Scalable and Template-Free Aqueous Synthesis of Zirconium-Based Metal–Organic Framework Coating on Textile Fiber

Abstract

Organophosphonate-based nerve agents, such as VX, Sarin (GB), and Soman (GD), are among the most toxic chemicals to humankind. Recently, we have shown that Zr-based metal–organic frameworks (Zr-MOFs) can effectively catalyze the hydrolysis of these toxic chemicals for diminishing their toxicity. On the other hand, utilizing these materials in powder form is not practical, and developing scalable and economical processes for integrating these materials onto fibers is crucial for protective gear. Herein, we report a scalable, template-free, and aqueous solution-based synthesis strategy for the production of Zr-MOF-coated textiles. Among all MOF/fiber composites reported to date, the MOF-808/polyester fibers exhibit the highest rates of nerve agent hydrolysis. Moreover, such highly porous fiber composites display significantly higher protection time compared to that of its parent fabric for a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). A decreased diffusion rate of toxic chemicals through the MOF layer can provide time needed for the destruction of the harmful species.

Doubly Protective MOF‐Photo‐Fabrics: Facile Template‐Free Synthesis of PCN‐222‐Textiles Enables Rapid Hydrolysis, Photo‐Hydrolysis and Selective Oxidation of Multiple Chemical Warfare Agents and Simulants

“…For example, to protect military and civilians against potential CWA threats, there is critical need for catalytically active composites that can be deployed in engineered clothing, field‐shelters, surface decontamination towels, sensors, wound dressings and other PPE [5, 32, 33] . These and related needs will benefit from new synthesis methods for MOF‐fabric composites employing simple, safe, and chemically mild procedures such as electrospinning, direct solvothermal growth, spray‐coating, or adhesives [22, 30, 42–44, 34–41] …”

“…[5,32,33] These and related needs will benefit from new synthesis methods for MOF-fabric composites employing simple, safe, and chemically mild procedures such as electrospinning, direct solvothermal growth, spray-coating,o ra dhesives. [22,30,[42][43][44][34][35][36][37][38][39][40][41] For any protective garment using MOF-fabrics, the safety of the fabric itself will be an important concern. While there are only af ew reports regarding MOF safety, [45,46] toxicityi se xpected to depend on MOF crystal size, composition, and stability, with the smallest crystals (< 100 nm) of primary concern.…”

“…Table 1 summarizes MOF‐fabric composites and their catalytic activity for CWA (GD and HD) degradation, including t 1/2 , turn‐over‐frequency evaluated at t 1/2 (TOF , described in the Supporting Information), and the time needed for 100 % conversion. Data includes previously reported UiO‐66 derivatives on nylon [34] and MOF‐808 on cotton with solid PEI buffer, [41] and polyester, [42] as well as new data for PCN‐222 on PP, presented below. Analogous results using MOF powders are given in Table S1, and data collected using CWA simulants (with MOF‐fabric and MOF powder catalysts) are in Table S2.…”

Spray‐Coating of Catalytically Active MOF–Polythiourea through Postsynthetic Polymerization

“…Moreover, the ALD materials lack covalent attachment to the polymer backbone, making them potentially susceptible to physical agitation. Recently, Farha and co‐workers also reported a method for coating textiles with Zr‐based MOFs . These materials displayed good activity for the degradation of nerve agents; however, laundry simulation tests with detergent to test physical durability were not described.…”

Capture of Sulfur Mustard by Pillar[5]arene: From Host-Guest Complexation to Efficient Adsorption Using Nonporous Adaptive Crystals

“…Recently, the adsorption and photocatalytic oxidation of SM simulants by MOFs have been well demonstrated ( Ma et al., 2019 ; Cao et al., 2019 ; Lee et al., 2020 ; Giannakoudakis and Bandosz, 2020 ). The present system based on organic macrocycles has the following characteristics (the advantages of pillar[5]arene over MOF are summarized in Table S1 ): (1) easy accessibility: EtP5 can be prepared through a single-step reaction in high yield of more than 70%, and all reagents are cheap and commercially available; (2) good stability: crystalline materials of EtP5 are stable to moisture; (3) high complexation ability and adsorption stability: SM and its simulants can be quantitatively prisoned in pillar[5]arene containers for quite a long time; (4) convenient modification: mono-, di-, tetra-, and per-substituted pillar[5]arenes can be conveniently obtained.…”