Stretchable and Multi-Metal–Organic Framework Fabrics Via High-Yield Rapid Sorption-Vapor Synthesis and Their Application in Chemical Warfare Agent Hydrolysis

Abstract

Protocols to create metal−organic framework (MOF)/polymer composites for separation, chemical capture, and catalytic applications currently rely on relatively slow solution-based processing to form single MOF composites. Here, we report a rapid, high-yield sorption-vapor method for direct simultaneous growth of single and multiple MOF materials onto untreated flexible and stretchable polymer fibers and films. The synthesis utilizes favorable reactant absorption into polymers coupled with rapid vapor-driven MOF crystallization to form high surface area (>250 m 2 /g composite ) composites, including UiO-66-NH 2 , HKUST-1, and MOF-525 on spandex, nylon, and other fabrics. The resulting composites are robust and maintain their functionality even after stretching. Stretchable MOF fabrics enable rapid solid-state hydrolysis of the highly toxic chemical warfare agent soman and paraoxon-methyl simulant. We show that this approach can readily be scaled by solution spray-coating of MOF precursors and to large area substrates.

Green MOF-Fabrics: Benign, Scalable Sorption-Vapor Synthesis of Catalytic Composites to Protect against Phosphorus-Based Toxins

“…Previously, using DMF-based solvents, polyamide@UiO-66-NH 2 fabrics formed by vapor-sorption synthesis showed that the extent of MOF loading changed in proportion to the concentration of MOF precursors in the starting solution . Therefore, the results in Figure suggest that any resulting changes in the concentration of the precursor solution do not significantly influence the MOF growth.…”

“…As presented in Scheme , MOF-fabrics were synthesized by submerging fabric swatches in a precursor solution to absorb MOF precursors, followed by suspending the damp samples above a heated modulator solution. The modulator vapor then promoted MOF reactants to diffuse from the fabric and form well-adhered crystalline MOFs on the surface of each fiber . The precursor solutions used the same solvent compositions as for the powder synthesis (Table S1).…”

“…The modulator vapor then promoted MOF reactants to diffuse from the fabric and form well-adhered crystalline MOFs on the surface of each fiber. 24 The precursor solutions used the same solvent compositions as for the powder synthesis (Table S1). The vapor modulator was DMF(84%)/HOAc(16%) for full DMF and H 2 O(50%)/ HOAc(50%) for partial DMF, EtOH, and GVL.…”

“…Chemical warfare agent degradation was tested using the dose extraction method, which has been previously defined. 24 Briefly, 10−40 mg of MOF-fabrics or MOF powders was placed in small vials to minimize vapor loss, dried at 60 °C for 1 h, and humidified at 50% relative humidity (RH) overnight. CWA was then delivered to the vials and dispersed by vortexing.…”

“…12,22,23 In this report, we describe the synthesis of MOF-fabrics using only nontoxic solvents and evaluate their performance for degradation and permeation of chemical warfare agents and simulants. The MOF-fabrics are formed by sorption-vapor synthesis, 24 as shown in Scheme 1, where a fabric swatch first absorbs the solvent/reactant mixture from the precursor solution, followed by suspension over a heated solvent/ modulator mixture for 3−24 h, allowing the reactants to diffuse out of the polymer and form MOF crystals firmly attached on the polymer fiber surface. As an experimental control, using the same reactant/solvent/modulator system, we also formed MOF powders homogeneously via solvothermal synthesis, and the MOFs in powder form were analyzed and compared directly to the MOFs formed on the polymer fabrics.…”