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Title: Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space

Abstract

Gas capture and sequestration are valuable properties of metal–organic frameworks (MOFs) driving tremendous interest in their use as filtration materials for chemical warfare agents. Recently, the Zr-based MOF UiO-67 was shown to effectively adsorb and decompose the nerve-agent simulant, dimethyl methylphosphonate (DMMP). Understanding mechanisms of MOF-agent interaction is challenging due to the need to distinguish between the roles of the MOF framework and its particular sites for the activation and sequestration process. Here, we demonstrate the quantitative tracking of both framework and binding component structures using in situ X-ray total scattering measurements of UiO-67 under DMMP exposure, pair distribution function analysis, and theoretical calculations. The sorption and desorption of DMMP within the pores, association with linker-deficient Zr6 cores, and decomposition to irreversibly bound methyl methylphosphonate were directly observed and analyzed with atomic resolution.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [2];  [1];  [5];  [5]; ORCiD logo [6]
  1. Max Planck Inst. for Solid State Research, Stuttgart (Germany)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., NY (United States)
  4. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  5. U.S. Army Combat Capabilities Development Command Chemical Biological Center, Aberdeen, MD (United States)
  6. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Army Research Office (ARO)
OSTI Identifier:
1756298
Report Number(s):
BNL-220776-2021-JAAM
Journal ID: ISSN 2399-3669
Grant/Contract Number:  
SC0012704; W911NF-15-2-0107
Resource Type:
Accepted Manuscript
Journal Name:
Communications Chemistry
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2399-3669
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal-organic frameworks; porous materials

Citation Formats

Terban, Maxwell W., Ghose, Sanjit K., Plonka, Anna M., Troya, Diego, Juhás, Pavol, Dinnebier, Robert E., Mahle, John J., Gordon, Wesley O., and Frenkel, Anatoly I.. Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space. United States: N. p., 2021. Web. https://doi.org/10.1038/s42004-020-00439-1.
Terban, Maxwell W., Ghose, Sanjit K., Plonka, Anna M., Troya, Diego, Juhás, Pavol, Dinnebier, Robert E., Mahle, John J., Gordon, Wesley O., & Frenkel, Anatoly I.. Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space. United States. https://doi.org/10.1038/s42004-020-00439-1
Terban, Maxwell W., Ghose, Sanjit K., Plonka, Anna M., Troya, Diego, Juhás, Pavol, Dinnebier, Robert E., Mahle, John J., Gordon, Wesley O., and Frenkel, Anatoly I.. Mon . "Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space". United States. https://doi.org/10.1038/s42004-020-00439-1. https://www.osti.gov/servlets/purl/1756298.
@article{osti_1756298,
title = {Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space},
author = {Terban, Maxwell W. and Ghose, Sanjit K. and Plonka, Anna M. and Troya, Diego and Juhás, Pavol and Dinnebier, Robert E. and Mahle, John J. and Gordon, Wesley O. and Frenkel, Anatoly I.},
abstractNote = {Gas capture and sequestration are valuable properties of metal–organic frameworks (MOFs) driving tremendous interest in their use as filtration materials for chemical warfare agents. Recently, the Zr-based MOF UiO-67 was shown to effectively adsorb and decompose the nerve-agent simulant, dimethyl methylphosphonate (DMMP). Understanding mechanisms of MOF-agent interaction is challenging due to the need to distinguish between the roles of the MOF framework and its particular sites for the activation and sequestration process. Here, we demonstrate the quantitative tracking of both framework and binding component structures using in situ X-ray total scattering measurements of UiO-67 under DMMP exposure, pair distribution function analysis, and theoretical calculations. The sorption and desorption of DMMP within the pores, association with linker-deficient Zr6 cores, and decomposition to irreversibly bound methyl methylphosphonate were directly observed and analyzed with atomic resolution.},
doi = {10.1038/s42004-020-00439-1},
journal = {Communications Chemistry},
number = 1,
volume = 4,
place = {United States},
year = {2021},
month = {1}
}

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