Metal−organic framework (MOF)-fabric composites are important for coupling wide-ranging MOF chemistry with portable, flexible substrates; however, synthesis methods reported to date rely on harmful solvents and typically use batch, solution-based processing. Here, using only ethanol, water, acetic acid, and γvalerolactone solvents, we show facile synthesis of MOF-fabric composites using a scalable, sorption-vapor approach. UiO-66-NH 2 was integrated onto spandex, polyethylene terephthalate, cotton, nyco, and polypropylene fabrics. MOF-fabrics made with green solvents had higher MOF loading, Brunauer−Emmett−Teller (BET) surface area, and superior performance for pesticide paraoxon-methyl hydrolysis than corresponding composites made with dimethylformamide (DMF). MOF loading, BET surface area, and performance increased with consecutive coatings of UiO-66-NH 2 . Process scalability was confirmed by coating 40 in. 2 of fabric using only 20 mL of precursor solution, resulting in 76% total MOF heterogeneous yield. Moreover,
Current approaches to create zirconium‐based metal–organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO‐66‐NH2 synthesis in common low‐boiling‐point solvents (water, ethanol, and acetic acid) and revealed acid–base chemistry promoting full linker dissolution and vapor‐based crystallization. The mechanism enabled scalable roll‐to‐roll production of mechanically resilient UiO‐66‐NH2 fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post‐processing, producing an activated composite in less than 165 min, far outpacing conventional MOF‐fabric synthesis approaches. The MOF‐fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection‐standard activated carbon cloth. This work presents both chemical insights into Zr‐MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high‐performing personal protective equipment.
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