Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal–Organic Framework

Xie, Yi; Shi, Yanshu; Cedeño Morales, Eder M.; El Karch, Ayoub; Wang, Bin; Arman, Hadi; Tan, Kui; Chen, Banglin

doi:10.1021/jacs.2c11365

Title: Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal–Organic Framework

Journal Article · Mon Jan 23 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c11365· OSTI ID:2307855

Xie, Yi ^[1]; Shi, Yanshu ^[1];

^[2]; El Karch, Ayoub ^[2];

^[1]; Arman, Hadi ^[1];

^[2];

^[1]

University of Texas at San Antonio, TX (United States)
University of Texas at Dallas, Richardson, TX (United States)

Highly efficient adsorptive separation of propylene from propane offers an ideal alternative method to replace the energy-intensive cryogenic distillation technology. Molecular sieving-type separation via high-performance adsorbents is targeted for superior selectivity, but the limit in adsorption capacity remains a great challenge. Here, we report an oxyfluoride-based ultramicroporous metal–organic framework UTSA-400, [Ni(WO₂F₄)(pyz)₂] (pyz = pyrazine), featuring one-dimensional pore channels that can accommodate the propylene molecules with optimal binding affinity while specifically excluding the propane molecules. The exposed oxide/fluoride pairs in UTSA-400 serve as strong functional sites for strengthened propylene–host interactions, accounting for a significantly enhanced propylene uptake, while the propane molecules are excluded due to the regulated host framework dynamics. The strong propylene binding enables near-saturation of propylene in the pore confinement at ambient conditions, leading to full utilization of pore space and superior packing density. Combined in situ infrared spectroscopy measurements and dispersion-corrected density functional theory calculations clearly unveil the nature of boosted host–guest binding. Direct production of polymer-grade (>99.5%) propylene with remarkable dynamic productivity is demonstrated by column breakthrough experiments. Furthermore, this work presents an example of pore engineering with atomic precision to break the trade-off in adsorptive separation through guest binding optimization.

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Research Organization:: Univ. of North Texas, Denton, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0019902

OSTI ID:: 2307855

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 4; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Alkyls
Anions
Metal organic frameworks
Molecules

Title: Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal–Organic Framework

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