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Title: Thermal desorption of dimethyl methylphosphonate from MoO 3

Organophosphonates are used as chemical warfare agents, pesticides, and corrosion inhibitors. New materials for the sorption, detection, and decomposition of these compounds are urgently needed. To facilitate materials and application innovation, a better understanding of the interactions between organophosphonates and surfaces is required. To this end, we have used diffuse reflectance infrared Fourier transform spectroscopy to investigate the adsorption geometry of dimethyl methylphosphonate (DMMP) on MoO 3, a material used in chemical warfare agent filtration devices. We further applied ambient pressure X-ray photoelectron spectroscopy and temperature programmed desorption to study the adsorption and desorption of DMMP. While DMMP adsorbs intact on MoO 3, desorption depends on coverage and partial pressure. At low coverages under UHV conditions, the intact adsorption is reversible. Decomposition occurs with higher coverages, as evidenced by PCH x and PO x decomposition products on the MoO 3 surface. Heating under mTorr partial pressures of DMMP results in product accumulation.
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [3] ;  [1] ;  [4] ;  [5] ;  [1] ;  [6] ;  [6] ;  [3] ;  [2] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
  3. Univ. of Maryland, College Park, MD (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Maryland, College Park, MD (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Aarhus (Denmark)
  6. Naval Research Lab. (NRL), Washington, DC (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Catalysis, Structure & Reactivity
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1-2; Journal ID: ISSN 2055-074X
Publisher:
Taylor & Francis
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (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:
1379760

Head, Ashley R., Tang, Xin, Hicks, Zachary, Wang, Linjie, Bleuel, Hannes, Holdren, Scott, Trotochaud, Lena, Yu, Yi, Kyhl, Line, Karslıoǧlu, Osman, Fears, Kenan, Owrutsky, Jeffrey, Zachariah, Michael, Bowen, Kit H., and Bluhm, Hendrik. Thermal desorption of dimethyl methylphosphonate from MoO3. United States: N. p., Web. doi:10.1080/2055074X.2017.1278891.
Head, Ashley R., Tang, Xin, Hicks, Zachary, Wang, Linjie, Bleuel, Hannes, Holdren, Scott, Trotochaud, Lena, Yu, Yi, Kyhl, Line, Karslıoǧlu, Osman, Fears, Kenan, Owrutsky, Jeffrey, Zachariah, Michael, Bowen, Kit H., & Bluhm, Hendrik. Thermal desorption of dimethyl methylphosphonate from MoO3. United States. doi:10.1080/2055074X.2017.1278891.
Head, Ashley R., Tang, Xin, Hicks, Zachary, Wang, Linjie, Bleuel, Hannes, Holdren, Scott, Trotochaud, Lena, Yu, Yi, Kyhl, Line, Karslıoǧlu, Osman, Fears, Kenan, Owrutsky, Jeffrey, Zachariah, Michael, Bowen, Kit H., and Bluhm, Hendrik. 2017. "Thermal desorption of dimethyl methylphosphonate from MoO3". United States. doi:10.1080/2055074X.2017.1278891. https://www.osti.gov/servlets/purl/1379760.
@article{osti_1379760,
title = {Thermal desorption of dimethyl methylphosphonate from MoO3},
author = {Head, Ashley R. and Tang, Xin and Hicks, Zachary and Wang, Linjie and Bleuel, Hannes and Holdren, Scott and Trotochaud, Lena and Yu, Yi and Kyhl, Line and Karslıoǧlu, Osman and Fears, Kenan and Owrutsky, Jeffrey and Zachariah, Michael and Bowen, Kit H. and Bluhm, Hendrik},
abstractNote = {Organophosphonates are used as chemical warfare agents, pesticides, and corrosion inhibitors. New materials for the sorption, detection, and decomposition of these compounds are urgently needed. To facilitate materials and application innovation, a better understanding of the interactions between organophosphonates and surfaces is required. To this end, we have used diffuse reflectance infrared Fourier transform spectroscopy to investigate the adsorption geometry of dimethyl methylphosphonate (DMMP) on MoO3, a material used in chemical warfare agent filtration devices. We further applied ambient pressure X-ray photoelectron spectroscopy and temperature programmed desorption to study the adsorption and desorption of DMMP. While DMMP adsorbs intact on MoO3, desorption depends on coverage and partial pressure. At low coverages under UHV conditions, the intact adsorption is reversible. Decomposition occurs with higher coverages, as evidenced by PCHx and POx decomposition products on the MoO3 surface. Heating under mTorr partial pressures of DMMP results in product accumulation.},
doi = {10.1080/2055074X.2017.1278891},
journal = {Catalysis, Structure & Reactivity},
number = 1-2,
volume = 3,
place = {United States},
year = {2017},
month = {3}
}