Hot Press Synthesis of MOF/Textile Composites for Nerve Agent Detoxification

Abstract

Chemical nerve agents employed in warfare can induce paralysis and death within minutes of exposure. Zirconium-based metal–organic frameworks (MOFs), such as UiO-66-NH2, show promise for the fast and efficient decontamination of nerve agents, which motivates their incorporation into textiles as protective layers. Few scalable methods to produce MOF/textile composites for personal protective applications have been developed; however, they mainly require the use of toxic and flammable solvents. Here, we describe a scalable, single-step method to synthesize UiO-66-NH2 on cotton fabrics by hot pressing the monomers onto the fabric samples. The use of a preformed hexanuclear zirconium benzoate cluster with 1,8-bis­(dimethylamine)­naphthalene as a non-nucleophilic base improved the quality of MOFs synthesized from the hot press method, as determined by an increase in their surface area and crystallinity. Preactivation of the cotton fabric with carboxylic acids provided UiO-66-NH2/cotton composites of high MOF loadings with homogeneous coverage, which demonstrated efficient decontamination of a nerve agent simulant, dimethyl-4-nitrophenyl phosphate (DMNP).

Feasible Detoxification Coating Material for Chemical Warfare Agents Using Poly(methyl methacrylate)–Branched Poly(ethyleneimine) Copolymer and Metal–Organic Framework Composites

“…For comparison with the previous studies, the profiles of the solution-processable MOF and polymer composites are summarized in Table . Several MOF and polymer composites were reported as detoxification materials for CWA, but the degradation condition was generally limited to N-EM buffer solution. − Otherwise, the PMB composite could detoxify MPO without additional buffer with the fastest kinetics (4.71 h –1 k value). The strategically designed PMMA-BPEI polymer could simultaneously act as a binder and a buffer, resulting in superior catalytic activity for CWA hydrolysis even without an additional buffer (N-EM).…”

Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

“…9,29 The incorporation of MOFs into textiles represents current research goals/achievements with the challenge of maintaining the flexibility and permeability of common fabrics while still imbuing potent reactivity. 30 Though research on MOF development and integration has grown tremendously over the years, issues with scalability and cost for these materials remain one of the main limiting factors hindering widespread implementation. Alternatively, reactive nucleophilic polymeric materials have been explored for applications in protective gear and selfdetoxifying materials for the removal and degradation of CWAs.…”

“…) , have demonstrated exceptional reactivity toward the degradation of nerve agents and simulants. For example, Farha, Peterson, and co-workers have developed a series of Zr-based MOFs with various chemical functionalities to detoxify nerve agent simulants such as dimethyl-4-nitrophenyl phosphate (DMNP) and diisopropyl fluorophosphate (DFP), as well as nerve agents such as GA (tabun), GB (sarin), GD (soman) and VX. , The incorporation of MOFs into textiles represents current research goals/achievements with the challenge of maintaining the flexibility and permeability of common fabrics while still imbuing potent reactivity . Though research on MOF development and integration has grown tremendously over the years, issues with scalability and cost for these materials remain one of the main limiting factors hindering widespread implementation.…”

MOF–Polymer Mixed Matrix Membranes as Chemical Protective Layers for Solid-Phase Detoxification of Toxic Organophosphates

“…The typical powdered form of Zr-MOFs makes them unfeasible for direct application as protective layers. To solve this problem, Zr-MOFs can be integrated with polymeric fibers ( e.g., cotton, polyester, polysulfone, and polyamide) to produce MOF/polymer composite catalysts that can be readily processed to afford the desired form for improved practicality. − These Zr-MOFs/polymer composites could efficiently catalyze the hydrolysis of nerve agents/simulants in aqueous solutions, but these reactions are typically much slower in the solid phase due to their reliance on water media. The low efficiency of MOF/polymer composites in the solid phase is a major obstacle to their utility as protective layers for CWAs.…”