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Doubly-Protective MOF-Photo-Fabrics: Template-Free Synthesis of PCN-222-Textiles for Rapid Hydrolysis, Photo-Hydrolysis and Selective Oxidation of Multiple Chemical Warfare Agents.

Attacks using chemical warfare agents (CWAs,) including organophosphate soman (GD) and thioether mustard gas (HD) threaten both innocent civilians and military personnel, spawning significant research into catalytically-active composite textiles and new wearable protective gear. In this work, we report the first metal-organic framework (MOF) fabric composite capable of both rapid catalytic hydrolysis and photo-oxidation of multiple chemical warfare agents (GD and HD) and their simulants. A simple template-free low-temperature synthesis yields new zirconium-porphyrin based nano-crystalline PCN-222 MOF-fabrics with adjustable MOF loading and robust mechanical adhesion on low-cost nonwoven polypropylene fibers. Importantly, we report the discovery of visible photo-activation of GD hydrolysis by a MOF-fabric, which is ascribed to oxidation at the active metal node site, significantly increasing the rate over that observed without illumination. Moreover, because the active MOF catalysts are uniformly displayed on the MOF-textile, the composite geometry enhances the kinetics of active agent photo-degradation relative to the same mass of MOF in common powder form. These results provide important new insights into the design of future materials and chemical systems to protect military, first-responders, and civilians upon exposure to complex chemical toxins.