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

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, 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. Our 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 [1] ;  [1] ;  [2] ;  [2] ; ORCiD logo [3] ;  [4] ;  [3] ;  [5] ;  [3] ;  [4] ; ORCiD logo [1]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. U.S. Army Edgewood Chemical Biological Center APG, Aberdeen Proving Ground, MD (United States)
  3. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
  4. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
BNL-113713-2017-JA
Journal ID: ISSN 0002-7863; R&D Project: CO040; KC0302010
Grant/Contract Number:
SC00112704; AC02-06CH11357; AC02-76SF00515; SC0012335
Type:
Accepted Manuscript
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)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1349576

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., 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. 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., and Frenkel, Anatoly I.. 2016. "In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks". United States. doi:10.1021/jacs.6b11373. https://www.osti.gov/servlets/purl/1349576.
@article{osti_1349576,
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 = {Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, 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. Our 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},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 139,
place = {United States},
year = {2016},
month = {12}
}