Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs
Abstract
The adsorption of chemical warfare agents and their simulants by Zr (UiO-66) and rare-earth (Y, UiO-66-DOBDC analog)-based metal–organic frameworks (MOFs) is explored here using density functional theory. In particular, we investigate the role of linker functional group (OH, H) and metal atom identity on the binding energies of organophosphorous compounds. Commonly used cluster approximations for MOF secondary building units and various optimization constraints are compared with three-dimensional periodic results. An in-depth scan of potential binding sites and orientations reveals little effect due to metal identity, whereas the effect of linker functionalization depends on the substrate. This finding strongly suggests that full linkers and functional groups should be included in cluster models. Importantly, defect sites show considerably improved binding of organophosphorous compounds as compared to ideal clusters. Favorable binding is also demonstrated at two additional adsorption sites, ZrOH and μ3-OH, that likely play a role in the initial adsorption process. Finally, the results presented here portray the importance of including full three-dimensional pore structures in the adsorption process of organophosphorous compounds in MOFs; a critical first step in the degradation of these harmful chemicals.
- Authors:
-
[1];
[1];
[2]
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Geochemistry Dept.
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Nanoscale Sciences Dept.
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1485826
- Report Number(s):
- SAND-2018-12980J
Journal ID: ISSN 1932-7447; 669789
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 47; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Harvey, Jacob A., Greathouse, Jeffery A., and Sava Gallis, Dorina F. Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b06198.
Harvey, Jacob A., Greathouse, Jeffery A., & Sava Gallis, Dorina F. Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs. United States. https://doi.org/10.1021/acs.jpcc.8b06198
Harvey, Jacob A., Greathouse, Jeffery A., and Sava Gallis, Dorina F. Tue .
"Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs". United States. https://doi.org/10.1021/acs.jpcc.8b06198. https://www.osti.gov/servlets/purl/1485826.
@article{osti_1485826,
title = {Defect and Linker Effects on the Binding of Organophosphorous Compounds in UiO-66 and Rare-Earth MOFs},
author = {Harvey, Jacob A. and Greathouse, Jeffery A. and Sava Gallis, Dorina F.},
abstractNote = {The adsorption of chemical warfare agents and their simulants by Zr (UiO-66) and rare-earth (Y, UiO-66-DOBDC analog)-based metal–organic frameworks (MOFs) is explored here using density functional theory. In particular, we investigate the role of linker functional group (OH, H) and metal atom identity on the binding energies of organophosphorous compounds. Commonly used cluster approximations for MOF secondary building units and various optimization constraints are compared with three-dimensional periodic results. An in-depth scan of potential binding sites and orientations reveals little effect due to metal identity, whereas the effect of linker functionalization depends on the substrate. This finding strongly suggests that full linkers and functional groups should be included in cluster models. Importantly, defect sites show considerably improved binding of organophosphorous compounds as compared to ideal clusters. Favorable binding is also demonstrated at two additional adsorption sites, ZrOH and μ3-OH, that likely play a role in the initial adsorption process. Finally, the results presented here portray the importance of including full three-dimensional pore structures in the adsorption process of organophosphorous compounds in MOFs; a critical first step in the degradation of these harmful chemicals.},
doi = {10.1021/acs.jpcc.8b06198},
journal = {Journal of Physical Chemistry. C},
number = 47,
volume = 122,
place = {United States},
year = {Tue Nov 13 00:00:00 EST 2018},
month = {Tue Nov 13 00:00:00 EST 2018}
}
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Works referencing / citing this record:
Structure and electronic properties of rare earth DOBDC metal–organic-frameworks
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