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Title: Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study

Abstract

The mechanism and kinetics of interactions between dimethyl methylphosphonate (DMMP), a key chemical warfare agent (CWA) simulant, and Zr6-based metal organic frameworks (MOFs) have been investigated with in situ infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), and DFT calculations. DMMP was found to adsorb molecularly to UiO-66 through the formation of hydrogen bonds between the phosphoryl oxygen and the free hydroxyl groups associated with Zr6 nodes on the surface of crystallites and not within the bulk MOF structure. Unlike UiO-66, the infrared spectra for UiO-67 and MOF-808, recorded during DMMP exposure, suggest that uptake occurs through both physisorption and chemisorption. The XPS spectra of MOF-808 zirconium 3d electrons reveal a charge redistribution following exposure to DMMP. In addition, analysis of the phosphorus 2p electrons following exposure and thermal annealing to 600 K indicates that two types of stable phosphorus-containing species exist within the MOF. DFT calculations, used to guide the IR band assignments and to help interpret the XPS features, suggest that uptake is driven by nucleophilic addition of an OH group to DMMP with subsequent elimination of a methoxy substituent to form strongly bound methyl methylphosphonic acid (MMPA). The rates of product formation indicate thatmore » there are likely two distinct uptake processes, requiring rate constants that differ by approximately an order of magnitude. However, the rates of molecular uptake were found to be nearly identical to the rates of reaction, which strongly suggests that the reaction rates are diffusion-limited. Here, the final products were found to inhibit further reactions within the MOFs, and these products could not be thermally driven from the MOFs prior to decomposition of the MOFs themselves.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [3]; ORCiD logo [3];  [1];  [4]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Stony Brook Univ., NY (United States)
  3. Emory Univ., Atlanta, GA (United States)
  4. Kennesaw State Univ., GA (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1368346
Grant/Contract Number:  
AC02-06CH11357; W911NF-15-2-0107
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 21; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; adsorption; metal organic frameworks; infrared light; noncovalent interactions; X-ray photoelectron spectroscopy

Citation Formats

Wang, G., Sharp, C., Plonka, A. M., Wang, Q., Frenkel, A. I., Guo, W., Hill, C., Smith, C., Kollar, J., Troya, D., and Morris, J. R. Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b00070.
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Wang, G., Sharp, C., Plonka, A. M., Wang, Q., Frenkel, A. I., Guo, W., Hill, C., Smith, C., Kollar, J., Troya, D., & Morris, J. R. Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study. United States. https://doi.org/10.1021/acs.jpcc.7b00070
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Wang, G., Sharp, C., Plonka, A. M., Wang, Q., Frenkel, A. I., Guo, W., Hill, C., Smith, C., Kollar, J., Troya, D., and Morris, J. R. Mon . "Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study". United States. https://doi.org/10.1021/acs.jpcc.7b00070. https://www.osti.gov/servlets/purl/1368346.
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@article{osti_1368346,
title = {Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study},
author = {Wang, G. and Sharp, C. and Plonka, A. M. and Wang, Q. and Frenkel, A. I. and Guo, W. and Hill, C. and Smith, C. and Kollar, J. and Troya, D. and Morris, J. R.},
abstractNote = {The mechanism and kinetics of interactions between dimethyl methylphosphonate (DMMP), a key chemical warfare agent (CWA) simulant, and Zr6-based metal organic frameworks (MOFs) have been investigated with in situ infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), and DFT calculations. DMMP was found to adsorb molecularly to UiO-66 through the formation of hydrogen bonds between the phosphoryl oxygen and the free hydroxyl groups associated with Zr6 nodes on the surface of crystallites and not within the bulk MOF structure. Unlike UiO-66, the infrared spectra for UiO-67 and MOF-808, recorded during DMMP exposure, suggest that uptake occurs through both physisorption and chemisorption. The XPS spectra of MOF-808 zirconium 3d electrons reveal a charge redistribution following exposure to DMMP. In addition, analysis of the phosphorus 2p electrons following exposure and thermal annealing to 600 K indicates that two types of stable phosphorus-containing species exist within the MOF. DFT calculations, used to guide the IR band assignments and to help interpret the XPS features, suggest that uptake is driven by nucleophilic addition of an OH group to DMMP with subsequent elimination of a methoxy substituent to form strongly bound methyl methylphosphonic acid (MMPA). The rates of product formation indicate that there are likely two distinct uptake processes, requiring rate constants that differ by approximately an order of magnitude. However, the rates of molecular uptake were found to be nearly identical to the rates of reaction, which strongly suggests that the reaction rates are diffusion-limited. Here, the final products were found to inhibit further reactions within the MOFs, and these products could not be thermally driven from the MOFs prior to decomposition of the MOFs themselves.},
doi = {10.1021/acs.jpcc.7b00070},
journal = {Journal of Physical Chemistry. C},
number = 21,
volume = 121,
place = {United States},
year = {Mon Apr 10 00:00:00 EDT 2017},
month = {Mon Apr 10 00:00:00 EDT 2017}
}
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