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We use the free radical polymerization initiator 4,4′-azobis(cyanovaleric acid) coordinated to the open metal sites of metal-organic frameworks (MOFs) to give rise to highly uniform MOF/polymer hybrids. We demonstrate this strategy on two robust zirconium MOFs (NU-1000 and MOF-808), which are the most effective catalysts for degradation of chemical warfare nerve agents. The resulting hybrid materials maintain their hydrolytic catalytic activity and have substantially improved adhesion to polypropylene and activated carbon textile fibers, yielding highly robust MOF/polymer/textile hybrid systems. These composites are suitable for the green production of active protective clothing and filters capable of detoxifying organophosphorus warfare agents.

We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal–organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1–cat8, exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.