Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Univ. of Maryland, College Park, MD (United States). Materials Science and Engineering Dept.
- Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry
- Naval Research Lab. (NRL), Washington, DC (United States). Chemistry Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Vrije Univ. Brussel, Brussels (Netherlands). Dept. of Materials and Chemistry, SURF Research Group
- Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry
- Univ. of Maryland, College Park, MD (United States). Materials Science and Engineering Dept.
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here in this paper, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron and infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO-CH3, P-OCH3, and P-CH3 bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOD
- Grant/Contract Number:
- AC02-05CH11231; DMR-130077; HDTRA11510005
- OSTI ID:
- 1456977
- Journal Information:
- Chemistry of Materials, Vol. 29, Issue 17; ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Various spectroelectrochemical cells for in situ observation of electrochemical processes at solid–liquid interfaces
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journal | October 2018 |
Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO 3 ) 3 clusters
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journal | January 2018 |
Adsorption and Decomposition of DMMP on Size-Selected (WO 3 ) 3 Clusters
|
journal | April 2018 |
Facile Decomposition of Organophosphonates by Dual Lewis Sites on a Fe 3 O 4 (111) Film
|
journal | May 2020 |
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