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Engineered Beads for Chem-Bio Defense (CBD) Personal Protective Equipment (PPE)

Description:

TECHNOLOGY AREA(S): Materials, Chem Bio Defense

OBJECTIVE: The Joint Chemical and Biological Defense Program seeks innovative solutions for engineering robust spherical beads containing metal-organic frameworks (MOFs) and/or metal oxyhydroxides (MOs) for use in chemical-biological (CB) personal protective equipment (PPE).

DESCRIPTION: Current military CB suits utilize activated carbon as a protective barrier against chemical warfare agents (CWAs).While effective, carbon does not efficiently detoxify CWAs.The ability to integrate a reactive material into suits represents an advantage for mitigating the chemical hazard.MOFs and MOs in particular have shown promise for decomposing and detoxifying CWAs and toxic industrial chemicals (TICs).1-7However, integration into uniforms has lagged due to the difficulty of making MOF/MO beads.This is particularly difficult with MOFs and MOs, especially when considering traditional techniques such as emulsion polymerization followed by polymerization and carbonization, which would render the MOFs and MOs inactive towards CWAs.Thus, this topic seeks novel and innovative techniques for engineering MOFs and MOs into spherical beads.The engineered beads should be high mass loading of MOF or MO without significant attrition of the particle.The polymer used should be such that the MOF or MO is accessible to toxic compounds, that is, the polymer should not interact with active sites or block pores of the MOF or MO.Successful approaches will focus on engineering design principles and develop methods (and materials) in a variety of spherical diameters, focusing primarily on 100-500 µm (micrometers).Beads that are developed will be robust enough such that further processing into suits and other applications using techniques such as hot pressing, use with adhesives, and even extrusion are feasible.

PHASE I: Demonstrate the ability to make spherical particles containing high (>80%) MOF/MO materials in a variety of sizes (focus on 100-500 µm).Demonstrate activity using probe molecules and Chemical Weapon Agents (CWA) and/or simulants, as appropriate, with minimal loss in activity as compared to the native powder.

PHASE II: Fully optimize bead processing.Scale the process of bead manufacturing (> 1 kg quantities) and develop techniques for integrating beads into/onto textiles.Understand structure-activity-processing relationships, especially pertaining to bead size, MOF/MO loading, and barrier properties (e.g., permeation of simulants, air/moisture permeability, etc.).Achieve 100% reactivity of CWAs/simulants after 24 hours.

PHASE III: Collaborate with industry partners to develop full protective suits and ensembles for military applications.Determine additional use applications for the MOF/MO materials, such as filtration and decontamination.PHASE III DUAL USE APPLICATIONS:First responder personnel, pesticide applications personnel, etc. would all benefit from a health & safety perspective resulting from the proposed technology

KEYWORDS: Metal-organic framework, MOF, metal oxyhydroxides, zirconium hydroxide, polymer, bead, protective suit

References:

1. Bandosz, T. J.; Laskoski, M.; Mahle, J.; Mogilevsky, G.; Peterson, G. W.; Rossin, J. A.; Wagner, G. W., Reactions of VX, GD, and HD with Zr(OH)(4): Near Instantaneous Decontamination of VX. Journal of Physical Chemistry C 2012, 116, (21), 11606-11614.2.De Coste, J. B.; Peterson, G. W., Metal-Organic Frameworks for Air Purification of Toxic Chemicals. Chem. Rev. (Washington, DC, U. S.) 2014, 114, (11), 5695-5727.3.Mondloch, J. E.; Katz, M. J.; Isley Iii, W. C.; Ghosh, P.; Liao, P.; Bury, W.; Wagner, G. W.; Hall, M. G.; DeCoste, J. B.; Peterson, G. W.; Snurr, R. Q.; Cramer, C. J.; Hupp, J. T.; Farha, O. K., Destruction of chemical warfare agents using metal–organic frameworks. Nat Mater 2015, advance online publication.4.Moon, S.-Y.; Wagner, G. W.; Mondloch, J. E.; Peterson, G. W.; DeCoste, J. B.; Hupp, J. T.; Farha, O. K., Effective, Facile, and Selective Hydrolysis of the Chemical Warfare Agent VX Using Zr6-Based Metal–Organic Frameworks. Inorganic Chemistry 2015, 54, (22), 10829-10833.5.Moon, S. Y.; Proussaloglou, E.; Peterson, G. W.; DeCoste, J. B.; Hall, M. G.; Howarth, A. J.; Hupp, J. T.; Farha, O. K., Detoxification of Chemical Warfare Agents Using a Zr-6-Based Metal-Organic Framework/Polymer Mixture. Chemistry-a European Journal 2016, 22, (42), 14864-14868.6.Peterson, G. W.; Destefano, M. R.; Garibay, S. J.; Ploskonka, A.; McEntee, M.; Hall, M.; Karwacki, C. J.; Hupp, J. T.; Farha, O. K., Optimizing Toxic Chemical Removal through Defect-Induced UiO-66-NH2 Metal-Organic Framework. Chemistry-a European Journal 2017, 23, (63), 15913-15916.7.Lu, A. X.; McEntee, M.; Browe, M. A.; Hall, M. G.; DeCoste, J. B.; Peterson, G. W., MOFabric: Electrospun Nanofiber Mats from PVDF/UiO-66-NH2 for Chemical Protection and Decontamination. ACS Applied Materials & Interfaces 2017, 9, (15), 13632-13636.

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