Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 58, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202201926
Keywords
acid gas separation; AIMD; DOBDC; metal-organic frameworks; rare earth element
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Funding
- Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012577]
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA0003525]
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This study investigates the selectivity of rare earth 2,5-dihydroxyterephthalic acid (RE-DOBDC) metal-organic frameworks (MOFs) towards ternary gas mixtures (H2O-NO2-SO2) through ab initio molecular dynamic simulations (AIMD). It reveals that stronger gas-metal binding between H2O and the MOF arises from thermal vibrations, hindering the access of SO2 and NO2 molecules to the metal sites. Additionally, the study identifies multiple secondary gas species formed through gas-gas and gas-linker interactions within the MOF, and proposes a new de-protonation reaction mechanism.
Understanding the selectivity of metal-organic frameworks (MOFs) to complex acid gas streams will enable their use in industrial applications. Herein, 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, it also provides important chemical insights into transient chemical reactions and mechanisms.
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