Mapping the Complete Reaction Energy Landscape of a Metal–Organic Framework Phase Transformation

Hanna, Sylvia L.; Barsoum, Michael; Debela, Tekalign Terfa; Malliakas, Christos D.; Gaidimas, Madeleine A.; Knapp, Julia G.; Kirlikovali, Kent O.; Hendon, Christopher H.; Dravid, Vinayak P.; Farha, Omar K.

doi:10.1021/acsmaterialslett.3c00598

Mapping the Complete Reaction Energy Landscape of a Metal–Organic Framework Phase Transformation

Journal Article · Thu Aug 17 00:00:00 EDT 2023 · ACS Materials Letters

DOI:https://doi.org/10.1021/acsmaterialslett.3c00598· OSTI ID:1996827

^[1]; Barsoum, Michael ^[2]; ^[3]; ^[2]; ^[2]; ^[2]; ^[2]; ^[3]; ^[2]; ^[2]

Northwestern University, Evanston, IL (United States); University of Notre Dame
Northwestern University, Evanston, IL (United States)
University of Oregon, Eugene, OR (United States)

Crystalline materials undergo valuable phase transformations, and the energetic processes that underlie these transformations can be fully characterized through a combination of thermodynamic and kinetic studies. Here, we report the first complete reaction energy landscape of metal–organic framework (MOF) interpenetration, specifically in the phase transformation of NU-1200 to its doubly interpenetrated counterpart, STA-26. We characterized the thermodynamics of this phase transformation by pairing experiments with density functional theory (DFT) calculations. This analysis revealed that factors such as the increase in crystal density likely drive Zr- and Hf-NU-1200 to STA-26 interpenetration, while other chemical interactions such as steric repulsions prevent Th-NU-1200 from interpenetrating. Using time-resolved in situ X-ray diffraction, we monitored phase transformation reaction profiles and extracted quantitative kinetic information using the Avrami-Erofe’ev model. As a result, we obtained activation energies for the Zr- and Hf-NU-1200 transformations to Zr- and Hf-STA-26, respectively, revealing slower phase change kinetics for MOFs with stronger bonds. Finally, we paired the kinetic data with experimental observations to classify the mechanistic model of this phase transformation as partial dissolution. Here, we anticipate that this thermodynamic, kinetic, and mechanistic understanding will broadly inform further studies on the energetics of crystallization.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

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

Grant/Contract Number:: NA0003763; SC0022332; NA0003960

OSTI ID:: 1996827

Journal Information:: ACS Materials Letters, Journal Name: ACS Materials Letters Journal Issue: 9 Vol. 5; ISSN 2639-4979

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Crystallization
Kinetics
Metal organic frameworks
Phase transitions
Thermodynamics

Mapping the Complete Reaction Energy Landscape of a Metal–Organic Framework Phase Transformation

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