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Title: Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters

Abstract

The adsorption and decomposition of dimethyl methylphosphonate (DMMP), a chemical warfare agent (CWA) simulant, on size-selected molybdenum oxide trimer clusters, i.e. (MoO3)3, was studied both experimentally and theoretically. X-ray photoelectron spectroscopy (XPS), temperature programmed reaction (TPR), and density functional theory (DFT)-based simulations were utilized in this study. The XPS and TPR results showed both, desorption of intact DMMP, and decomposition of DMMP through the elimination of methanol at elevated temperatures on (MoO3)3 clusters. Theoretical investigation of DMMP on (MoO3)3 clusters suggested that, in addition to pure (MoO3)3 clusters, reduced molybdenum oxide clusters and hydroxylated molybdenum oxide clusters also play an important role in decomposing DMMP via a “reverse Mars–van Krevelen mechanism”. The present study, which focused on oxide clusters, underlines the importance of surface defects, e.g., the oxygen vacancies and surface hydroxyls, in determining the reaction pathway of DMMP, in agreement with previous studies on thin films. In addition, the structural fluxionality and the Lewis acidity of molybdenum oxide clusters, i.e. (MoO3)3, may make them good candidates for adsorption and decomposition of chemical warfare agents with similar structures to DMMP.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [3];  [4]; ORCiD logo [3]
  1. Department of Chemistry; Johns Hopkins University; Baltimore; USA
  2. Department of Physics; University of Konstanz; 78464 Konstanz; Germany
  3. Department of Materials Science; University of Maryland; College Park; USA
  4. Department of Physics; Tulane University; New Orleans; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1492845
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 20; Journal Issue: 7; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
English

Citation Formats

Tang, Xin, Hicks, Zachary, Wang, Linjie, Ganteför, Gerd, Bowen, Kit H., Tsyshevsky, Roman, Sun, Jianwei, and Kuklja, Maija M. Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters. United States: N. p., 2018. Web. doi:10.1039/c7cp08427g.
Tang, Xin, Hicks, Zachary, Wang, Linjie, Ganteför, Gerd, Bowen, Kit H., Tsyshevsky, Roman, Sun, Jianwei, & Kuklja, Maija M. Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters. United States. doi:10.1039/c7cp08427g.
Tang, Xin, Hicks, Zachary, Wang, Linjie, Ganteför, Gerd, Bowen, Kit H., Tsyshevsky, Roman, Sun, Jianwei, and Kuklja, Maija M. Mon . "Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters". United States. doi:10.1039/c7cp08427g.
@article{osti_1492845,
title = {Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters},
author = {Tang, Xin and Hicks, Zachary and Wang, Linjie and Ganteför, Gerd and Bowen, Kit H. and Tsyshevsky, Roman and Sun, Jianwei and Kuklja, Maija M.},
abstractNote = {The adsorption and decomposition of dimethyl methylphosphonate (DMMP), a chemical warfare agent (CWA) simulant, on size-selected molybdenum oxide trimer clusters, i.e. (MoO3)3, was studied both experimentally and theoretically. X-ray photoelectron spectroscopy (XPS), temperature programmed reaction (TPR), and density functional theory (DFT)-based simulations were utilized in this study. The XPS and TPR results showed both, desorption of intact DMMP, and decomposition of DMMP through the elimination of methanol at elevated temperatures on (MoO3)3 clusters. Theoretical investigation of DMMP on (MoO3)3 clusters suggested that, in addition to pure (MoO3)3 clusters, reduced molybdenum oxide clusters and hydroxylated molybdenum oxide clusters also play an important role in decomposing DMMP via a “reverse Mars–van Krevelen mechanism”. The present study, which focused on oxide clusters, underlines the importance of surface defects, e.g., the oxygen vacancies and surface hydroxyls, in determining the reaction pathway of DMMP, in agreement with previous studies on thin films. In addition, the structural fluxionality and the Lewis acidity of molybdenum oxide clusters, i.e. (MoO3)3, may make them good candidates for adsorption and decomposition of chemical warfare agents with similar structures to DMMP.},
doi = {10.1039/c7cp08427g},
journal = {Physical Chemistry Chemical Physics},
issn = {1463-9076},
number = 7,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

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