Facile Decomposition of Organophosphonates by Dual Lewis Sites on a Fe3O4(111) Film

Walenta, Constantin A.; Xu, Fang; Tesvara, Celine; O’Connor, Christopher R.; Sautet, Philippe; Friend, Cynthia M.

doi:10.1021/acs.jpcc.0c01708

Facile Decomposition of Organophosphonates by Dual Lewis Sites on a Fe₃O₄(111) Film

Journal Article · Wed May 13 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c01708· OSTI ID:1802398

^[1]; ^[2]; Tesvara, Celine ^[3]; O’Connor, Christopher R. ^[2]; ^[4]; ^[5]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry & Chemical Biology; OSTI
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry & Chemical Biology
Univ. of California, Los Angeles, CA (United States). Chemical and Biomolecular Engineering Dept.
Univ. of California, Los Angeles, CA (United States). Chemical and Biomolecular Engineering Dept. Chemistry and Biochemistry Dept.
Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry & Chemical Biology. John A. Paulson School of Engineering and Applied Sciences

Dimethyl methylphosphonate (DMMP) is used as a simulant for toxic nerve agents and pesticides, rendering the understanding of surface chemistry requisite to design effective materials for organophosphonate (catalytic) decomposition at room temperature. In this work, DMMP surface chemistry is studied on an iron oxide surface in a very well-defined environment using temperature-programmed reaction, isotopic labeling, scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory. DMMP, (CH₃O)₂P(O)(CH₃), dissociates to yield methoxy and methyl methylphosphonate, (CH₃O)P(O)₂(CH₃), on the surface at room temperature. At higher temperatures, dimethyl ether is formed via intramolecular reaction, followed by the formation of formaldehyde and methanol from adsorbed methoxy decomposition during temperature-programmed reaction. Ultimately, stochiometric combustion at 870 K produces CO, H₂C=O, and CO₂ via reaction with lattice oxygen, with PO_x remaining on the surface. Excess oxygen from the bulk is required to drive these higher temperature pathways. Neither hydrolysis nor a photoreaction is observed, when exposing the adsorbed DMMP to water or light above the band gap, respectively. No evolution of P-containing species is detected, indicating efficient trapping of this contaminant. The activity for DMMP decomposition at room temperature is reduced by the accumulation of PO_x. However, a significant amount of reaction persists after multiple temperature-programmed reaction experiments.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012573; SC0012704

OSTI ID:: 1802398

Alternate ID(s):: OSTI ID: 1843927

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 23 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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