Prediction of Reactive Nitrous Acid Formation in Rare‐Earth MOFs via ab initio Molecular Dynamics

Reactive gas formation in pores of metal–organic frameworks (MOFs) is a known mechanism of framework destruction; understanding those mechanisms for future durability design is key to next generation adsorbents. Herein, an extensive set of ab initio molecular dynamics (AIMD) simulations are used for...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2021-05, Vol.60 (20), p.11514-11522
Main Authors: Vogel, Dayton J., Rimsza, Jessica M., Nenoff, Tina M.
Format: Article
Language:English
Subjects:
ab initio calculations
adsorption
Durability
Gas formation
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metal clusters
Metal-organic frameworks
metal–organic frameworks (MOFs)
Molecular dynamics
Nitrogen dioxide
Nitrous acid
rare-earth metals
Reaction mechanisms
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Summary:Reactive gas formation in pores of metal–organic frameworks (MOFs) is a known mechanism of framework destruction; understanding those mechanisms for future durability design is key to next generation adsorbents. Herein, an extensive set of ab initio molecular dynamics (AIMD) simulations are used for the first time to predict competitive adsorption of mixed acid gases (NO2 and H2O) and the in‐pore reaction mechanisms for a series of rare earth (RE)‐DOBDC MOFs. Spontaneous formation of nitrous acid (HONO) is identified as a result of deprotonation of the MOF organic linker, DOBDC. The unique DOBDC coordination to the metal clusters allows for proton transfer from the linker to the NO2 without the presence of H2O and may be a factor in DOBDC MOF durability. This is a previously unreported mechanisms of HONO formation in MOFs. With the presented methodology, prediction of future gas interactions in new nanoporous materials can be achieved. Ab initio molecular dynamics (AIMD) simulations are used to predict competitive adsorption of mixed acid gases (NO2 and H2O) and the in‐pore reaction mechanisms for a series of rare‐earth metal–organic frameworks with DOBDC linkers. For the first time, spontaneous formation of nitrous acid (HONO) is identified as a result of deprotonation of the MOF organic linker.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202102956