Structurally Driven Selective Adsorption of Hydrocarbons by Metal Substitution in Isostructural Rare-Earth Metal–Organic Frameworks

Li, Chunyi; Sarswat, Akriti; Henkelis, Susan Elizabeth; Nenoff, Tina M.; Lively, Ryan P.; Rimsza, Jessica M.

doi:10.1021/acs.iecr.4c03523

Structurally Driven Selective Adsorption of Hydrocarbons by Metal Substitution in Isostructural Rare-Earth Metal–Organic Frameworks

Journal Article · Thu Mar 06 04:00:00 EST 2025 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.4c03523· OSTI ID:2563816

Li, Chunyi ^[1]; Sarswat, Akriti ^[1]; ^[2]; ^[2]; ^[1]; ^[2]

Georgia Institute of Technology, Atlanta, GA (United States)
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

The design and realization of highly selective nanoporous materials are necessary to target critical separations across industries. By leveraging pore size, pore shape, and linker functionalization, the design of nanoporous solid adsorbents will enable the rapid production of energy efficient separation materials for high-value gas mixtures. This study uses a combination of modeling, synthesis, and gas adsorption testing to investigate a new class of small-pore isostructural rare-earth (RE) 2,5-dihydroxyterephthalic acid (DOBDC) metal–organic frameworks (MOFs) (RE: Pr-, Gd-, Er-, Yb; DOBDC = 2,5-dihydroxyterephthalic acid) and their adsorption selectivity for acetylene/ethylene mixtures. Density functional theory simulations identified that selective binding of acetylene over ethylene in the Gd-, Er-, and Yb-DOBDC MOFs was due to hydrogen-bonding between acetylene and the linker hydroxyl. Adsorption experiments validated the computational results by identifying mechanisms that control the acetylene/ethylene adsorption selectivity and high acetylene adsorption. Furthermore, dynamic column breakthrough experiments with the Gd-DOBDC MOF validated the simulations and indicated that ethylene can be separated from acetylene in a mixture containing 1 vol % acetylene and 39 vol % ethylene (balance argon). In conclusion, the results highlight the complexity of gas binding in functional porous materials and how combining modeling and experiment enables a fundamental understanding of gas–framework interactions that can be leveraged for the design of future separation materials.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: NA0003525; SC0012577

OSTI ID:: 2563816

Report Number(s):: SAND--2025-05293J

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 11 Vol. 64; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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