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Title: In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

Abstract

Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

Authors:
ORCiD logo; ; ; ; ORCiD logo; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE; U.S. ARMY RESEARCH
OSTI Identifier:
1349937
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 2; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., and Frenkel, Anatoly I. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks. United States: N. p., 2017. Web. doi:10.1021/jacs.6b11373.
Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., & Frenkel, Anatoly I. In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks. United States. https://doi.org/10.1021/jacs.6b11373
Plonka, Anna M., Wang, Qi, Gordon, Wesley O., Balboa, Alex, Troya, Diego, Guo, Weiwei, Sharp, Conor H., Senanayake, Sanjaya D., Morris, John R., Hill, Craig L., and Frenkel, Anatoly I. 2017. "In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks". United States. https://doi.org/10.1021/jacs.6b11373.
@article{osti_1349937,
title = {In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks},
author = {Plonka, Anna M. and Wang, Qi and Gordon, Wesley O. and Balboa, Alex and Troya, Diego and Guo, Weiwei and Sharp, Conor H. and Senanayake, Sanjaya D. and Morris, John R. and Hill, Craig L. and Frenkel, Anatoly I.},
abstractNote = {Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.},
doi = {10.1021/jacs.6b11373},
url = {https://www.osti.gov/biblio/1349937}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 2,
volume = 139,
place = {United States},
year = {2017},
month = {1}
}

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Works referencing / citing this record:

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