Abstract
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. We anticipate that this thermodynamic, kinetic, and mechanistic understanding will broadly inform further studies on the energetics of crystallization.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2518-2527 |
| Number of pages | 10 |
| Journal | ACS Materials Letters |
| Volume | 5 |
| Issue number | 9 |
| DOIs | |
| State | Published - Sep 4 2023 |
Funding
O.K.F., S.L.H., and J.G.K acknowledge support from the U.S. Department of Energy, National Nuclear Security Administration, under award number DE-NA0003763 and the U.S. Department of Energy award number DE-SC0022332. S.L.H. gratefully acknowledges support from the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship (DOE NNSA SSGF) under award number DE-NA0003960. M.B. and V.P.D. acknowledge support from the Ryan Fellowship and the Department of Energy (DOE-BES DE-SC0022332). C.D.M. gratefully acknowledges support from Northwestern University. T.T.D. and C.H.H. are supported by the National Science Foundation under Grant No. [2237345] and the Camille and Henry Dreyfus Foundation. They are also grateful for access to the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (ACI-1548562) and the PICS Coeus High Performance Computer, which is supported by the National Science Foundation (1624776). M.A.G. is supported by the Army Research Office under award number W911NF2020136. J.G.K. is supported by the National Science Foundation (NSF) Graduate Research Fellowship under Grant No. DGE-2234667. K.O.K. gratefully acknowledges support from the IIN Postdoctoral Fellowship and the Northwestern University International Institute for Nanotechnology. This work made use of the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which has received support from the State of Illinois, Northwestern University, the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), NSF CHE-1048773, and the International Institute for Nanotechnology (IIN). This work also made use of the Electron Probe Instrumentation Center (EPIC) of the Northwestern University Atomic and Nanoscale Characterization Experimental Center (NUANCE), which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). S.L.H. acknowledges Shengyi Su for his assistance in the early stages of this project, Prof. Austin M. Evans and Prof. Timur Islamoglu for thought-provoking conversations over the course of this project, and Nathaniel Barker for assistance with adjusting the STADI MP instrument hardware.
ASJC Scopus subject areas
- General Chemical Engineering
- Biomedical Engineering
- General Materials Science