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Title: Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal–organic framework

Abstract

The degradation of a chemical warfare agent simulant using a catalytically active Zr-based metal-organic framework (MOF) as a function of different solvent systems was explored here. Complementary molecular modelling studies suggest that the differences in the degradation rates are related to the increasing size in the nucleophile, which hinders the rotation of the product molecule during degradation. Methanol was identified as an appropriate solvent for non-aqueous degradation applications and demonstrated to support the MOF-based destruction of both Sarin and Soman.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Army Research, Aberdeen, MD (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1574483
Alternate Identifier(s):
OSTI ID: 1570783
Report Number(s):
SAND-2019-12693J
Journal ID: ISSN 1477-9226; ICHBD9; 680530
Grant/Contract Number:  
AC04-94AL85000; NA-0003525
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 43; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Harvey, Jacob A., Pearce, Charles J., Hall, Morgan G., Bruni, Eric J., DeCoste, Jared B., and Sava Gallis, Dorina F. Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal–organic framework. United States: N. p., 2019. Web. doi:10.1039/C9DT03710A.
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Harvey, Jacob A., Pearce, Charles J., Hall, Morgan G., Bruni, Eric J., DeCoste, Jared B., & Sava Gallis, Dorina F. Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal–organic framework. United States. https://doi.org/10.1039/C9DT03710A
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Harvey, Jacob A., Pearce, Charles J., Hall, Morgan G., Bruni, Eric J., DeCoste, Jared B., and Sava Gallis, Dorina F. Fri . "Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal–organic framework". United States. https://doi.org/10.1039/C9DT03710A. https://www.osti.gov/servlets/purl/1574483.
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@article{osti_1574483,
title = {Insights into the solvent-assisted degradation of organophosphorus compounds by a Zr-based metal–organic framework},
author = {Harvey, Jacob A. and Pearce, Charles J. and Hall, Morgan G. and Bruni, Eric J. and DeCoste, Jared B. and Sava Gallis, Dorina F.},
abstractNote = {The degradation of a chemical warfare agent simulant using a catalytically active Zr-based metal-organic framework (MOF) as a function of different solvent systems was explored here. Complementary molecular modelling studies suggest that the differences in the degradation rates are related to the increasing size in the nucleophile, which hinders the rotation of the product molecule during degradation. Methanol was identified as an appropriate solvent for non-aqueous degradation applications and demonstrated to support the MOF-based destruction of both Sarin and Soman.},
doi = {10.1039/C9DT03710A},
journal = {Dalton Transactions},
number = 43,
volume = 48,
place = {United States},
year = {Fri Oct 11 00:00:00 EDT 2019},
month = {Fri Oct 11 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C9DT03710A
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Citation Metrics:
Cited by: 7 works
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Figures / Tables:

Fig. 1 Fig. 1: (a,b) Ball-and-stick representation of the channels in ZrTCPB along two different directions. Atoms color scheme: Zr= blue; C. grey; 0= red; H. white; (c) representative TEM; (d) N2 sorption isotherm measured at 77K.
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    Figures / Tables found in this record:

    Fig. 1 (p. 1)figure
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    Figure S1 (p. 9)figure
    Figure S2 (p. 10)figure
    Table S1 (p. 13)table
    Table S2 (p. 13)table
    Figure S3 (p. 14)figure
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    Figure S12 (p. 23)figure
    Table S3 (p. 24)table
    Figure S13 (p. 25)figure
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