrane morphology (Figure 1). The time and length scale mismatch between the ReaxFF predication and filtration data is minimized using a common liquid, such as water, to normalize the diffusion rate calculated by the ReaxFF model and flux results from filtration tests, respectively. The direct comparison between ReaxFF model calculation, electron ptychography, and filtration results using the high quality single crystal TAPB-DMPDA COF provides much needed insights for next-generation COF design and synthesis based on targeted applications, further narrowing the gap between their designed properties and final separation performance.

References

  1. Mapping TpPa-1 Covalent Organic Framework (COF) Molecular Interactions in Mixed Solvents via Atomistic Modeling and Experimental Study, Anastasia Barnes*, Mohammad M. Afroz*, Yun Kyung Shin, Adri C. T. van Duin and Katie D. Li-Oakey, Journal of Membrane Science, Journal of Membrane Science, 698 (2024) 122613. https://doi.org/10.1016/j.memsci.2024.122613
  2. ReaxFF Reactive Force Field Model Enables Accurate Prediction of Physiochemical and Mechanical Properties of Crystalline and Amorphous Shape-memory Polyurethane, Mohammad Afroz, Yun Kyung Shin, Adri C. T. van Duin, Katie D. Li-Oakey, Journal of Applied Polymer Science, 140, 39 (2023), e54466. https://DOI:10.1002/app.54466
  3. Experimental and Molecular Dynamic Modeling Studies of Electrospun Carbon Fiber Electrode Performance Enhancement by Potassium Ferricyanide Addition, Charmaine SJ. Lamiel, Mohammad M. Afroz, Robert E.F. Cincotta, Maximillian Krödel, Katie D. Li-Oakey, Electrochimica Acta, 446, 142076 (2023). https://doi.org/10.1016/j.electacta.2023.142076
  4. 3D Imaging Reveals Widespread Stacking Disorder in Single Crystal 2D Covalent Organic Frameworks, Priti KharelPatrick T. CarmichaelAnusree NatrajChloe E. PelkowskiSang hyun BaeWilliam R. DichtelPinshane Y. Huang*. J. Am. Chem. Soc. 2025, XXXX, XXX, XXX-XXX. https://doi.org/10.1021/jacs.4c16207