Abstract
We describe a composite in which reactive hexa-nuclear zirconium (Zr6) clusters were encapsulated in the micropores of processable polymers of intrinsic microporosity (PIMs). By varying the amount of Zr6 clusters in PIMs, it was possible to tune the loading of Zr6 in two polymer matrices: the pristine PIM-1 and the amidoxime-functionalized PIM (PIM-1-AO). Aggregation of Zr6 clusters was suppressed in both Zr6@PIM composites to achieve improved hydrolysis performance of a nerve agent simulant, dimethyl 4-nitrophenylphosphate (DMNP). Low-loading Zr6@PIM-1-AO was found to be the best catalyst, with a DMNP hydrolysis half-life of less than 1 h, which is comparable to some zirconium metal–organic frameworks (Zr-MOFs) at higher catalyst loading. Further, these composites can be electrospun into reactive nanofibers. This demonstrates a new route to apply porous polymers as matrices to encapsulate, stabilize, and utilize the reactivity of soluble Zr6 clusters, which could act as effective candidate materials for the fabrication of personal protective equipment (PPE) against nerve agents.
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