In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

Plonka, Anna M.; Wang, Qi; Gordon, Wesley O.; Balboa, Alex; Troya, Diego; Guo, Weiwei; Sharp, Conor H.; Senanayake, Sanjaya D.; Morris, John R.; Hill, Craig L.; Frenkel, Anatoly I.

doi:10.1021/jacs.6b11373

Title: In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

Journal Article · Thu Dec 29 23:00:00 EST 2016 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.6b11373 · OSTI ID:1349576

^[1]; Wang, Qi ^[1]; Gordon, Wesley O. ^[2]; Balboa, Alex ^[2];

^[3]; Guo, Weiwei ^[4]; Sharp, Conor H. ^[3]; Senanayake, Sanjaya D. ^[5]; Morris, John R. ^[3]; Hill, Craig L. ^[4];

^[1]

Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
U.S. Army Edgewood Chemical Biological Center APG, Aberdeen Proving Ground, MD (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry

Recently, Zr-based metal organic frameworks (MOFs) were shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. Here, we report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. Our experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

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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:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1349576

Report Number(s):: BNL--113713-2017-JA; KC0302010

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 2 Vol. 139; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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