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Title: Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808

Abstract

Developing novel and more efficient filters for chemical warfare agent (CWA) decomposition remains an important challenge for modern technology due to the continuous threat those weapons present in the event of use. Recently, metal–organic frameworks (MOFs) have attracted attention as potential catalysts for nerve agent decomposition. However, in order to improve their performance under battlefield conditions, it is crucial to understand the influence of ambient contaminants such as carbon dioxide on CWA adsorption and decomposition. In this paper, we present a comprehensive experimental and computational study on the influence of CO2 on the adsorption and decomposition of the CWA simulant dimethyl methyl phosphonate (DMMP) by the Zr-based MOF-808. The study combined in situ synchrotron powder X-ray diffraction (PXRD) with variable-temperature infrared spectroscopy (VTIR) and computations. PXRD and experiments with pure CO2 revealed that the MOF framework contracts by 0.2% after CO2 saturation and CO2 adsorbs within the MOF-808 framework via dispersion forces with an enthalpy of adsorption of -32.2 ± 1.8 kJ/mol. From five DRIFTS experiments conducted in various gas flow regimes we established that CO2 interferes with the decomposition of DMMP due to the formation of carbonate species, while if it is used as a regeneration agent, it acceleratesmore » the desorption of DMMP and DMMP decomposition products. In situ PXRD experiments showed that CO2 also limited expansion of the framework due to the formation of carbonate species by 40% in comparison to values in a control experiment with N2. The main conclusions of the computational study are (a) CO2 reversibly adsorbs onto MOF-808 via both μ3-OH groups located within the tetrahedral pores of the MOF and/or to the MOF surface with stabilizing dispersion interactions, (b) the presence of DMMP provides stability to the CO2–(μ3-OH) moiety, which hinders the μ3-OH transfer to the DMMP molecule required for the nerve-agent decomposition until the carbonyl to carbonate transformation is completed, and (c) CO2 molecules are not sufficient for the regeneration of the MOF when DMMP decomposition products are present but rather there is desorption of bound DMMP.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [4];  [5];  [6]; ORCiD logo [1];  [1];  [7];  [5]; ORCiD logo [2]; ORCiD logo [8]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Emory Univ., Atlanta, GA (United States). Cherry L. Emerson Center for Scientific, and Dept. of Chemistry
  4. U.S. Army CCDC Chemical Biological Center, Aberdeen Proving Ground, MD (United States)
  5. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  7. Kennesaw State Univ., Kennesaw, GA (United States). Dept. of Chemistry
  8. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1577425
Report Number(s):
BNL-212375-2019-JAAM
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 23; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Plonka, Anna M., Grissom, Tyler G., Musaev, Djamaladdin G., Balboa, Alex, Gordon, Wesley O., Collins-Wildman, Daniel L., Ghose, Sanjit K., Tian, Yiyao, Ebrahim, Amani M., Mitchell, Mark B., Hill, Craig L., Morris, John R., and Frenkel, Anatoly I.. Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.chemmater.9b04565.
Plonka, Anna M., Grissom, Tyler G., Musaev, Djamaladdin G., Balboa, Alex, Gordon, Wesley O., Collins-Wildman, Daniel L., Ghose, Sanjit K., Tian, Yiyao, Ebrahim, Amani M., Mitchell, Mark B., Hill, Craig L., Morris, John R., & Frenkel, Anatoly I.. Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808. United States. https://doi.org/10.1021/acs.chemmater.9b04565
Plonka, Anna M., Grissom, Tyler G., Musaev, Djamaladdin G., Balboa, Alex, Gordon, Wesley O., Collins-Wildman, Daniel L., Ghose, Sanjit K., Tian, Yiyao, Ebrahim, Amani M., Mitchell, Mark B., Hill, Craig L., Morris, John R., and Frenkel, Anatoly I.. Mon . "Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808". United States. https://doi.org/10.1021/acs.chemmater.9b04565. https://www.osti.gov/servlets/purl/1577425.
@article{osti_1577425,
title = {Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808},
author = {Plonka, Anna M. and Grissom, Tyler G. and Musaev, Djamaladdin G. and Balboa, Alex and Gordon, Wesley O. and Collins-Wildman, Daniel L. and Ghose, Sanjit K. and Tian, Yiyao and Ebrahim, Amani M. and Mitchell, Mark B. and Hill, Craig L. and Morris, John R. and Frenkel, Anatoly I.},
abstractNote = {Developing novel and more efficient filters for chemical warfare agent (CWA) decomposition remains an important challenge for modern technology due to the continuous threat those weapons present in the event of use. Recently, metal–organic frameworks (MOFs) have attracted attention as potential catalysts for nerve agent decomposition. However, in order to improve their performance under battlefield conditions, it is crucial to understand the influence of ambient contaminants such as carbon dioxide on CWA adsorption and decomposition. In this paper, we present a comprehensive experimental and computational study on the influence of CO2 on the adsorption and decomposition of the CWA simulant dimethyl methyl phosphonate (DMMP) by the Zr-based MOF-808. The study combined in situ synchrotron powder X-ray diffraction (PXRD) with variable-temperature infrared spectroscopy (VTIR) and computations. PXRD and experiments with pure CO2 revealed that the MOF framework contracts by 0.2% after CO2 saturation and CO2 adsorbs within the MOF-808 framework via dispersion forces with an enthalpy of adsorption of -32.2 ± 1.8 kJ/mol. From five DRIFTS experiments conducted in various gas flow regimes we established that CO2 interferes with the decomposition of DMMP due to the formation of carbonate species, while if it is used as a regeneration agent, it accelerates the desorption of DMMP and DMMP decomposition products. In situ PXRD experiments showed that CO2 also limited expansion of the framework due to the formation of carbonate species by 40% in comparison to values in a control experiment with N2. The main conclusions of the computational study are (a) CO2 reversibly adsorbs onto MOF-808 via both μ3-OH groups located within the tetrahedral pores of the MOF and/or to the MOF surface with stabilizing dispersion interactions, (b) the presence of DMMP provides stability to the CO2–(μ3-OH) moiety, which hinders the μ3-OH transfer to the DMMP molecule required for the nerve-agent decomposition until the carbonyl to carbonate transformation is completed, and (c) CO2 molecules are not sufficient for the regeneration of the MOF when DMMP decomposition products are present but rather there is desorption of bound DMMP.},
doi = {10.1021/acs.chemmater.9b04565},
journal = {Chemistry of Materials},
number = 23,
volume = 31,
place = {United States},
year = {2019},
month = {11}
}

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