Abstract
AbstractOrganophosphonates 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. ...
Highlights
Organophosphonates are used as pesticides, corrosion inhibitors, and chemical warfare agents, and their chemistry has been widely studied.[1]
Organophosphonates are used as chemical warfare agents
a material used in chemical warfare agent filtration devices
Summary
Organophosphonates are used as pesticides, corrosion inhibitors, and chemical warfare agents, and their chemistry has been widely studied.[1]. Undercoordinated metal atoms and hydroxyl groups are the common surface binding sites for the phosphoryl moiety of DMMP.[1] The most stable (010) surface of MoO3 is oxygen-terminated with no inherent undercoordinated Mo atoms on the surface[4] and does not hydroxylate; this surface contrasts with those previously studied.[1,5] Here, we continue our previous investigations of the adsorption of dimethyl methylphosphonate (DMMP), a common chemical warfare agent simulant, on polycrystalline MoO3.6 Our past studies with ambient pressure X-ray photoelectron spectroscopy (APXPS) and density functional theory found evidence for weak, intact adsorption on pristine MoO3 surfaces at room temperature, while decomposition to methanol upon adsorption was observed for hydroxylated surfaces. In both cases the molecular coverage depended on the DMMP partial pressure
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