Discovery of Complex Binding and Reaction Mechanisms from Ternary Gases in Rare Earth Metal–Organic Frameworks

Christian, Matthew S.; Nenoff, Tina M.; Rimsza, Jessica M.

doi:10.1002/chem.202201926

Discovery of Complex Binding and Reaction Mechanisms from Ternary Gases in Rare Earth Metal–Organic Frameworks

Journal Article · Fri Jul 22 00:00:00 EDT 2022 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202201926· OSTI ID:1887394

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Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Geochemistry Department
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Material, Chemical, and Physical Sciences

Understanding the selectivity of metal–organic frameworks (MOFs) to complex acid gas streams will enable their use in industrial applications. In this study, ab initio molecular dynamic simulations (AIMD) were used to simulate ternary gas mixtures (H₂O-NO₂-SO₂) in rare earth 2,5-dihydroxyterephthalic acid (RE-DOBDC) MOFs. Stronger H₂O gas-metal binding arose from thermal vibrations in the MOF sterically hindering access of SO₂ and NO₂ molecules to the metal sites. Gas-gas and gas-linker interactions within the MOF framework resulted in the formation of multiple secondary gas species including HONO, HNO₂, NOSO, and HNO₃⁻. Four gas adsorption sites were identified along with a new de-protonation reaction mechanism not observable through experiment. This study not only provides valuable information on competitive gas binding energies in the MOF, but it also provides important chemical insights into transient chemical reactions and mechanisms.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: NA0003525; SC0012577

OSTI ID:: 1887394

Alternate ID(s):: OSTI ID: 1882962

Report Number(s):: SAND2022-11432J; 709261

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 58 Vol. 28; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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