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Destruction of chemical warfare agents using metal–organic frameworks

Abstract

Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind1. Recent global military events, such as the conflict and disarmament in Syria2, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills3. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents4,5,6. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal–organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

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Figure 1: Molecular representations of the NU-1000 node and linker (left), MOF topology (two views, centre), and the dehydration of the NU-1000 node (right).
Figure 2: Hydrolysis data and reactions for DMNP and GD.
Figure 3: Association and reaction energies predicted by DFT.

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Acknowledgements

O.K.F., R.Q.S. and J.T.H. gratefully acknowledge DTRA for financial support (grant HDTRA-1-10-0023). C.J.C. gratefully acknowledges funding from the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-12ER16362). R.Q.S. acknowledges the National Energy Research Scientific Computing Center (NERSC) for computational resources. J.B.D. and G.W.P. gratefully acknowledge Joint Science and Technology Office for Chemical Biological Defense (JSTO–CBD) for funding (Project Number BA13PHM210).

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J.E.M., M.J.K., J.T.H. and O.K.F. developed the concept. J.E.M., M.J.K. and W.B. carried out the materials synthesis, characterization, and catalysis with the simulant DMNP under the supervision of O.K.F. and J.T.H.; P.G. and P.L. carried out DFT simulations with DMNP under the supervision of R.Q.S.; W.C.I.III carried out DFT simulations with GD and VX under the supervision of C.J.C.; G.W.W. and M.G.H. carried out GD NMR degradation experiments under the guidance of J.B.D. and G.W.P.; J.E.M., M.J.K., J.T.H., and O.K.F. wrote the manuscript first draft and the rest of the authors contributed to the editing.

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Correspondence to Joseph T. Hupp or Omar K. Farha.

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Competing interests

R.Q.S., J.T.H. and O.K.F. have a financial interest in the start-up company NuMat Technologies, which is seeking to commercialize metal–organic frameworks.

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Mondloch, J., Katz, M., Isley III, W. et al. Destruction of chemical warfare agents using metal–organic frameworks. Nature Mater 14, 512–516 (2015). https://doi.org/10.1038/nmat4238

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