Ultra-selective CANAL Polymers for Hydrogen-based Membrane Separations after Long-Term Aging

Yeo, Jing Ying; Tapia, Brandon C.; Benedetti, Francesco M.; Robinson, Ashley M.; Richardson, Julian; Pedretti, Benjamin J.; Lee, Tae Hoon; Freeman, Benny D.; Xia, Yan; Smith, Zachary P.

doi:10.1016/j.memsci.2025.125038

Ultra-selective CANAL Polymers for Hydrogen-based Membrane Separations after Long-Term Aging

Journal Article · Mon Dec 01 00:00:00 EST 2025 · Journal of Membrane Science

DOI:https://doi.org/10.1016/j.memsci.2025.125038· OSTI ID:3009952

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Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)
Stanford University, CA (United States)
The University of Texas at Austin, TX (United States)
Massachusetts Institute of Technology (MIT), Cambridge, MA (United States); Sungkyunkwan University, Suwon (Korea, Republic of)

Hydrogen is a critically important molecule in the chemicals and energy industries, driving the need for efficient purification technologies such as membrane-based separations. However, polymer membranes often suffer from physical aging, leading to decreased gas permeability over time. This study leverages the unique aging behavior of contorted microporous polymers, synthesized via catalytic arene-norbornene annulation (CANAL) polymerization, to enhance molecular sieving for H₂ separations. While prior studies demonstrated a 1000% increase in H₂/CH₄ selectivity with minimal permeability loss over 150 days, we extend this investigation to hyperaged (∼1 year) CANAL polymers and evaluate their performance under various conditions of industrial relevance. We report a remarkable 6100% increase in H₂/CH₄ selectivity and a 2400% improvement in H₂/N₂ selectivity, with only a 55% decline in H₂ permeability. These membranes exhibit excellent long-term stability in binary and ternary gas mixtures and at elevated temperatures. Additionally, extended aging enhances H₂/CO₂ selectivity beyond the 2008 upper bound due to improved size-sieving. High-temperature permeation experiments and grand canonical Monte Carlo simulations reveal that H₂ permeability increases from 570 to 3500 barrer as the temperature rises from 35 °C to 190 °C, while H₂/CO₂ selectivity declines from 14 to 3 due to the higher diffusion activation energy of CO₂. Despite this tradeoff, hyperaged CANAL membranes maintain performance beyond the 200 °C upper bound, having selectivity–permeability performance comparable to many state-of-the-art membranes for H₂/CO₂ separations. As a result, this study highlights the robustness and industrial viability of ultra-selective CANAL polymers for hydrogen purification, contributing to advancements in clean energy and sustainable separation technologies.

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Institute of Technology (MIT), Cambridge, MA (United States); Stanford University, CA (United States); University of Texas at Austin, TX (United States)

Sponsoring Organization:: The Welch Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-02ER15362; SC0023252

OSTI ID:: 3009952

Journal Information:: Journal of Membrane Science, Journal Name: Journal of Membrane Science; ISSN 0376-7388

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

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