Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

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dc.contributor.authorWang, Qien
dc.contributor.authorChapleski, Robert C. Jr.en
dc.contributor.authorPlonka, Anna M.en
dc.contributor.authorGordon, Wesley O.en
dc.contributor.authorGuo, Weiweien
dc.contributor.authorThuy-Duong Nguyen-Phanen
dc.contributor.authorSharp, Conor H.en
dc.contributor.authorMarinkovic, Nebojsa S.en
dc.contributor.authorSenanayake, Sanjaya D.en
dc.contributor.authorMorris, John R.en
dc.contributor.authorHill, Craig L.en
dc.contributor.authorTroya, Diegoen
dc.contributor.authorFrenkel, Anatoly I.en
dc.contributor.departmentChemistryen
dc.date.accessioned2019-01-09T17:29:48Zen
dc.date.available2019-01-09T17:29:48Zen
dc.date.issued2017-04-10en
dc.description.abstractAmbient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs-8[Nb6O19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb6O19](8)-polyanion, its Cs+ counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general base (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs-8[Nb6O19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M) MPA) product to the polyanions, which ultimately inhibits catalytic turnover.en
dc.description.notesThis work is supported by the U.S. Army Research Laboratory and the U.S. Army Research Office under grant number W911NF-15-2-0107. The authors thank the Defense Threat Reduction Agency for support under program BB11PHM156. Use of Argonne Advanced Photon Source, and Stanford Synchrotron Radiation Lightsource, was supported by DOE under Contracts No. DE-AC02-06CH11357, DE-AC02-76SF00515 and DE-SC0012704, respectively. In situ operations at the BL2-2 beamline at SLAC were made possible by the DOE grant No. DE-SC0012335. The authors gratefully acknowledge the beamline staff at SSRL BL2-2, APS BL 9BM, and APS 17BM, particularly Dr. Matthew Latimer (SSRL) and Dr. Tianpin Wu (APS) for their assistance in beamline operation. The authors acknowledge Advanced Research Computing at Virginia Tech for providing computational resources and technical support.en
dc.description.sponsorshipU.S. Army Research Laboratory; U.S. Army Research Office [W911NF-15-2-0107]; Defense Threat Reduction Agency [BB11PHM156]; DOE [DE-AC02-06CH11357, DE-AC02-76SF00515, DE-SC0012704, DE-SC0012335]en
dc.format.extent8en
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1038/s41598-017-00772-xen
dc.identifier.issn2045-2322en
dc.identifier.other773en
dc.identifier.pmid28396583en
dc.identifier.urihttp://hdl.handle.net/10919/86647en
dc.identifier.volume7en
dc.language.isoenen
dc.publisherSpringer Natureen
dc.rightsCreative Commons Attribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectchemical warfare agentsen
dc.subjectmetal-organic frameworksen
dc.subjectray-absorption-spectroscopyen
dc.subjectenhanced raman-spectroscopyen
dc.subjectnormal-coordinate analysisen
dc.subjectmethylphosphonic aciden
dc.subjectvibrational analysisen
dc.subjectnerve agentsen
dc.subjectspectraen
dc.subjectsurfaceen
dc.titleAtomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decompositionen
dc.title.serialScientific Reportsen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten

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