Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

Lopez-Cazares, Jose Edgardo; Kim, Kyungtae; Lin, Jerry S.; Jin, Kailong

doi:10.1021/acs.iecr.3c04303

Title: Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

Journal Article · Thu Feb 15 00:00:00 EST 2024 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.3c04303· OSTI ID:2315663

Lopez-Cazares, Jose Edgardo ^[1];

^[2];

^[1];

^[1]

Arizona State Univ., Tempe, AZ (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Microporous two-dimensional covalent organic framework (2D COF) membranes offer promise for gas separation applications, but their gas transport mechanism remains unclear. In this study, a TpHz 2D COF membrane supported on a macroporous nylon substrate is prepared by substrate-assisted interfacial polymerization under mild conditions. The formation of a continuous and dense thin (~300 nm thick) TpHz layer is confirmed by scanning electron microscopy and Fourier transform infrared spectroscopy. Characterization by X-ray diffraction, grazing incidence wide-angle X-ray scattering, and N₂ porosimetry qualitatively reveals the microstructures of the supported TpHz membranes, i.e., they comprise partially oriented 2D COF lamellar crystallites with moderate crystallinity in an eclipsed (AA) stacking geometry, centering the effective membrane pore size distribution at ~1.1 nm. Further, single gas permeation data show that the transport of common molecular gases, including H₂, He, CH₄, N₂, and CO₂, through the synthesized TpHz membranes follows the Knudsen transport mechanism, where single gas permeance decreases with an increasing molecular weight and permeation temperature. Binary gas separation results show that in the equimolar CO₂/N₂ mixture, the presence of the CO₂ surface flow slightly hinders the N₂ flow at room temperature due to the reduced membrane channel size by the adsorbed CO₂ gas layer on TpHz’s pore wall. In contrast, permeation of the equimolar CH₄/N₂ binary mixture does not exhibit a discernible surface flow of both gases due to their much lower gas uptake on TpHz, and their transport mechanism follows Knudsen-like behavior.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); ACS-Petroleum Research Fund (PRF)

Grant/Contract Number:: 89233218CNA000001; CBET-2216843; 65612-DNI5; CBET-2031087

OSTI ID:: 2315663

Report Number(s):: LA-UR-23-33431

Journal Information:: Industrial and Engineering Chemistry Research, Vol. 63, Issue 8; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

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