Correlated Multimodal Approach Reveals Key Details of Nerve-Agent Decomposition by Single-Site Zr-Based Polyoxometalates

Journal Article · Fri Apr 19 00:00:00 EDT 2019 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.9b01002· OSTI ID:1525399

Tian, Yiyao ^[1]; Plonka, Anna M. ^[1]; Ebrahim, Amani M. ^[1]; Palomino, Robert M. ^[2]; Senanayake, Sanjaya D. ^[2]; Balboa, Alex ^[3]; Gordon, Wesley O. ^[3]; Troya, Diego ^[4]; Musaev, Djamaladdin G. ^[5]; Morris, John R. ^[4]; Mitchell, Mark B. ^[6]; Collins-Wildman, Daniel L. ^[5]; Hill, Craig L. ^[5]; Frenkel, Anatoly I. ^[7]

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1. Stony Brook Univ., Stony Brook, NY (United States)
2. Brookhaven National Lab. (BNL), Upton, NY (United States)
3. U.S. Army Edgewood Chemical Biological Center, Aberdeen Proving Ground, MD (United States)
4. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
5. Emory Univ., Atlanta, GA (United States)
6. Kennesaw State Univ., Kennesaw, GA (United States)
7. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Development of technologies for protection against chemical warfare agents (CWAs) is critically important. Recently, polyoxometalates have attracted attention as potential catalysts for nerve-agent decomposition. Improvement of their effectiveness in real operating conditions requires an atomic-level understanding of CWA decomposition at the gas–solid interface. We investigated decomposition of the nerve agent Sarin and its simulant, dimethyl chlorophosphate (DMCP), by zirconium polytungstate. Using a multimodal approach, we showed that upon DMCP and Sarin exposure the dimeric tungstate undergoes monomerization, making coordinatively unsaturated Zr(IV) centers available, which activate nucleophilic hydrolysis. Furthermore, DMCP is shown to be a good model system of reduced toxicity for studies of CWA deactivation at the gas–solid interface.

• Research Organization: Brookhaven National Laboratory (BNL), Upton, NY (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• Grant/Contract Number: SC0012704
• OSTI ID: 1525399
• Report Number(s): BNL--211759-2019-JAAM
• Journal Information: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 9 Vol. 10; ISSN 1948-7185
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY