Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy
Abstract
Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm–1) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligandsmore »
- Authors:
-
[1];
[1];
[1];
[1];
[1]
- Univ. of California, Davis, CA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1924280
- Alternate Identifier(s):
- OSTI ID: 1897313
- Grant/Contract Number:
- SC0010419; SC0012702; AC02-05CH11231; AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Materials Horizons
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2051-6347
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., and Moulé, Adam J. Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy. United States: N. p., 2022.
Web. doi:10.1039/d2mh00914e.
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., & Moulé, Adam J. Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy. United States. https://doi.org/10.1039/d2mh00914e
Cavalcante, Lucas S. R., Dettmann, Makena A., Sours, Tyler, Yang, Dong, Daemen, Luke L., Gates, Bruce C., Kulkarni, Ambarish R., and Moulé, Adam J. Mon .
"Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy". United States. https://doi.org/10.1039/d2mh00914e. https://www.osti.gov/servlets/purl/1924280.
@article{osti_1924280,
title = {Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy},
author = {Cavalcante, Lucas S. R. and Dettmann, Makena A. and Sours, Tyler and Yang, Dong and Daemen, Luke L. and Gates, Bruce C. and Kulkarni, Ambarish R. and Moulé, Adam J.},
abstractNote = {Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (<100 cm–1) which correspond to phonon modes only present in certain defective topologies. Specifically, this analysis suggests that our sample of UiO-66 consists of predominantly defect-free fcu regions with smaller domains corresponding to a defective bcu topology with 4 and 2 acetate ligands bound to the Zr6O8 nodes. Importantly, the INS/DFT approach provides detailed structural insights (e.g., relative positions and numbers of acetate ligands) that are not accessible with microscopy-based techniques. Furthermore, the quantitative agreement between DFT simulations and the experimental INS spectrum combined with the relative simplicity of sample preparation, suggests that this methodology may become part of the standard and preferred protocol for the characterization of MOFs, and, in particular, for elucidating the structure defects in these materials.},
doi = {10.1039/d2mh00914e},
journal = {Materials Horizons},
number = 1,
volume = 10,
place = {United States},
year = {Mon Oct 31 00:00:00 EDT 2022},
month = {Mon Oct 31 00:00:00 EDT 2022}
}
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